CN104356741B - Water-soluble planar is conjugated the method that phthalocyanine porphyrin dyad carries out micro-printing as micro-contact printing ink - Google Patents
Water-soluble planar is conjugated the method that phthalocyanine porphyrin dyad carries out micro-printing as micro-contact printing ink Download PDFInfo
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- CN104356741B CN104356741B CN201410619388.3A CN201410619388A CN104356741B CN 104356741 B CN104356741 B CN 104356741B CN 201410619388 A CN201410619388 A CN 201410619388A CN 104356741 B CN104356741 B CN 104356741B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
- B41M5/04—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet using solvent-soluble dyestuffs on the master sheets, e.g. alcohol-soluble
Abstract
The invention discloses and water-soluble planar is conjugated the method that phthalocyanine porphyrin dyad carries out micro-printing as micro-contact printing ink.Comprise the concrete steps that: by 5, the aqueous solution of 10,15,20 p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine is as the print paste of micro-contact printing, the pattern of PDMS seal is transferred to polytetrafluoroethylene (PTFE) substrate, then in substrate, is obtained the argent pattern of fineness by the method for absorbing and reducing silver.By by 5,10,15, the aqueous solution of 20 p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine prepares metal pattern as micro-contact printing ink at the ptfe surface that electron trade is conventional, raw material is easy to get, low cost, stable, commercial Application has the biggest potentiality, provides new approaches for micro-contact printing industry.
Description
Technical field
The invention belongs to modern electronic technology field, particularly to a kind of water-soluble planar conjugation phthalocyanine porphyrin
Dyad is as the application in micro-contact printing of the environmental protection ink.
Background technology
The micro-constructing technology in surface the most gradually embodies in significant application value, particularly microcontact printing techniques,
It can in small size micro-patterning, in multiple fields, particularly modern electronic technology field has important
Meaning.Current alternative micro-contact printing ink is less, has also limited to surface and can carry out micro-contact print
The material of brush, substantial amounts of material cannot prepare picture on surface by the method for micro-contact printing.Thus exploitation is new
, stable ink has a very big significance.
For enriching micro-contact printing ink and the selection of substrate further, and promote micro-contact printing quality,
It is necessary further development of metallic porphyrin, phthalocyanine compound application in micro-contact printing.Planar conjugate
Phthalocyanine porphyrin dyad stable performance, quality of forming film is high, can be applied to many as a kind of stable ink
Plant the micro-contact printing of material surface.Planar conjugate phthalocyanine porphyrin dyad is as micro-contact printing ink at present
The application of water has no report.
Summary of the invention
It is an object of the invention to provide a kind of water-soluble planar conjugation phthalocyanine porphyrin dyad as a kind of new
Ink carries out the application of micro-contact printing in polytetrafluoroethylene (PTFE) substrate.Be the technical scheme is that
1) water-soluble planar conjugation phthalocyanine porphyrin dyad is 5,10,15,20-p-aminophenyl porphyrin aluminium six
Carboxyl aluminum phthalocyanine, has a following structural formula:
2) using the aqueous solution of 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine as micro-contact
The print paste of printing, is transferred to the pattern of PDMS seal polytetrafluoroethylene (PTFE) substrate, then is gone back by absorption
The method of former silver obtains the argent pattern of fineness in substrate, specifically comprises the following steps that
Step 1: substrate is polytetrafluoroethylene (PTFE), by substrate with EtOH Sonicate clean 1 hour, after taking-up
It is vacuum dried under the conditions of 80 DEG C, substrate is immersed in gamma-aminopropyl-triethoxy-silane ethanol solution 24
Hour, taking-up ethanol washs, then steeps in the polyacrylic acid aqueous solution 1 hour, takes out at 100 DEG C of bars
It is dried under part；
Step 2: by 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine use water dissolve, and obtain
The 5,10,15,20-p-aminophenyl porphyrin aluminium of 0.2-0.8wt% six carboxyl aluminum phthalocyanine；
Step 3: PDMS seal is soaked in 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl phthaleins
30-40s in cyanines aluminum water solution, in N after taking-up2Air-flow is dried 30-60s, 5,10,15,20-pairs will be scribbled
The PDMS seal of aminophenyl porphyrin aluminium the six carboxyl aluminum phthalocyanine aqueous solution is placed in carboxylated substrate, gently
Pressure 10-20s, is transferred to substrate surface by PDMS seal designs, obtains printing figuratum substrate；
Step 4: figuratum for print substrate is soaked in AgNO310-30s in solution, puts into boron after taking-up
In sodium hydride solution, reduction obtains argent pattern.
