U.S. patent application number 12/824220 was filed with the patent office on 2011-06-30 for polyimide polymers for flexible electrical device substrate materials and flexible electrical devices comprising the same.
This patent application is currently assigned to INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE. Invention is credited to Chyi-Ming Leu, Hsueh-Yi Liao, Chi-Fu Tseng, Yung-Lung Tseng.
Application Number | 20110155235 12/824220 |
Document ID | / |
Family ID | 44185982 |
Filed Date | 2011-06-30 |
United States Patent
Application |
20110155235 |
Kind Code |
A1 |
Tseng; Chi-Fu ; et
al. |
June 30, 2011 |
POLYIMIDE POLYMERS FOR FLEXIBLE ELECTRICAL DEVICE SUBSTRATE
MATERIALS AND FLEXIBLE ELECTRICAL DEVICES COMPRISING THE SAME
Abstract
A polyimide polymer of Formula (I) for flexible electrical
device substrate material is provided. ##STR00001## In Formula (I),
B is a polycyclic aliphatic group, A is an aromatic group
containing at least one ether bond, A' is an aromatic or aliphatic
group, and 1.ltoreq.n/m.ltoreq.4. The invention also provides a
flexible electrical device including the polyimide polymer.
Inventors: |
Tseng; Chi-Fu; (Taipei,
TW) ; Leu; Chyi-Ming; (Hsinchu County, TW) ;
Liao; Hsueh-Yi; (Yonghe City, TW) ; Tseng;
Yung-Lung; (Zhubei City, TW) |
Assignee: |
INDUSTRIAL TECHNOLOGY RESEARCH
INSTITUTE
Hsinchu County
TW
|
Family ID: |
44185982 |
Appl. No.: |
12/824220 |
Filed: |
June 27, 2010 |
Current U.S.
Class: |
136/256 ;
349/158; 359/267; 359/290; 359/296; 428/1.1; 428/473.5;
528/322 |
Current CPC
Class: |
C08G 73/1046 20130101;
C08L 79/08 20130101; Y02E 10/549 20130101; C08G 73/1039 20130101;
Y02E 10/50 20130101; H01L 31/03926 20130101; C08G 73/1064 20130101;
C09K 2323/00 20200801; C08G 73/1078 20130101; C08G 73/1075
20130101; H01L 51/0035 20130101; C08G 73/105 20130101; C08G 73/1042
20130101; Y10T 428/31721 20150401 |
Class at
Publication: |
136/256 ;
349/158; 359/296; 359/290; 359/267; 528/322; 428/473.5;
428/1.1 |
International
Class: |
C08G 73/10 20060101
C08G073/10; G02F 1/1333 20060101 G02F001/1333; G02F 1/167 20060101
G02F001/167; G02B 26/00 20060101 G02B026/00; G02F 1/153 20060101
G02F001/153; B32B 27/28 20060101 B32B027/28; C09K 19/00 20060101
C09K019/00; H01L 31/0216 20060101 H01L031/0216 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 31, 2009 |
TW |
098146298 |
Claims
1. A polyimide polymer for flexible electrical device substrate
material, of Formula (I): ##STR00051## wherein B is a polycyclic
aliphatic group; A is an aromatic group containing at least one
ether bond; A' is an aromatic or aliphatic group; and
1.ltoreq.n/m.ltoreq.4.
2. The polyimide polymer for flexible electrical device substrate
material as claimed in claim 1, wherein B comprises:
##STR00052##
3. The polyimide polymer for flexible electrical device substrate
material as claimed in claim 1, wherein A comprises:
##STR00053##
4. The polyimide polymer for flexible electrical device substrate
material as claimed in claim 1, wherein A' comprises:
##STR00054##
5. A flexible electrical device, comprising: a first substrate; a
second substrate opposed to the first substrate, wherein one of the
first and second substrates comprises a polyimide polymer as
claimed in claim 1; and a medium layer disposed between the first
substrate and the second substrate.
6. The flexible electrical device as claimed in claim 5, wherein
the medium layer comprises liquid crystal or polymer.
