Using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application
Technical field
The invention belongs to modern electronic technology field, more particularly to it is a kind of using beta-cyclodextrin and rare earth β-diketone complex complex as
Application of the composite green Environment-friendlyink ink in micro-contact printing.
Background technology
The micro- constructing technology in surface is just gradually being embodied in significant application value, especially microcontact printing techniques, can
The micro-patterning in small size is of great significance in multiple fields especially modern electronic technology field.It is available at present
Micro-contact printing ink it is less, also limited to the material that surface can carry out micro-contact printing, a large amount of material can not be connect with micro-
The method for touching printing prepares picture on surface.Ink that is new, stablizing thus is developed to have a very big significance.
In order to adapt to requirement of the ink of new generation for environmental protection and health, it is necessary to which further exploitation cyclodextrin is micro-
Application in contact printing.Cyclodextrin is nontoxic, has good human compatibility.Beta-cyclodextrin and rare earth β-diketone complex complex are compound molten
Fluidity can be stablized, and quality of forming film is high, and the micro-contact printing of surfaces of various materials can be applied to as a kind of ink of stabilization.Mesh
Preceding beta-cyclodextrin and rare earth β-diketone complex complex composite solution have not been reported as the application of micro-contact printing ink.
Invention content
The object of the present invention is to provide a kind of using beta-cyclodextrin and rare earth β-diketone complex complex composite solution in micro-contact printing
Application the pattern of PDMS seals is turned using beta-cyclodextrin and rare earth β-diketone complex complex solution as the print paste of micro-contact printing
Move to the PET substrate of carboxylated, then by the method for chemical plating in polyethylene terephthalate
Exquisite metal pattern is obtained in substrate.
In order to realize purposes and other advantages according to the present invention, provide multiple using beta-cyclodextrin and rare earth β-diketone complex complex
Application of the solution in micro-contact printing is closed, including:
Beta-cyclodextrin is obtained the beta-cyclodextrin aqueous solution of a concentration of 3-6g/L by step 1 with water dissolution, and in gained β-
Rare earth β-diketone complex complex is added in cyclodextrin aqueous solution, 20KHz ultrasonic vibration 30-60min obtain beta-cyclodextrin and rare earth β-diketone complex cooperation
Object composite solution;
PDMS seals are soaked in 30-40s in beta-cyclodextrin and rare earth β-diketone complex complex composite solution, after taking-up by step 2
In N2Dry 30-60s, carboxylated is placed on by the PDMS seals for being coated with beta-cyclodextrin and rare earth β-diketone complex complex composite solution in air-flow
PET substrate on, gently press 10-20s, PDMS seal designs be transferred to poly terephthalic acid second two
Alcohol ester substrate surface obtains printing figuratum PET substrate;
Step 3 will print figuratum PET substrate and be soaked in 0.1g/L PdCl2In solution
10-30s is put into the solution for electroless copper after taking-up and carries out chemical plating, time 1-10min, by poly terephthalic acid
After glycol ester substrate is taken out, you can obtain metal copper pattern on PET substrate.
Preferably, it is described using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application,
The rare earth β-diketone complex complex is that 1- biphenyl -1,3- diacetyl closes dysprosium, and structural formula is as follows:
Preferably, it is described using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application,
Beta-cyclodextrin aqueous solution and the usage ratio of rare earth β-diketone complex complex are in step 1, and 0.8g is added in every liter of beta-cyclodextrin aqueous solution
Rare earth β-diketone complex complex.
Preferably, it is described using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application,
It is by the method that PET substrate carries out carboxylated:By PET substrate in 45-
55% isopropanol water solution impregnates 30-60min, then impregnates 15-20min under the conditions of 55-65 DEG C with 2-3mol/L sulfuric acid,
60-65 DEG C of vacuum drying, obtains carboxylated PET substrate.
Preferably, it is described using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application,
In step 3, for electroless copper solution by 4-6wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides,
32wt% formaldehyde and the distilled water of surplus composition.
The present invention includes at least following advantageous effect:
1. normal in electronics industry by regarding beta-cyclodextrin and rare earth β-diketone complex complex composite solution as micro-contact printing ink
PET substrate surface prepares metal pattern, and new approaches are provided for micro-contact printing industry.
2. the benzene ring structure containing alkynyl link in rare earth β-diketone complex complex molecule, containing big conjugated system, structural rigidity, together
Contain beta-diketon in molecular configurational, combined with rare earth β-diketone complex coordination and obtain stable Dy complexs, is conducive to obtain stable gold
Metal patterns.
3. rare earth β-diketone complex complex has very strong magnetism, magnetism of material can be assigned, obtained material is expected to be used for making
Energy converter, broadband machinery resonating tube and the high precision liquid fuel injector etc. of standby a new generation's micromation.
