CN108727640A - A kind of Transient Thin-Film, the preparation method of Transient Thin-Film and Transient Thin-Film device - Google Patents
A kind of Transient Thin-Film, the preparation method of Transient Thin-Film and Transient Thin-Film device Download PDFInfo
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- CN108727640A CN108727640A CN201810556322.2A CN201810556322A CN108727640A CN 108727640 A CN108727640 A CN 108727640A CN 201810556322 A CN201810556322 A CN 201810556322A CN 108727640 A CN108727640 A CN 108727640A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
Abstract
The invention discloses a kind of Transient Thin-Film, the preparation method of Transient Thin-Film and Transient Thin-Film devices, the Transient Thin-Film includes substrate, the material for preparing substrate includes modified cellulose and micromolecular compound, wherein modified cellulose is the cellulose that hydroxyl degree of substitution is 0.6~1.8, and modified cellulose viscosity number is 200mpa.s~5000mpa.s.Transient Thin-Film, the preparation method of Transient Thin-Film and the Transient Thin-Film device of the present invention, pass through modified cellulose and micromolecular compound, to obtain a kind of degradable and controllable degradation rate Transient Thin-Film, and Transient Thin-Film product after organism surface or in vivo degradation is carbon dioxide and water, toxic action is not generated to organism, can be used as the substrate for preparing implantable medical device；In addition the Transient Thin-Film elasticity modulus prepared is controllable, and compliance is good, is easily attached on skin.
Description
Technical field
The present invention relates to biologic medical fields, more particularly to a kind of Transient Thin-Film, the preparation method of Transient Thin-Film and wink
State thin-film device.
Background technology
Currently, up to 10,000,000 tons of the biologic medical high molecular material that the whole world consumes every year, the biologic medical high score in China
The usage amount of sub- material probably at 2,000,000 tons, accounts for 1/5th of global consumption.These high molecular materials are primarily used to
Prepare disposable biomedical device, and these materials are mainly nondegradable high molecular materials, after use mainly with
The means buried and burned are handled, this has resulted in huge environmental pollution and the wasting of resources；Meanwhile in rehabilitation medical side
Face, the electronic equipment for needing implantable electronic monitoring equipment, the auxiliary treatment equipment for attaching wound, rehabilitation efficacy to monitor
Deng, but most implantable medical devices are all nondegradable in vivo now, can only be passed through from the method removed in vivo
Operation is taken out.Medical expense increase can thus be made while more importantly it can make patient experience second operation, again body
Test the pain of operation.If being designed to be able to implanted equipment by being removed naturally after metabolic natural degradation or dissolving,
By the very big quality of life for improving implanted equipment user, reduces patient suffering and operation is spent.
Invention content
To solve the above-mentioned problems of the prior art, the present invention provides the preparations of a kind of Transient Thin-Film, Transient Thin-Film
Method and Transient Thin-Film device so that Transient Thin-Film is degradable and degradation rate is controllable.
In order to reach foregoing invention purpose, present invention employs the following technical solutions：
In a general aspect, a kind of Transient Thin-Film is provided, the Transient Thin-Film includes substrate, prepares the material of the substrate
Material includes modified cellulose and micromolecular compound, wherein the modified cellulose is the fiber that hydroxyl degree of substitution is 0.6~1.8
Element, the modified cellulose viscosity number are 200mpa.s~5000mpa.s.
Preferably, the micromolecular compound is glycerine or polyethylene glycol.
Preferably, the elasticity modulus of the Transient Thin-Film is 0.05~100MPa, and stretching ratio is 50%~300%.
In another general aspect, a kind of preparation method of above-mentioned Transient Thin-Film, includes the following steps：
Modified cellulose is dissolved in deionized water by step 1, obtains the modified fibre that mass concentration is 0.1%~10%
Plain solution；
Micromolecular compound is added into the modified cellulose solution for step 2, and the micromolecular compound changes with described
Property cellulose solution mass concentration ratio be 0.1%~50%, obtain mixed solution；
The mixed solution of acquisition is positioned in surface plate, and by the surface plate in drying box by step 3, is obtained
Transient Thin-Film.