7. The flexible electrical device as claimed in claim 5, wherein
the flexible electrical device comprises a particle display, liquid
crystal display or micro electro mechanical system (MEMS)
display.
8. The flexible electrical device as claimed in claim 7, wherein
the particle display comprises a electrochromic display (ECD) or
electro-phoretic display (EPD).
9. The flexible electrical device as claimed in claim 7, wherein
the liquid crystal display comprises cholesteric liquid crystal
display (ChLCD) or bistable twisted-nematic (TN) liquid crystal
display.
10. The flexible electrical device as claimed in claim 5, wherein
the flexible electrical device comprises a solar cell.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority of Taiwan Patent
Application No. 98146298, filed on Dec. 31, 2009, the entirety of
which is incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to a polymer, and in particular to a
polyimide polymer for flexible electrical device substrate material
and a flexible electrical device comprising the polymer.
[0004] 2. Description of the Related Art
[0005] The applications of flexible displays have been valued. This
technology is actively researched by various large global companies
and the development of flexible display technology has
progressively matured. The development of active flexible displays
which can substitute for passive displays has become the focus of
the technology. Development of a flexible display that is light,
portable, rigid and flexible has become the new trend in
next-generation displays. In the development of an active flexible
display, providing a transparent substrate with high thermal
resistance which is capable of enduring the TFT processes plays an
important role.
[0006] While a transparent substrate material is applied in
flexible flat panel display fabrication, it must be capable of
enduring the TFT processes. For example, TFT processes may include
high-temperature processes (>200.degree. C.), a washing
processes and chemical erosion from etching and a development
processes. Thus, performing chemical structure modifications or
specific processes on present flexible transparent plastic film
material with high glass transition temperature (Tg) to achieve
high thermal resistance (300.degree. C.) and dimensional stability
is desirable. Additionally, while the plastic material is coated on
a glass substrate to form a film, forming a tensile film possessing
high chemical resistance capable of enduring the TFT plating and
etching processes of the flexible flat panel display fabrication is
required. Development of such flexible plastic film material with
the aforesaid characteristics is desirable.
[0007] A conventional polyimide plastic substrate with high thermal
resistance can be directly coated on a glass and can endure
processing temperatures exceeding 200.degree. C., and thus achieves
dimensional stability. However, such polyimide substrate is
yellow.
BRIEF SUMMARY OF THE INVENTION
[0008] One embodiment of the invention provides a polyimide polymer
for flexible electrical device substrate material, of Formula
(I):
##STR00002##
[0009] In Formula (I), B is a polycyclic aliphatic group, A is an
aromatic group containing at least one ether bond, A' is an
aromatic or aliphatic group, and 1.ltoreq.n/m.ltoreq.4.
[0010] One embodiment of the invention provides a flexible
electrical device comprising a first substrate, a second substrate
opposed to the first substrate, wherein one of the first and second
substrates comprises a polyimide polymer of Formula (I), and a
medium layer disposed between the first substrate and the second
substrate.
##STR00003##
[0011] In Formula (I), B is a polycyclic aliphatic group, A is an
aromatic group containing at least one ether bond, A' is an
aromatic or aliphatic group, and 1.ltoreq.n/m.ltoreq.4.
[0012] The invention provides a soluble polyimide polymer (film)
which is colorless, has high transparency, high thermal resistance,
is high flexibility and is suitable for application in flexible
flat panel display fabrication using existing equipment. Polycyclic
aliphatic dianhydride, aromatic diamine and diamine containing
ether bonds are copolymerized under a high temperature with a
specific ratio to form a soluble polyimide solution. The polyimide
solution is then coated on a glass substrate to form a film. The
tensile film possesses highly chemically resistant and endures the
TFT plating and etching processes during flexible flat panel
display fabrication. It is also highly thermally resistant
(Tg>300.degree. C.) and it has a high chemical resistance
(capable of resisting photoresist, oxalic acid, developer and
stripper).