4, the hydrophobic cavities of inside " V " font of beta-cyclodextrin are suitble to accommodate 1- biphenyl -1,3- diacetyl conjunction dysprosium molecule
Into and be fixed on beta-cyclodextrin intramolecule.
5. beta-cyclodextrin and rare earth β-diketone complex complex composite solution raw material are easy to get, are at low cost, is stable, environmentally protective, in industry
There are prodigious potentiality using upper.
Specific implementation mode
The present invention is described in further detail below, to enable those skilled in the art being capable of evidence with reference to specification word
To implement.
Using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application, including:
Step 1, substrate carboxylated soak PET substrate with the isopropanol water solution of 45-55%
30-60min is steeped, then 15-20min is impregnated under the conditions of 55-65 DEG C with 2-3mol/L sulfuric acid, is then washed with water, 60-65 DEG C true
Sky is dry, obtains carboxylated PET substrate.
Step 2, prepares beta-cyclodextrin and rare earth β-diketone complex complex composite solution, and beta-cyclodextrin is obtained concentration with water dissolution
For the beta-cyclodextrin aqueous solution of 3-6g/L, 0.8g rare earth β-diketone complex complexs, 20kHz ultrasounds are added in every liter of beta-cyclodextrin aqueous solution
30-60min obtains evenly dispersed beta-cyclodextrin and rare earth β-diketone complex complex composite solution, wherein rare earth β-diketone complex complex joins for 1-
Benzene -1,3- diacetyl closes dysprosium, and structural formula is as follows:
PDMS seals are soaked in 30- in beta-cyclodextrin and rare earth β-diketone complex complex composite solution by step 3, micro-contact printing
40s, in N after taking-up2Dry 30-60s, will be coated with the PDMS seals of beta-cyclodextrin and rare earth β-diketone complex complex composite solution in air-flow
It is placed on carboxylated PET substrate, gently presses 10-20s, PDMS seal designs are transferred to poly- to benzene two
Formic acid glycol ester substrate surface obtains printing figuratum PET substrate.
Step 4, chemical plating will print figuratum PET substrate and be soaked in 0.1g/L PdCl2
10-30s in solution is put in after taking-up by 4-6wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides, 32wt% first
Chemical plating, time 1-10min are carried out in the chemical bronze plating liquid of aldehyde and the distilled water of surplus composition.It can be poly- to benzene after taking-up
Exquisite metal copper pattern is obtained in naphthalate substrate.
Embodiment 1
Using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application, including:
Step 1, substrate carboxylated impregnate PET substrate with 45% isopropanol water solution
30min, then 15min is impregnated under the conditions of 55 DEG C with 2mol/L sulfuric acid, it then washes with water, 60 DEG C of vacuum drying obtain carboxyl
Change PET substrate.
Step 2, prepares beta-cyclodextrin and rare earth β-diketone complex complex composite solution, and beta-cyclodextrin is obtained concentration with water dissolution
For the beta-cyclodextrin aqueous solution of 3g/L, 0.8g rare earth β-diketone complex complexs, 20kHz ultrasounds are added in every liter of beta-cyclodextrin aqueous solution
30min obtains evenly dispersed beta-cyclodextrin and rare earth β-diketone complex complex composite solution.
PDMS seals are soaked in beta-cyclodextrin and rare earth β-diketone complex complex composite solution by step 3, micro-contact printing
30s, in N after taking-up2Dry 30s, will be coated with the PDMS seal lids of beta-cyclodextrin and rare earth β-diketone complex complex composite solution in air-flow
In on carboxylated PET substrate, 10s is gently pressed, PDMS seal designs are transferred to poly terephthalic acid second
Terephthalate substrate surface obtains printing figuratum PET substrate.
Step 4, chemical plating will print figuratum PET substrate and be soaked in 0.1g/L PdCl2
10s in solution, be put in after taking-up by 4wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides, 32wt% formaldehyde and
Chemical plating, time 5min are carried out in the chemical bronze plating liquid of 51wt% distilled water composition.It can be in poly terephthalic acid after taking-up
Exquisite metal copper pattern is obtained in glycol ester substrate.
Embodiment 2
Using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application, including:
Step 1, substrate carboxylated impregnate PET substrate with 50% isopropanol water solution
50min, then 20min is impregnated under the conditions of 55-65 DEG C with 2.5mol/L sulfuric acid, it then washes with water, 60 DEG C of vacuum drying obtain
Carboxylated PET substrate.
Step 2, prepares beta-cyclodextrin and rare earth β-diketone complex complex composite solution, and beta-cyclodextrin is obtained concentration with water dissolution
For the beta-cyclodextrin aqueous solution of 5g/L, 0.8g rare earth β-diketone complex complexs, 20kHz ultrasounds are added in every liter of beta-cyclodextrin aqueous solution
50min obtains evenly dispersed beta-cyclodextrin and rare earth β-diketone complex complex composite solution.