Preferably, the micromolecular compound is glycerine or polyethylene glycol.
Preferably, the modified cellulose is the cellulose that hydroxyl degree of substitution is 0.6~1.8, and the modified cellulose is viscous
Angle value is 200mpa.s~5000mpa.s.
Preferably, in step 1, after modified cellulose being dissolved in deionized water, also to dissolved with the molten of modified cellulose
Liquid carries out stirring in water bath, wherein bath temperature is 0~100 DEG C, and mixing speed is 500~1000rmp/min, a length of 2 when stirring
~4h；And/or
In step 2, after micromolecular compound being added into the modified cellulose solution, also to small molecule chemical combination is added
The solution of object carries out stirring in water bath, wherein bath temperature is 0~100 DEG C, and mixing speed is 500~1000rmp/min, stirring
2~4h of Shi Changwei；And/or
In step 3, after the surface plate is positioned in drying box, control drying box temperature is 10~200 DEG C, dry
1~72h.
Preferably, in step 3, the mixed solution of acquisition is fallen also needs to carry out the mixed solution before surface plate
Go the processing of bubble removing, described to go the processing procedure of bubble removing include step：
Step a, the bubble in the mixed solution is removed using ultrasound, wherein ultrasonic power is 20~100W, when ultrasonic
A length of 0.5~1h obtains the mixed solution for removing bubble removing for the first time；
Step b, the mixed solution of bubble removing is gone to be placed in 24~72h in the environment that temperature is 10~40 DEG C for the first time by described,
Obtain the mixed solution for removing bubble removing.
Preferably, in step 3, the mixed solution of acquisition is fallen also needs to carry out the mixed solution before surface plate
Go the processing of bubble removing, described to go the processing procedure of bubble removing include step：
Step a ', the bubble in the mixed solution is removed using ultrasound, wherein ultrasonic power is 20~100W, ultrasound
0.5~1h of Shi Changwei obtain the mixed solution for removing bubble removing for the first time；
Step b ', anti-inflammation drugs and/or antibiotic is added into the first mixed solution for removing bubble removing of acquisition, and carries out machine
Tool stirs, and obtains the mixed solution of addition drug；
Step c ', the mixed solution of the addition drug of acquisition is placed in 24~72h in the environment that temperature is 10~40 DEG C, obtained
It must remove the mixed solution of bubble removing.
In another general aspect, a kind of Transient Thin-Film device is provided, including above-mentioned Transient Thin-Film and is set to the wink
The metal electrode of state film surface.
Compared with prior art, Transient Thin-Film of the invention, the preparation method of Transient Thin-Film and Transient Thin-Film device, pass through
Modified cellulose is mixed with micromolecular compound, to obtain a kind of degradable and controllable degradation rate Transient Thin-Film, and the wink
State film product after organism surface or in vivo degradation is carbon dioxide and water, does not generate toxic action to organism, can be used as
Prepare the substrate of implantable medical device；In addition the Transient Thin-Film elasticity modulus prepared is controllable, and compliance is good, is easily attached to skin
On.
Description of the drawings
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to embodiment or description of the prior art
Needed in attached drawing be briefly described, it should be apparent that, the accompanying drawings in the following description be only the present invention some
Embodiment for those of ordinary skill in the art without having to pay creative labor, can also be according to these
Attached drawing obtains other attached drawings.
Fig. 1 is the structural schematic diagram of the Transient Thin-Film device of the embodiment of the present invention；
Fig. 2 is the flow diagram of the preparation method of the Transient Thin-Film of the embodiment of the present invention；
Fig. 3 is that 3 small molecular compound of the embodiment of the present invention is prepared under modified cellulose solution different quality concentration ratio
Transient state film mechanical test figure.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention is retouched in detail
It states, it is clear that described embodiment is only a part of example of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained without making creative work,
Belong to the scope of the present invention.