[0013] A detailed description is given in the following
embodiments.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The following description is of the best-contemplated mode
of carrying out the invention. This description is made for the
purpose of illustrating the general principles of the invention and
should not be taken in a limiting sense. The scope of the invention
is best determined by reference to the appended claims.
[0015] One embodiment of the invention provides a polyimide polymer
for flexible electrical device substrate material, of Formula
(I):
##STR00004##
[0016] In Formula (I), B may be a polycyclic aliphatic group, for
example:
##STR00005##
[0017] A may be an aromatic group containing at least one ether
bond, for example:
##STR00006##
[0018] A' may be an aromatic or aliphatic group, for example:
##STR00007##
[0019] One embodiment of the invention provides a flexible
electrical device comprising a first substrate, a second substrate
and a medium layer. The first substrate is opposed to the second
substrate. One of the first and second substrates comprises a
polyimide polymer of Formula (I). The medium layer is disposed
between the first substrate and the second substrate.
##STR00008##
[0020] In Formula (I), B may be a polycyclic aliphatic group, for
example:
##STR00009##
[0021] A may be an aromatic group containing at least one ether
bond, for example:
##STR00010##
[0022] A' may be an aromatic or aliphatic group, for example:
##STR00011##
[0023] The medium layer may comprise liquid crystal, microcapsule
electrophoresis or a polymer, for example; nematic liquid crystal,
smectic liquid crystal, cholesteric liquid crystal, E-ink,
fluorescent small molecule or fluorescent polymer.
[0024] The disclosed flexible electrical device may comprise a
particle display, liquid crystal display or micro electro
mechanical system (MEMS) display. The particle display may comprise
an electrochromic display (ECD) or electro-phoretic display (EPD).
The liquid crystal display may comprise cholesteric liquid crystal
display (ChLCD) or a bistable twisted-nematic (TN) liquid crystal
display.
[0025] The disclosed flexible electrical device may further
comprise a solar cell.
[0026] The invention provides a soluble polyimide polymer (film)
which is colorless, highly transparent, has a high thermal
resistance and is highly flexible, and is suitable for application
for flexible flat panel display fabrication using existing
equipment. Polycyclic aliphatic dianhydride, aromatic diamine and
diamine containing ether bonds are copolymerized under high
temperature with a specific ratio to form a soluble polyimide
solution. The polyimide solution is then coated on a glass
substrate to form a film. The tensile film possesses high chemical
resistance and endures the TFT plating and etching processes of
flexible flat panel display fabrication, with high thermal
resistance (Tg>300.degree. C.) and high chemical resistance
(capable of resisting photoresist, oxalic acid, developer and
stripper).
EXAMPLES
[0027] The disclosed polyimide polymer possesses high thermal
resistance and a low coefficient of thermal expansion (CTE). The
polycyclic aliphatic dianhydride improves the solubility of the
polymer solution. The aromatic diamine or diamine containing ether
bond improves chemical resistance. The aromatic diamine (for
example
##STR00012##
diamine containing ether bond (for example
##STR00013##
and polycyclic aliphatic dianhydride are copolymerized with a
specific ratio to form a soluble polyimide solution. The polyimide
solution is then coated on a glass substrate to form a film. The
film possesses high transparency, is colorless, is highly thermally
resistant, (Tg>300.degree. C.), high flexibility and has a high
chemical resistance (capable of resisting photoresist, oxalic acid,
developer and stripper).
[0028] The polyimide is synthesized by polycondensation, which is
disclosed as follows. One method is that diamine monomer and
dianhydride monomer are reacted in a polar solvent to form a poly
(amic acid) (PAA) (precursor of polyimide). PAA is then thermally
imidized (300 to 400.degree. C.) or chemically imidized to
dehydrate to form polyimide. The other method involves reacting a
diamine monomer and dianhydride monomer in a phenolic solvent (for
example m-cresol or Cl-phenol). After heating to reflux
temperature, the polyimide is then prepared.
