U.S. patent number 10,385,237 [Application Number 15/735,018] was granted by the patent office on 2019-08-20 for organic electronic device.
This patent grant is currently assigned to LG CHEM, LTD.. The grantee listed for this patent is LG CHEM, LTD.. Invention is credited to Kyung Yul Bae, Yoon Gyung Cho, Sang Min Park, Se Woo Yang, Hyun Jee Yoo.
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United States Patent |
10,385,237 |
Bae , et al. |
August 20, 2019 |
Organic electronic device
Abstract
The present application relates to an organic electronic device,
a method for preparing same, and a lighting apparatus and a display
device comprising same. The present application enables an organic
electronic device to show excellent moisture-blocking properties
and have flexibility as well as excellent and reliable durability
at high temperature and high humidity.
Inventors: |
Bae; Kyung Yul (Daejeon,
KR), Yoo; Hyun Jee (Daejeon, KR), Yang; Se
Woo (Daejeon, KR), Cho; Yoon Gyung (Daejeon,
KR), Park; Sang Min (Daejeon, KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
LG CHEM, LTD. |
Seoul |
N/A |
KR |
|
|
Assignee: |
LG CHEM, LTD. (Seoul,
KR)
|
Family
ID: |
57504718 |
Appl.
No.: |
15/735,018 |
Filed: |
June 9, 2016 |
PCT
Filed: |
June 09, 2016 |
PCT No.: |
PCT/KR2016/006126 |
371(c)(1),(2),(4) Date: |
December 08, 2017 |
PCT
Pub. No.: |
WO2016/200176 |
PCT
Pub. Date: |
December 15, 2016 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20180171179 A1 |
Jun 21, 2018 |
|
Foreign Application Priority Data
|
|
|
|
|
Jun 9, 2015 [KR] |
|
|
10-2015-0081475 |
Aug 20, 2015 [KR] |
|
|
10-2015-0117379 |
Dec 11, 2015 [KR] |
|
|
10-2015-0177030 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09J
7/30 (20180101); H01L 51/5237 (20130101); H01L
51/5253 (20130101); C08L 23/22 (20130101); H01L
51/56 (20130101); C08F 210/10 (20130101); H01L
51/52 (20130101); C09J 4/06 (20130101); H01L
51/00 (20130101); H01L 51/0001 (20130101); C09J
7/20 (20180101); C09J 123/22 (20130101); C09J
153/00 (20130101); H01L 51/5246 (20130101); C08L
53/02 (20130101); C09J 4/00 (20130101); C09D
4/06 (20130101); C08F 2/50 (20130101); C09D
4/06 (20130101); C08F 255/10 (20130101); C08L
53/02 (20130101); C08L 63/00 (20130101); C08L
63/00 (20130101); C09J 2463/00 (20130101); Y02E
10/549 (20130101); C09J 2423/00 (20130101); H01L
51/0097 (20130101); C09J 2301/414 (20200801); H01L
2251/5361 (20130101); H01L 2251/5338 (20130101); C09J
2203/326 (20130101); C09J 2423/00 (20130101); C09J
2463/00 (20130101) |
Current International
Class: |
C09J
4/06 (20060101); C09J 123/22 (20060101); C08L
23/22 (20060101); H01L 51/00 (20060101); H01L
51/52 (20060101); H01L 51/56 (20060101); C09J
7/20 (20180101); C09J 4/00 (20060101); C08F
210/10 (20060101); C09J 7/30 (20180101); C09D
4/06 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
2 913 372 |
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Sep 2015 |
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2003-13023 |
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Jan 2003 |
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2014-167051 |
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Sep 2014 |
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JP |
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2014-194942 |
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Oct 2014 |
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JP |
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10-2008-0014021 |
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Feb 2008 |
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KR |
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10-2010-0130898 |
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Dec 2010 |
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KR |
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10-2014-0049278 |
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Apr 2014 |
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KR |
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10-2015-0010667 |
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Jan 2015 |
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KR |
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10-2015-0033581 |
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Apr 2015 |
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KR |
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10-2015-0033582 |
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Apr 2015 |
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KR |
|
2011062167 |
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May 2011 |
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WO |
|
2013108731 |
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Jul 2013 |
|
WO |
|
2014/069398 |
|
May 2014 |
|
WO |
|
2014084352 |
|
Jun 2014 |
|
WO |
|
2014190151 |
|
Nov 2014 |
|
WO |
|
Primary Examiner: Mandala; Michelle
Attorney, Agent or Firm: Dentons US LLP
Claims
The invention claimed is:
1. An organic electronic device comprising a substrate in which an
organic electronic element is formed on a first surface of said
substrate and an adhesive layer formed on a second surface of said
substrate and comprising a polymer derived from butylene and a
curable oligomer.
2. The organic electronic device according to claim 1, wherein the
polymer derived from butylene is a homopolymer of a butylene
monomer; a copolymer obtained by copolymerizing another monomer
polymerizable with a butylene monomer; a reactive oligomer using a
butylene monomer; or a mixture thereof.
3. The organic electronic device according to claim 2, wherein
another monomer polymerizable with a butylene monomer is isoprene,
styrene or butadiene.
4. The organic electronic device according to claim 2, wherein the
reactive oligomer using a butylene monomer comprises a butylene
polymer having a reactive functional group, and said butylene
polymer is associated with another polymer having a reactive
functional group.
5. The organic electronic device according to claim 1, wherein the
polymer derived from butylene has a weight average molecular weight
in a range of 10,000 to 2,000,000.