A kind of Transient Thin-Film as the present invention prepares the base wherein the Transient Thin-Film includes degradable substrate
The material at bottom includes modified cellulose and micromolecular compound.
Wherein, the modified cellulose that the embodiment of the present invention is selected is the cellulose that hydroxyl degree of substitution is 0.6~1.8,
And the modified cellulose viscosity number is 200mpa.s~5000mpa.s, by adjusting cellulose hydroxyl group degree of substitution, changes fiber
The quantity of hydroxyl in element, obtains the cellulose of different modifications, with further can dissolve/degrade and rate of dissolution/degradation
The Transient Thin-Film of controllable-rate.But in practical modifying process, hydroxyl excessive number, cellulosic molecule intermolecular forces are too strong,
Chain will be tightly wound around together, many organic solvents and water not dissolved in, it is difficult to degrade；Hydroxyl quantity is very few, between cellulosic molecule
Active force is small, is not easy to form a film, and intensity is not high after film forming, limitation application.Based on this, the modified cellulose that the present invention selects is
The cellulose that hydroxyl degree of substitution is 0.6~1.8, modified cellulose viscosity number are 200mpa.s~5000mpa.s, are taken by adjusting
Dai Du is controlled with viscosity number with the degradation time to Transient Thin-Film, realizes controlled degradation.It should be noted that due to fiber
Element and modified cellulose are polymer, the molecular weight not determined, therefore we are with the viscous of cellulose or modified cellulose
Degree is illustrates object, but viscosity and molecular weight have certain linear relationship, the more big corresponding molecular weight of viscosity bigger.Separately
Outside, cellulosic material is a kind of natural degradable, reproducible high molecular material, is mainly extract from plant, right
The Transient Thin-Film that cellulose is prepared after being modified, organism surface or in vivo degradation after product be carbon dioxide and water, it is not right
Organism generates toxic action.
Preferably, modified cellulose is the hydroxyethyl cellulose (HEC) that degree of substitution is 0.6~1.8, due to low degree of substitution
Its degree of substitution of HEC is dissolved at 0.2~0.3 in alkaline solution, is slightly soluble in water, is unfavorable for degrading；The HEC of medium degree of substitution takes
Dai Du is water-soluble 0.6~1.8, solution in freezing, melt, be heated to boiling and all generated without gel and precipitation, very surely
It is fixed, while solution viscosity is stablized in 2~12 ranges of pH, no gel and precipitation generate；Compared with the HEC degree of substitution 1.8 of high substituted degree
~2.8, synthesis condition is harsh, of high cost, poor water retention property.
It further, will necessarily be with human body skin since the Transient Thin-Film prepared by the present invention is mainly used in medical treatment
Skin contacts, and human skin has certain flexibility and ductility, the elasticity modulus and ductility of skin and the age of the mankind
Related with the different parts of body, as human age increases, skin elasticity modulus gradually increases, and stretching ratio is gradually reduced,
Elasticity modulus substantial scope between 0.02~200MPa, stretching ratio between 10%~100%, age bracket 10~60 years old it
Between human skin elasticity modulus mainly in 1~150MPa, stretching ratio 20%~100%.Hydroxyl degree of substitution be 0.6~
1.8, viscosity number be 200mpa.s~5000mpa.s modified cellulose obtain Transient Thin-Film elasticity modulus ranging from 0.05~
100MPa, stretching ratio ranging from 50%~300% substantially cover all answer with good compliance and sense of touch
With demand, elasticity modulus and stretching ratio matching degree higher with human skin.
Preferably, micromolecular compound is glycerine or polyethylene glycol, and more preferably, micromolecular compound is glycerine,
Glycerine with when polyethylene glycol is as the mixed proportion of modified cellulose, the results showed that, prepared when being selected as glycerine
Transient Thin-Film, film forming is more preferable, film evenly, light transmittance it is also more preferable, be provided simultaneously with ductility, mechanical property is strong, can be into
One step obtains compliance and the better Transient Thin-Film of sense of touch.