Wherein, γ-aminopropyl triethoxysilane in described gamma-aminopropyl-triethoxy-silane ethanol solution
Mass fraction be 5%.
Wherein, substrate is cleaned in the step of 1 hour with EtOH Sonicate, described substrate and described ethanol weight
Amount ratio is 1:5-10.
Wherein, described substrate and described gamma-aminopropyl-triethoxy-silane ethanol solution weight ratio are 1:5-10.
Wherein, described substrate and described polyacrylic acid aqueous solution weight ratio are 1:10.
Wherein, the concentration of the described polyacrylic acid aqueous solution is 1-20g/L.
Wherein, described AgNO3AgNO in solution3Mass fraction is 0.8%.
Wherein, in described sodium borohydride solution, the mass fraction of sodium borohydride is 5%.
The invention have the benefit that
1, by 5,10,15,20-p-aminophenyl porphyrin aluminium the six carboxyl aluminum phthalocyanine aqueous solution are connect as micro-
Touch printing ink and prepare metal pattern, for micro-contact printing at the ptfe surface that electron trade is conventional
Industry provides new approaches.
2, act on substrate surface by the chemical bonding of silane coupler and introduce acrylate copolymer, with logical
Crossing the carboxylated surface that hydrolysis obtains to compare, it is more that its a large amount of carboxyls having can adsorb combination
Phthalocyanine porphyrin dyad complex, the reaction for next step absorbing and reducing Ag provides more site,
To combining more close Ag metallic circuit；And by changing the polyacrylic acid molecular weight used, permissible
Adjust the acrylic acid units quantity introduced, therefore can according to product requirements, parameter be adjusted easily
Whole.
3, introducing polyacrylic acid by silane coupler, this method of modifying is to carry out, no at substrate surface
Affect the chemical constitution of substrate, therefore more conducively property at the bottom of protection group compared with the method that hydrolysis obtains carboxyl
Energy.
4,5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine water solubles, solvent green ring
Protect.
5, relative to single metal phthalocyanine, Porphyrin and its Complexes, 5,10,15,20-p-aminophenyl porphyrins
Aluminium six some special natures of carboxyl aluminum phthalocyanine, phthalocyanine moiety in its structure and porphyrin moiety are all same
In plane, forming the bigger conjugated system being made up of phthalocyanine and porphyrin, its pi-pi bond effect is higher, institute
To have the strongest stability when film forming.Meanwhile, reactive site is more, can draw as required
Enter new group and regulate its physical and chemical performance.
6,5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine aqueous feed solution be easy to get, cost
Low, stable, commercial Application has the biggest potentiality.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, to make those skilled in the art with reference to explanation
Book word can be implemented according to this.
Embodiment 1:
1, substrate is polytetrafluoroethylene (PTFE), takes out after 100g substrate being cleaned 1 hour with 500g EtOH Sonicate,
It is vacuum dried under the conditions of 80 DEG C, above-mentioned substrate is immersed in the gamma-aminopropyl-triethoxy of 500g5wt%
In silane ethanol 24 hours, taking-up ethanol washed, then steep in 1000g concentration be the polypropylene of 1g/L
In aqueous acid 1 hour, take out and be dried at 100 DEG C.
2, by 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine use water dissolve, and obtain
The 5,10,15,20-p-aminophenyl porphyrin aluminium of 0.2wt% six carboxyl aluminum phthalocyanine.
3, PDMS seal is soaked in 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine water
30s in solution, in N after taking-up2Air-flow is dried 30s, 5,10,15,20-p-aminophenyl porphyrins will be scribbled
The PDMS seal of aluminium the six carboxyl aluminum phthalocyanine aqueous solution is placed in carboxylated substrate, gently presses 10s, will
PDMS seal designs is transferred to substrate surface, obtains printing figuratum substrate.
4, the figuratum substrate of print is soaked in the AgNO of mass fraction 1wt%3Middle 10s, puts after taking-up
Enter reduction in 5wt% sodium borohydride and obtain argent pattern.