##STR00014##
Example 1
Preparation of B1317-BAPB (0.3)-BAPPm (0.7)
[0029] 0.0103 mole of
##STR00015##
and 0.0044 mole of
##STR00016##
were
[0030] completely dissolved in 38.29 g of m-cresol in a
three-necked flask under nitrogen at room temperature. 0.0150 mole
of B1317 dianhydride
##STR00017##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes.
Example 2
Preparation of B1317-BAPB (0.5)-BAPPm (0.5)
[0031] 0.0074 mole of
##STR00018##
and 0.0074 mole of
##STR00019##
were completely dissolved in 46.62 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00020##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes. Next, the reaction solution was dropped into methanol to
precipitate silk polyimide. The polyimide was then baked in a
vacuum oven for 12 hours. The silk polyimide was then dissolved in
DMAc, with a solid content of 15%.
Example 3
Preparation of B1317-BAPB (0.7)-BAPPm (0.3)
[0032] 0.0044 mole of
##STR00021##
and 0.0103 mole of
##STR00022##
were completely dissolved in 35.08 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00023##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes. Next, the reaction solution was dropped into methanol to
precipitate silk polyimide. The polyimide was then baked in a
vacuum oven for 12 hours. The silk polyimide was then dissolved in
DMAc, with a solid content of 15%.
Example 4
Preparation of B1317-BAPB (0.8)-BAPPm (0.2)
[0033] 0.0029 mole of
##STR00024##
and 0.0118 mole of
##STR00025##
were completely dissolved in 37.05 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00026##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes. Next, the reaction solution was dropped into methanol to
precipitate silk polyimide. The polyimide was then baked in a
vacuum oven for 12 hours. The silk polyimide was then dissolved in
DMAc, with a solid content of 15%.
Example 5
Preparation of B1317-BAPB (0.9)-BAPPm (0.1)
[0034] 0.0015 mole of
##STR00027##
and 0.0132 mole of
##STR00028##
were completely dissolved in 38.79 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00029##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes.
TABLE-US-00001 TABLE 1 Solvent utilized in TFT processes
Compositions Photo- Oxalic Example B1317 BAPB BAPPm solubility
resist acid Developer Stripper 1 1 0.3 0.7 X -- -- -- -- 2 1 0.5
0.5 .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. 3 1 0.7 0.3 .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. 4 1 0.8 0.2 .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. 5 1 0.9 0.1 X -- -- --
--
[0035] The disclosed polyimide synthesized by diamine (BAPB and
BAPPm with various ratios) and polycyclic aliphatic dianhydride
(B1317) prepared from Examples 1 to 5 was further coated on a glass
to form a polyimide film. Table 1 shows the solubility of the
polyimide with various compositions and the test results of the
chemical resistance of the polyimide to the solvent utilized in TFT
processes (test condition: 50.degree. C./1 hour).
Example 6
Preparation of B1317-ODA (0.3)-BAPPm (0.7)
[0036] 0.0103 mole of
##STR00030##
and 0.0044 mole of
##STR00031##
were completely dissolved in 35.29 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00032##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes.
Example 7
Preparation of B1317-ODA (0.5)-BAPPm (0.5)
[0037] 0.0074 mole of
##STR00033##
and 0.0074 mole of
##STR00034##
were completely dissolved in 32.97 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00035##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes. Next, the reaction solution was dropped into methanol to
precipitate silk polyimide. The polyimide was then baked in a
vacuum oven for 12 hours. The silk polyimide was then dissolved in
DMAc, with a solid content of 15%.
Example 8
Preparation of B1317-ODA (0.7)-BAPPm (0.3)
[0038] 0.0044 mole of
##STR00036##
and 0.0103 mole of
##STR00037##
were completely dissolved in 30.38 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00038##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes. Next, the reaction solution was dropped into methanol to
precipitate silk polyimide. The polyimide was then baked in a
vacuum oven for 12 hours. The silk polyimide was then dissolved in
DMAc, with a solid content of 15%.
Example 9
Preparation of B1317-ODA (0.8)-BAPPm (0.2)
[0039] 0.0029 mole of
##STR00039##
and 0.0118 mole of
##STR00040##
were completely dissolved in 29.11 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00041##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes. Next, the reaction solution was dropped into methanol to
precipitate silk polyimide. The polyimide was then baked in a
vacuum oven for 12 hours. The silk polyimide was then dissolved in
DMAc, with a solid content of 15%.