Embodiment 1
The present invention provides a kind of methods preparing above-mentioned Transient Thin-Film, as shown in Figure 2 comprising：
Step S1, modified cellulose is dissolved in deionized water, obtains the modified fibre that mass concentration is 0.1%~10%
Plain solution；Wherein, the modified cellulose is the cellulose that hydroxyl degree of substitution is 0.6~1.8, the modified cellulose viscosity number
For 200mpa.s~5000mpa.s；In step sl, in order to further speed up dissolving, promote molecule diffusion, by modified cellulose
After being dissolved in deionized water, stirring in water bath is carried out to the solution dissolved with modified cellulose, wherein bath temperature is 0~100 DEG C,
Mixing speed is 500~1000rmp/min, when stirring a length of 2~4h；
Step S2, be added micromolecular compound into the modified cellulose solution, the micromolecular compound with it is described
The mass concentration ratio of modified cellulose solution is 0.1%~50%, obtains mixed solution；In step sl, in order to further plus
Fast dissolving promotes molecule diffusion, after micromolecular compound is added into the modified cellulose solution, to small molecule chemical combination is added
The solution of object carries out stirring in water bath, wherein bath temperature is 0~100 DEG C, and mixing speed is 500~1000rmp/min, stirring
2~4h of Shi Changwei；Wherein, the micromolecular compound is glycerine or polyethylene glycol.
Step S3, the mixed solution of acquisition is fallen and is positioned in drying box in surface plate, and by the surface plate,
Obtain Transient Thin-Film.Wherein, after the surface plate is positioned in drying box, control drying box temperature is 10~200 DEG C, is done
Dry 1~72h.
Preferably, in step s3, the mixed solution of acquisition is fallen also need before the surface plate to the mixed solution into
Row goes the processing of bubble removing, and described to go the processing procedure of bubble removing include step：
Step Sa, the bubble in the mixed solution is removed using ultrasound, wherein ultrasonic power is 20~100W, ultrasound
0.5~1h of Shi Changwei obtain the mixed solution for removing bubble removing for the first time；
Step Sb, the mixed solution of bubble removing is gone to be placed in 24~72h in the environment that temperature is 10~40 DEG C for the first time by described,
Obtain the mixed solution for removing bubble removing.
Finally, the mixed solution for removing bubble removing of acquisition is positioned over drying in surface plate, and by the surface plate
In case, Transient Thin-Film is obtained.
The elasticity modulus of the Transient Thin-Film prepared by above-mentioned preparation method is 0.05~100MPa, and stretching ratio is
50%~300%.
Wherein, it is preferred that modified cellulose is the hydroxyethyl cellulose (HEC) that degree of substitution is 0.6~1.8, is taken due to low
Its degree of substitution of the HEC of Dai Du is dissolved at 0.2~0.3 in alkaline solution, is slightly soluble in water, is unfavorable for degrading；Medium degree of substitution
HEC degree of substitution 0.6~1.8, it is water-soluble, solution in freezing, melt, be heated to boiling and all generated without gel and precipitation,
It is sufficiently stable, while solution viscosity is stablized in 2~12 ranges of pH, no gel and precipitation generate；HEC compared with high substituted degree takes
For degree 1.8~2.8, synthesis condition is harsh, of high cost, poor water retention property.
Preferably, micromolecular compound is glycerine or polyethylene glycol, and more preferably, micromolecular compound is glycerine,
Glycerine with when polyethylene glycol is as the mixed proportion of modified cellulose, the results showed that, prepared when being selected as glycerine
Transient Thin-Film, film forming is more preferable, film evenly, light transmittance it is also more preferable, be provided simultaneously with ductility, mechanical property is strong, can be into
One step obtains compliance and the better Transient Thin-Film of sense of touch.