PDMS seals are soaked in beta-cyclodextrin and rare earth β-diketone complex complex composite solution by step 3, micro-contact printing
35s, in N after taking-up2Dry 40s, will be coated with the PDMS seal lids of beta-cyclodextrin and rare earth β-diketone complex complex composite solution in air-flow
In on carboxylated PET substrate, 15s is gently pressed, PDMS seal designs are transferred to poly terephthalic acid second
Terephthalate substrate surface obtains printing figuratum PET substrate.
Step 4, chemical plating will print figuratum PET substrate and be soaked in 0.1g/L PdCl2
20s in solution, be put in after taking-up by 5wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides, 32wt% formaldehyde and
Chemical plating, time 10min are carried out in the chemical bronze plating liquid of 50wt% distilled water composition.It can be in poly terephthalic acid after taking-up
Exquisite metal copper pattern is obtained in glycol ester substrate.
Embodiment 3
Using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application, including:
Step 1, substrate carboxylated impregnate PET substrate with 55% isopropanol water solution
60min, then 20min is impregnated under the conditions of 55-65 DEG C with 3mol/L sulfuric acid, it then washes with water, 65 DEG C of vacuum drying obtain carboxylic
Base PET substrate.
Step 2, prepares beta-cyclodextrin and rare earth β-diketone complex complex composite solution, and beta-cyclodextrin is obtained concentration with water dissolution
For the beta-cyclodextrin aqueous solution of 6g/L, 0.8g rare earth β-diketone complex complexs, 20kHz ultrasounds are added in every liter of beta-cyclodextrin aqueous solution
60min obtains evenly dispersed beta-cyclodextrin and rare earth β-diketone complex complex composite solution.
PDMS seals are soaked in beta-cyclodextrin and rare earth β-diketone complex complex composite solution by step 3, micro-contact printing
40s, in N after taking-up2Dry 60s, will be coated with the PDMS seal lids of beta-cyclodextrin and rare earth β-diketone complex complex composite solution in air-flow
In on carboxylated PET substrate, 20s is gently pressed, PDMS seal designs are transferred to poly terephthalic acid second
Terephthalate substrate surface obtains printing figuratum PET substrate.
Step 4, chemical plating will print figuratum PET substrate and be soaked in 0.1g/L PdCl2
30s in solution, be put in after taking-up by 6wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides, 32wt% formaldehyde and
Chemical plating, time 10min are carried out in the chemical bronze plating liquid of 49wt% distilled water composition.It can be in poly terephthalic acid after taking-up
Exquisite metal copper pattern is obtained in glycol ester substrate.
Embodiment 4
Human normal epidermal cell HaCaT is incubated at Dahl Burke Improved Eagle Medium (DMEM) culture solution (to contain
10% newborn bovine serum) in, set 37 DEG C, 5%CO2Under the conditions of cultivate, 1~2d changes 1 culture solution.When cell growth to logarithmic phase
Untreated PET substrate is added respectively, 1,2 and 3 gained of embodiment is printed on the poly- of metal copper pattern
Ethylene glycol terephthalate base treatment.Cell is placed in 37 DEG C, 5%CO with 0.25% tryptose, 96 orifice plate2Incubator is trained
It supports.After 2~4h, every piece of culture plate is separately added into untreated PET substrate and embodiment 1-3 institutes
The cell of PET substrate and complete culture solution culture that metal copper pattern must be printed on are as a control group
And experimental group, the culture solution without cell and sample move into 37 DEG C, 5%CO as blank control, by culture plate2Incubator is trained
It supports.After for 24 hours, culture solution is abandoned, 2- (2- methoxyl group -4- nitrobenzophenones) -3- (4- are added in phosphate buffer (PBS) board-washing 2 times
Nitrobenzophenone) -5- (2,4- disulfonic acid benzene) -2H- tetrazolium list sodium (CCK-8) 10 μ l.Continue in 37 DEG C, 5%CO2Incubator culture
Each hole optical density (D values) is surveyed at 2~4h, microplate reader 550nm.Cell survival rate (%)=[(experimental port D values-blank well D values)/
(control wells D values-blank well D values)] × 100%, experimental result is as shown in table 1.
Table 1
As it can be seen from table 1 the cell survival rate of polypropylene substrate of the present invention after electroless copper is apparently higher than not
Processed polypropylene substrate illustrates beta-cyclodextrin and rare earth β-diketone complex complex composite solution as micro-contact printing ink biofacies
Capacitive is good, and cytotoxicity is low, safe and non-toxic, and harm to the human body is small.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.