Embodiment 2:
1, substrate is polytetrafluoroethylene (PTFE), takes out after 100g substrate being cleaned 1 hour with 700g EtOH Sonicate,
It is vacuum dried under the conditions of 80 DEG C.Substrate is immersed in the gamma-aminopropyl-triethoxy-silane of 700g5wt%
In ethanol 24 hours, taking-up ethanol washed, then to steep in 1000g concentration be that 10g/L polyacrylic acid is water-soluble
In liquid 1 hour, take out 100 DEG C and be dried.
2, by 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine use water dissolve, and obtain concentration
5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine for 0.5wt%.
3, PDMS seal is soaked in 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine water
35s in solution, in N after taking-up2Air-flow is dried 45s, 5,10,15,20-p-aminophenyl porphyrins will be scribbled
The PDMS seal of aluminium the six carboxyl aluminum phthalocyanine aqueous solution is placed in carboxylated substrate, gently presses 15s, will
PDMS seal designs is transferred to substrate surface, obtains printing figuratum substrate.
4, figuratum for print substrate is soaked in 0.8wt%AgNO3Middle 25s, puts into 5wt% boron after taking-up
In sodium hydride, reduction obtains argent pattern.
Embodiment 3:
1, substrate is polytetrafluoroethylene (PTFE), takes after being cleaned 1 hour by 100g substrate 1000g EtOH Sonicate
Go out, be vacuum dried under the conditions of 80 DEG C.Substrate is immersed in γ-aminopropyl three ethoxy of 1000g5wt%
In base silane ethanol 24 hours, taking-up ethanol washed, then steep in 1000g concentration be 20g/L polypropylene
In aqueous acid 1 hour, take out 100 DEG C and be dried.
2, by 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine use water dissolve, and obtain concentration
5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine for 0.8wt%.
3, PDMS seal is soaked in 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine water
40s in solution, in N after taking-up2Air-flow is dried 30-60s, 5,10,15,20-p-aminophenyls will be scribbled
The PDMS seal of porphyrin aluminium the six carboxyl aluminum phthalocyanine aqueous solution is placed in carboxylated substrate, gently presses 10-20s,
PDMS seal designs is transferred to substrate surface, obtains printing figuratum substrate.
4, figuratum for print substrate is soaked in 0.8wt%AgNO3Middle 30s, puts into 5wt% boron after taking-up
In sodium hydride, reduction obtains argent pattern.
Although embodiment of the present invention are disclosed as above, but it is not restricted to specification and embodiment party
Listed utilization in formula, it can be applied to various applicable the field of the invention completely, for being familiar with ability
For the personnel in territory, be easily achieved other amendment, therefore without departing substantially from claim and etc. homotype
Enclosing under limited universal, the present invention is not limited to specific details and shown here as the reality with description
Execute example.
Claims (8)
1. water-soluble planar is conjugated phthalocyanine porphyrin dyad and carries out micro-printing as micro-contact printing ink
Method, it is characterised in that:
Water-soluble planar conjugation phthalocyanine porphyrin dyad is 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxylics
Base aluminum phthalocyanine, has a following structural formula:
Using the aqueous solution of 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine as micro-contact print
The print paste of brush, is transferred to polytetrafluoroethylene (PTFE) substrate by the pattern of PDMS seal, then passes through absorbing and reducing
The method of silver obtains the argent pattern of fineness in substrate, specifically comprises the following steps that
Step 1: substrate is polytetrafluoroethylene (PTFE), by substrate with EtOH Sonicate clean 1 hour, after taking-up
It is vacuum dried under the conditions of 80 DEG C, substrate is immersed in gamma-aminopropyl-triethoxy-silane ethanol solution 24
Hour, taking-up ethanol washs, then steeps in the polyacrylic acid aqueous solution 1 hour, takes out at 100 DEG C of bars
It is dried under part；
Step 2: by 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl aluminum phthalocyanine use water dissolve, and obtain
The 5,10,15,20-p-aminophenyl porphyrin aluminium of 0.2-0.8wt% six carboxyl aluminum phthalocyanine；
Step 3: PDMS seal is soaked in 5,10,15,20-p-aminophenyl porphyrin aluminium six carboxyl phthaleins
30-40s in cyanines aluminum water solution, in N after taking-up2Air-flow is dried 30-60s, 5,10,15,20-pairs will be scribbled
The PDMS seal of aminophenyl porphyrin aluminium the six carboxyl aluminum phthalocyanine aqueous solution is placed in carboxylated substrate, gently
Pressure 10-20s, is transferred to substrate surface by PDMS seal designs, obtains printing figuratum substrate；
Step 4: figuratum for print substrate is soaked in AgNO310-30s in solution, puts into boron after taking-up
In sodium hydride solution, reduction obtains argent pattern.