Embodiment 2
The present embodiment also provides a kind of preparation method of Transient Thin-Film, the preparation method and embodiment 1 of the present embodiment
It differs only in, in step s3, the mixed solution of acquisition is fallen also to be needed to remove the mixed solution before surface plate
The processing of bubble removing, described to go the processing procedure of bubble removing include step：
Step Sa ', the bubble in the mixed solution is removed using ultrasound, wherein ultrasonic power is 20~100W, ultrasound
0.5~1h of Shi Changwei obtain the mixed solution for removing bubble removing for the first time；
Step Sb ', anti-inflammation drugs and/or antibiotic is added into the first mixed solution for removing bubble removing of acquisition, and carries out
Mechanical agitation obtains the mixed solution of addition drug；
Step Sc ', the mixed solution of the addition drug of acquisition is placed in 24~72h in the environment that temperature is 10~40 DEG C,
Obtain the mixed solution for removing bubble removing.
Finally, the mixed solution for removing bubble removing of acquisition is positioned over drying in surface plate, and by the surface plate
In case, Transient Thin-Film is obtained, drying condition is according to embodiment 1.
Wherein, the antiphlogistic in step Sb ' can be aspirin, antibiotic can be penicillin or cephalo, due to
The addition of antiphlogistic or antibiotic, after Transient Thin-Film is degraded in vivo, antiphlogistic or antibiotic dissolved and to wink
The part of state film degradation carries out anti-inflammatory, to prevent from infecting, accelerating wound healing.
Embodiment 3
In order to probe into micromolecular compound and modified cellulose concentration of polymer solution compare Transient Thin-Film elasticity modulus and
The influence of stretching ratio, wherein referring to Fig. 3, preparation method of the present embodiment based on embodiment 1, select viscosity number for
Hydroxyethyl cellulose that 2000mpa.s, degree of substitution are 1 selects micromolecular compound to carry out multigroup Experimental comparison, tool for glycerine
Body includes：
Step S1, select viscosity number be 2000mpa.s, the hydroxyethyl cellulose that degree of substitution is 1, hydroxyethyl cellulose is molten
In deionized water, and stirring in water bath is carried out, bath temperature is 80 DEG C, mixing speed 1000rmp/min, stirs 4h, obtains matter
Measure a concentration of 2% hydroxyethyl cellulose solution；
Step S2,5 groups of hydroxyethyl cellulose solution that the mass concentration for obtaining step S1 is 2% etc. point, and it is molten to 5 groups
Glycerine is separately added into liquid, glycerine is respectively with hydroxyethyl cellulose solution mass concentration ratio：0.1:100,1:100,2:
100,5:100,10:100,20:100, stirring in water bath is carried out respectively to 5 groups of solution, bath temperature is 80 DEG C, mixing speed
1000rmp/min stirs 4h, 5 groups of mixed solutions of acquisition；
Step S3 is specifically included：
Step Sa, the bubble in ultrasound 5 groups of mixed solutions of removal is utilized, wherein ultrasonic power 80W, it is a length of when ultrasonic
1h obtains 5 groups of mixed solutions for removing bubble removing for the first time；
Step Sb, the mixed solution of bubble removing will be gone to be placed in 48h in the environment that temperature is 20 DEG C described in 5 groups for the first time, obtained
Remove the mixed solution of bubble removing.
Finally, it goes the mixed solution of bubble removing to fall respectively in 5 surface plates, and by 5 surface plates by 5 groups of acquisition to put
It is placed in drying box, drying box temperature processed is 80 DEG C, is dried for 24 hours, to obtain 5 groups of Transient Thin-Films.Referring to Fig. 3,5 groups of Transient Thin-Films
Elasticity modulus and stretching ratio referring to table 1 (its elastic mould value and stretching ratio according to fig. 3 in data enumerated, because
This can have positive and negative 1 to 3 error, but the error is within the scope of reasonable error, similarly hereinafter)：
Table 1
As shown in Table 1, glycerol content accounting is higher, then the elasticity modulus of the Transient Thin-Film prepared is lower, stretching ratio
It is higher, but stretching ratio can decline after reaching peak value with continuing growing for glycerol content.Therefore, actual
It, can be by adjusting micromolecular compound and modified cellulose concentration of polymer solution ratio, to prepare different springforms in medical applications
The Transient Thin-Film of amount and stretching ratio is carried out controllable with adapting to different application demand further according to the Transient Thin-Film under different application
Degradation.