Example 10
Preparation of B1317-ODA (0.9)-BAPPm (0.1)
[0040] 0.0015 mole of
##STR00042##
and 0.0132 mole of
##STR00043##
were completely dissolved in 27.93 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of B1317
dianhydride
##STR00044##
was then added to the flask. After B1317 was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes.
TABLE-US-00002 TABLE 2 Solvent utilized in TFT processes
Compositions Photo- Oxalic Example B1317 ODA BAPPm solubility
resist acid Developer Stripper 6 1 0.3 0.7 X -- -- -- -- 7 1 0.5
0.5 .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. 8 1 0.7 0.3 .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. 9 1 0.8 0.2 .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. 10 1 0.9 0.1 X -- -- --
--
[0041] The disclosed polyimide synthesized by diamine (ODA and
BAPPm with various ratios) and polycyclic aliphatic dianhydride
(B1317) prepared from Examples 6 to 10 was further coated on a
glass to form a polyimide film. Table 2 shows the solubility of the
polyimide with various compositions and the test results of the
chemical resistance of the polyimide to solvents utilized in TFT
processes (test condition: 50.degree. C./1 hour).
Comparative Example 1
Preparation of 5-ring-BAPB (0.7)-BAPPm (0.3)
[0042] 0.0044 mole of
##STR00045##
and 0.0103 mole of
##STR00046##
were completely dissolved in 35.03 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of 5-ring
dianhydride
##STR00047##
was then added to the flask. After 5-ring was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes. Next, the reaction solution was dropped into methanol to
precipitate silk polyimide. The polyimide was then baked in a
vacuum oven for 12 hours. The silk polyimide was then dissolved in
DMAc, with a solid content of 15%.
Comparative Example 2
Preparation of 6FDA-BAPB (0.7)-BAPPm (0.3)
[0043] 0.0044 mole of
##STR00048##
and 0.0103 mole of
##STR00049##
were completely dissolved in 49.04 g of m-cresol in a three-necked
flask under nitrogen at room temperature. 0.0150 mole of 6FDA
dianhydride
##STR00050##
was then added to the flask. After 6FDA was completely dissolved,
the resulting solution was continuously stirred for 1 hour to form
a sticky poly(amic acid) (PAA) solution. Next, the PAA solution was
heated to 220.degree. C. to react for 3 hours. Water was
simultaneously removed using a water remover during the aforesaid
processes. Next, the reaction solution was dropped into methanol to
precipitate silk polyimide. The polyimide was then baked in a
vacuum oven for 12 hours. The silk polyimide was then dissolved in
DMAc, with a solid content of 15%.
TABLE-US-00003 TABLE 3 Solvent utilized in TFT processes
Compositions Oxalic No. Dianhydride Diamine solubility Photoresist
acid Developer Stripper 1 5-ring BAPB BAPPm .largecircle. X
.largecircle. .largecircle. X (0.7) (0.3) 2 6FDA BAPB BAPPm
.largecircle. X X .largecircle. .largecircle. (0.7) (0.3)
[0044] The polyimide synthesized by polycyclic aliphatic
dianhydride (5-ring and 6FDA) and diamine (BAPB (0.7) and BAPPm
(0.3)) prepared from Comparative Examples 1 and 2 was further
coated on a glass to form a polyimide film. Table 3 shows the
solubility of the polyimide and the test results of the chemical
resistance of the polyimide to solvent utilized in TFT processes
(test condition: 50.degree. C./1 hour).
[0045] While the invention has been described by way of example and
in terms of preferred embodiment, it is to be understood that the
invention is not limited thereto. To the contrary, it is intended
to cover various modifications and similar arrangements (as would
be apparent to those skilled in the art). Therefore, the scope of
the appended claims should be accorded the broadest interpretation
so as to encompass all such modifications and similar
arrangements.
* * * * *