2. the phthalocyanine porphyrin dyad that is conjugated by water-soluble planar as claimed in claim 1 is as micro-contact print
Brush ink carries out the method for micro-printing, it is characterised in that: described gamma-aminopropyl-triethoxy-silane ethanol is molten
In liquid, the mass fraction of γ-aminopropyl triethoxysilane is 5%.
3. the phthalocyanine porphyrin dyad that is conjugated by water-soluble planar as claimed in claim 1 is as micro-contact print
Brush ink carries out the method for micro-printing, it is characterised in that: substrate is cleaned with EtOH Sonicate the step of 1 hour
In Zhou, described substrate and described ethanol weight ratio are 1:5-10.
4. the phthalocyanine porphyrin dyad that is conjugated by water-soluble planar as claimed in claim 1 is as micro-contact print
Brush ink carries out the method for micro-printing, it is characterised in that: described substrate and described gamma-aminopropyl-triethoxy
Silane ethanol solution weight ratio is 1:5-10.
5. the phthalocyanine porphyrin dyad that is conjugated by water-soluble planar as claimed in claim 1 is as micro-contact print
Brush ink carries out the method for micro-printing, it is characterised in that: described substrate and described polyacrylic acid aqueous solution weight
Amount ratio is 1:10.
6. the phthalocyanine porphyrin dyad that is conjugated by water-soluble planar as claimed in claim 1 is as micro-contact print
Brush ink carries out the method for micro-printing, it is characterised in that: the concentration of the described polyacrylic acid aqueous solution is
1-20g/L。
7. the phthalocyanine porphyrin dyad that is conjugated by water-soluble planar as claimed in claim 1 is as micro-contact print
Brush ink carries out the method for micro-printing, it is characterised in that: described AgNO3AgNO in solution3Quality is divided
Number is 0.8%.
8. the phthalocyanine porphyrin dyad that is conjugated by water-soluble planar as claimed in claim 1 is as micro-contact print
Brush ink carries out the method for micro-printing, it is characterised in that: the matter of sodium borohydride in described sodium borohydride solution
Amount mark is 5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410619388.3A CN104356741B (en) | 2014-11-05 | 2014-11-05 | Water-soluble planar is conjugated the method that phthalocyanine porphyrin dyad carries out micro-printing as micro-contact printing ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410619388.3A CN104356741B (en) | 2014-11-05 | 2014-11-05 | Water-soluble planar is conjugated the method that phthalocyanine porphyrin dyad carries out micro-printing as micro-contact printing ink |
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| CN104356741B true CN104356741B (en) | 2016-08-24 |
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| KR20120013322A (en) * | 2009-04-14 | 2012-02-14 | 나노잉크, 인크. | Conducting lines, nanoparticles, inks, and patterning |
| JP5821313B2 (en) * | 2011-06-20 | 2015-11-24 | 東レ株式会社 | A printing ink composition for forming an insulating film, and an insulating film formed from the printing ink composition for forming an insulating film. |
| CN102516841B (en) * | 2011-11-21 | 2013-08-07 | 广西师范学院 | Application of zinc phthalocyanine complex as ink in micro-contact printing |
| CN102964910B (en) * | 2012-11-30 | 2014-03-19 | 广西师范学院 | Use of water-soluble tetra sodium sulfonate phenyl porphyrin metal complex in microcontact printing |
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Effective date of registration: 20181205 Address after: 214026 Tiandi 27-9-1402, Xinghui, Shanghe Garden, Liangxi District, Wuxi City, Jiangsu Province Patentee after: Wuxi Tongchun New Energy Technology Co., Ltd. Address before: 530001 Guangxi Teachers Education University, 175 Nanning Ming Xiu East Road, the Guangxi Zhuang Autonomous Region Patentee before: Guangxi Teachers College |