Embodiment 4
In order to further probe into the different elasticity modulus and stretching ratio to Transient Thin-Film of modified cellulose viscosity number
It influences, controllable to be carried out to Transient Thin-Film, the present embodiment is viscous with the modified cellulose for differing only in selection of embodiment 3
Angle value is different, and the present embodiment is tested using the modified cellulose that viscosity number is respectively 200mpa.s, 5000mpa.s, reference
Preparation method in embodiment 3, viscosity number are respectively Transient Thin-Film made from the modified cellulose of 200mpa.s, 5000mpa.s
Elasticity modulus and stretching ratio referring to table 2 and table 3：
Table 2
Table 3
Comparison 2 and table 3 and further table 1 in 3 in conjunction with the embodiments, identical glycerine and modified cellulose solution quality
Under concentration ratio, the viscosity number of modified cellulose is bigger, then corresponding molecular weight is bigger, then the springform for the Transient Thin-Film prepared
Measure bigger.Meanwhile table 2 and table 3 higher, the then elasticity of the Transient Thin-Film prepared that further demonstrates 3 glycerol content of embodiment
Modulus is lower, and stretching ratio is higher, after stretching ratio reaches peak value, can decline with continuing growing for glycerol content
Conclusion.It therefore, also can be by adjusting the viscosity number of modified cellulose to prepare dual extension-compression modulus in actual medical applications
With the Transient Thin-Film of stretching ratio, to adapt to different application demand.
Embodiment 5
In order to further control the degradation time of Transient Thin-Film, the present embodiment continue to probe into micromolecular compound with
When influence of the viscosity number to the degradation rate of Transient Thin-Film of modified cellulose concentration of polymer solution is directed to prepare to have more
Transient Thin-Film prepared by above-described embodiment 3, embodiment 4 is taken 10* by the Transient Thin-Film of property medical applications, the present embodiment respectively
10mm, the square that thickness is 0.5mm, are positioned in deionized water at 20 DEG C of room temperature, observe the rate of dissolution of Transient Thin-Film, have
Body, referring to table 4, table 5 and table 6；
Table 4
Table 5
Table 6
By table 4, table 5 and table 6 it is found that glycerol content is higher, rate of dissolution is faster.Viscosity number is bigger, then cellulose point
Son amount is bigger, and rate of dissolution is slower.It therefore, can be by regulating and controlling the third three in order to obtain Transient Thin-Film apply with targeted therapy
The viscosity number of alcohol and modified cellulose, to control preparation Transient Thin-Film degradation time, with provide it is degradable and degradation speed
The controllable implantable medical device of rate.
Embodiment 6
Shown in referring to Fig.1, the present embodiment additionally provides a kind of Transient Thin-Film device, and the Transient Thin-Film device includes upper
The Transient Thin-Film 1 stated and the metal electrode 2 set on the Transient Thin-Film surface.
Wherein, the thin-film device of the present embodiment further prepares metal electrode on the basis of above-mentioned preparation Transient Thin-Film 1
2 comprising step：
1, it is taken out after drying Transient Thin-Film, cuts into required size；
2, then the Transient Thin-Film of well cutting is blown with washes of absolute alcohol adsorption impurity and dust with nitrogen
It is dry, it is placed in clean surface plate；
3, pass through chemically or physically method protracting circuit pattern in the Transient Thin-Film of dust removal；Wherein method is vapor deposition, electronics
Beam evaporation, plasma sputtering, chemical meteorology deposition, physical vapor deposition, electronic printing, spraying, chemical etching and physics are carved
One or more of method for drafting of the methods of erosion kind.
Further, preparation method of the present embodiment based on Transient Thin-Film device, the elasticity modulus prepared in Example 3 are
0.8Mpa (elasticity modulus is small, and the comfort level that skin feel arrives is good), the Transient Thin-Film that stretching ratio is 300% are further tried
Test, and prepared in the Transient Thin-Film of selection by following methods can thermometric humidity and pressure and strain sensor sensing layer,
Specific preparation method is as follows：
Step a, nano silver wire is dispersed in absolute ethyl alcohol, mass concentration 0.01%, ultrasonic disperse 2 hours, ultrasonic work(
Rate 80W；
Step b, the Transient Thin-Film that the elasticity modulus of one piece of 4*10mm is 0.8Mpa, stretching ratio is 300% is taken, spray gun is used
By above-mentioned nano silver wire solution spraying on film, spray 10 minutes, testing film resistance is in 1000 ohms；
Step c, on the basis of step b, carbon nanotube is sprayed, obtains Transient Thin-Film device, it is specific as follows：
Single-walled carbon nanotube is dispersed in absolute ethyl alcohol, mass concentration 0.05%, is shaken 2 hours with breaking-wall cell machine,
Power 300W sprays second layer carbon nanotube in the one side for coating nano silver wire, sprays 30 minutes, test surfaces resistance 500
Ohms；
Step d, after 20 DEG C of room temperature stands 2 hours, in the one side for having sensitive layer one layer of spin coater spin coating and Transient Thin-Film
The modified cellulose solution of same ratio, spin coating rate 1000rmp/min, spin-coating time 30 seconds, the purpose of this step be into
One step protects sensor sensing layer.
It is attached to the Transient Thin-Film device of above-mentioned preparation on experimental white mouse back and shank, passes through oscillograph electricity
The amplitude variation of pressure can monitor crawler behavior and the variation of body surface humiture of mouse in real time.After the test, by Transient Thin-Film
Device is positioned in sink can natural degradation.
In addition, applicant also prepares above-mentioned same Transient Thin-Film device, a silver wire system with a diameter of 0.01mm is used in combination
It is standby that conducting wire is made on thin-film device.Experiment is cut with the vertebra of mouselet, cuts off spinal nerve, 200 μm of 4*10mm thickness
Transient Thin-Film device be inserted in the vertebra of mouse, then suture wound, powers on, and gives intermittent electro photoluminescence observation mouse
Motor behavior, device electrode loss of function after 20 min, dermal sutures out after one hour, it is observed that thin-film device has dropped
Solution is complete, cuts around tissue without finding inflammation and allergic symptom.
It is prepared compared with fibroin in the Transient Thin-Film of the present invention prepared with modified cellulose and micromolecular compound
Degradable Transient Thin-Film, since fibroin will be extracted from silk cocoon, extraction process is cumbersome, and preparation process is complicated, prepares thin
Film cost is very high, and fibroin hydrophily is poor, and elasticity modulus is high, is not easy to attach on the skin, while degradation time is not easy
Regulation and control it is big will to adjust difficulty by the crystallinity of adjusting fibroin.It is thin compared to the degradable transient state prepared with polylactic acid
Film, polylactic acid are also widely present in plant, and processing technology is ripe, but technology is monopolized by foreign countries, while polylactic acid elasticity
Modulus is big, and hydrophily is poor, is unfavorable for the contact with organism, because decomposition product has acidity, is not readily used for preparing implantable medical
The substrate of equipment.
The present invention Transient Thin-Film, the preparation method of Transient Thin-Film and Transient Thin-Film device, by modified cellulose with it is small
Molecular compound, to obtain a kind of degradable and controllable degradation rate Transient Thin-Film, and the Transient Thin-Film in organism surface or
Product is carbon dioxide and water after degradation in vivo, does not generate toxic action to organism, can be used as and prepare implantable medical device
Substrate；In addition the Transient Thin-Film elasticity modulus prepared is controllable, and compliance is good, is easily attached on skin.
Although the present invention has shown and described with reference to specific embodiment, it will be understood by those of skill in the art that
In the case where not departing from the spirit and scope of the present invention limited by claim and its equivalent, can carry out herein form and
Various change in details.
Claims (10)
1. a kind of Transient Thin-Film, which is characterized in that the Transient Thin-Film includes substrate, and the material for preparing the substrate includes being modified
Cellulose and micromolecular compound, wherein the modified cellulose is the cellulose that hydroxyl degree of substitution is 0.6~1.8, it is described to change
Property cellulose viscosity number be 200mpa.s~5000mpa.s.
2. Transient Thin-Film according to claim 1, which is characterized in that the micromolecular compound is glycerine or poly- second two
Alcohol.
3. Transient Thin-Film according to claim 1, which is characterized in that the elasticity modulus of the Transient Thin-Film be 0.05~
100MPa, stretching ratio are 50%~300%.
4. a kind of preparation method of Transient Thin-Film as described in claims 1 to 3 any one, which is characterized in that including as follows
Step：
Modified cellulose is dissolved in deionized water by step 1, and it is molten to obtain the modified cellulose that mass concentration is 0.1%~10%
Liquid；
Micromolecular compound, the micromolecular compound and the modified fibre are added into the modified cellulose solution for step 2
The mass concentration ratio of the plain solution of dimension is 0.1%~50%, obtains mixed solution；
The mixed solution of acquisition is positioned in surface plate, and by the surface plate in drying box by step 3, obtains transient state
Film.
5. the preparation method of Transient Thin-Film according to claim 4, which is characterized in that the micromolecular compound is the third three
Alcohol or polyethylene glycol.
6. the preparation method of Transient Thin-Film according to claim 4, which is characterized in that the modified cellulose takes for hydroxyl
The cellulose that Dai Du is 0.6~1.8, the modified cellulose viscosity number are 200mpa.s~5000mpa.s.
7. the preparation method of Transient Thin-Film according to claim 4, which is characterized in that in step 1, by modified cellulose
After being dissolved in deionized water, stirring in water bath also is carried out to the solution dissolved with modified cellulose, wherein bath temperature is 0~100
DEG C, mixing speed is 500~1000rmp/min, when stirring a length of 2~4h；And/or
In step 2, after micromolecular compound being added into the modified cellulose solution, also to micromolecular compound is added
Solution carries out stirring in water bath, wherein bath temperature is 0~100 DEG C, and mixing speed is 500~1000rmp/min, stirs duration
For 2~4h；And/or
In step 3, after the surface plate is positioned in drying box, control drying box temperature is 10~200 DEG C, drying 1
~72h.
8. the preparation method of the Transient Thin-Film according to claim 4~7 any one, which is characterized in that in step 3,
The mixed solution of acquisition is fallen also needs the processing that bubble is removed to the mixed solution before surface plate, described to go degasification
The processing procedure of bubble includes：
Step a, the bubble in the mixed solution is removed using ultrasound, wherein ultrasonic power is 20~100W, a length of when ultrasonic
0.5~1h obtains the mixed solution for removing bubble removing for the first time；
Step b, it goes the mixed solution of bubble removing to be placed in 24~72h in the environment that temperature is 10~40 DEG C for the first time by described, obtains
Remove the mixed solution of bubble removing.
9. the preparation method of the Transient Thin-Film according to claim 4~7 any one, which is characterized in that in step 3,
The mixed solution of acquisition is fallen also needs the processing that bubble is removed to the mixed solution before surface plate, described to go degasification
The processing procedure of bubble includes：
Step a ', the bubble in the mixed solution is removed using ultrasound, wherein ultrasonic power is 20~100W, ultrasonic duration
For 0.5~1h, the mixed solution for removing bubble removing for the first time is obtained；
Step b ', anti-inflammation drugs and/or antibiotic is added into the first mixed solution for removing bubble removing of acquisition, and carries out machinery and stirs
It mixes, obtains the mixed solution of addition drug；
Step c ', the mixed solution of the addition drug of acquisition is placed in 24~72h in the environment that temperature is 10~40 DEG C, is gone
The mixed solution of bubble removing.
10. a kind of Transient Thin-Film device, which is characterized in that include Transient Thin-Film as described in claims 1 to 3 any one and
Metal electrode set on the Transient Thin-Film surface.
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