6. The organic electronic device according to claim 1, wherein the
curable oligomer is a hydrogenated compound.
7. The organic electronic device according to claim 1, wherein the
curable oligomer is an aromatic compound.
8. The organic electronic device according to claim 1, wherein the
curable oligomer has a weight average molecular weight in a range
of 400 to 10,000.
9. The organic electronic device according to claim 1, wherein the
curable oligomer is a hydrogenated aromatic epoxy compound.
10. The organic electronic device according to claim 1, wherein the
curable oligomer has an epoxy equivalent in a range of 100 to 1500
g/eq.
11. The organic electronic device according to claim 1, wherein the
curable oligomer is included in an amount of 15 to 100 parts by
weight, relative to 100 parts by weight of the polymer derived from
butylene.
12. The organic electronic device according to claim 1, further
comprising a curable monomer.
13. The organic electronic device according to claim 12, wherein
the curable monomer has a weight average molecular weight of less
than 400.
14. The organic electronic device according to claim 12, wherein
the curable monomer has a cyclic structure in which ring
constituent atoms in the molecular structure are in a range of 3 to
10.
15. The organic electronic device according to claim 12, wherein
the curable monomer is included in an amount of 20 to 80 parts by
weight, relative to 100 parts by weight of the polymer derived from
butylene.
16. The organic electronic device according to claim 12, wherein
the curable monomer and the curable oligomer are included in ratios
of 10 to 50 parts by weight and 20 to 70 parts by weight,
respectively.
17. The organic electronic device according to claim 1, wherein the
adhesive layer comprises no tackifier.
18. The organic electronic device according to claim 1, wherein the
adhesive layer has a storage elastic modulus, as measured in
conditions of a temperature of 25.degree. C., a strain of 5% and a
frequency of 1 Hz after curing, in a range of 10.sup.5 Pa to
10.sup.9 Pa.
19. The organic electronic device according to claim 1, comprising
at least one folding portion satisfying Equation 1 below:
X.ltoreq.10% [Equation 1] wherein, X is a luminance change rate
before and after a folding test in which a process of folding the
folding portion of said organic electronic device to a curvature
radius of 1 R (1 mm) at a temperature of 25.degree. C. and a
relative humidity of 50%, is repeated 100,000 times.
20. The organic electronic device according to claim 1, further
comprising an encapsulating layer covering the entire surface of
the organic electronic element.
21. A method for manufacturing the organic electronic device
according to claim 1, comprising steps of forming the adhesive
layer comprising a polymer derived from butylene and a curable
oligomer on a second surface of said substrate, forming an organic
electronic element on a first surface of said substrate, and curing
said adhesive layer.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a National Stage Application of International
Application No. PCT/KR2016/006126 filed on Jun. 9, 2016, which
claims the benefit of Korean Patent Application No. 10-2015-0081475
filed on Jun. 9, 2015, Korean Patent Application No.
10-2015-0117379 filed on Aug. 20, 2015 and Korean Patent
Application No. 10-2015-0177030 filed on Dec. 11, 2015, all of
which are hereby incorporated by reference in their entirety for
all purposes as if fully set forth herein.
TECHNICAL FIELD
The present invention relates to an organic electronic device, a
method for manufacturing the same, and a lighting apparatus and a
display device comprising the same.
BACKGROUND ART
An organic electronic device (OED) means a device comprising an
organic material layer that generates alternate current of charges
using holes and electrons. An example of the organic electronic
device may include a photovoltaic device, a rectifier, a
transmitter, and an organic light emitting diode (OLED), and the
like.
In one embodiment, the organic light emitting diode (OLED) has a
lower power consumption and a faster response speed than an
existing light source, and is advantageous for thinning display
devices or illuminations. The OLEDs are also expected to be applied
in various fields covering various portable devices, monitors,
notebooks, and televisions because of their excellent space
utilization.
Recently, in the display field, weight reduction, miniaturization
and flexibilization of products have been emphasized, but since the
glass substrates currently used have disadvantages that they are
heavy, fragile and difficult to be continuously processed,
researches for applying plastic substrates having advantages of
being light and flexible, and allowing the continuous process by
replacing the glass substrate to mobile phones, notebooks, and PDAs
and the like are actively underway.
DISCLOSURE
Technical Problem
The present application provides a flexible organic electronic
device that does not only realize excellent moisture barrier
characteristics, but also has excellent endurance reliability under
high temperature and high humidity conditions while having flexible
characteristics.
Technical Solution
Hereinafter, embodiments of the present invention will be described
in more detail with reference to the accompanying drawings. Also,
in describing the present invention, detailed descriptions of known
general purpose functions and configurations incorporated herein
are omitted. Also, the accompanying drawings are those that are
schematic for helping the understanding of the present invention,
where parts that are not related to the description have been
omitted for more clearly explaining the present invention. In the
drawings, the thickness or size has been shown in an enlarged scale
in order to clearly represent layers and regions. The scope of the
present invention is not limited by the thickness, size, ratio and
the like as shown in the drawings.
The present application relates to an organic electronic device.
The organic electronic device may have flexible characteristics. In
one example, the organic electronic device may comprise, as shown
in FIG. 1 or 2, a substrate (1) in which an organic electronic
element (2) is formed on one surface and an adhesive layer (3)
formed on the other surface of the substrate (1) and comprising a
polymer derived from butylene and a curable oligomer. Considering
that the adhesive layer according to the present invention is
applied to a flexible organic electronic device, physical
properties, in which the flexible organic electronic device can
effectively suppress cracks capable of occurring in the organic
electronic device despite several folding processes and can
maintain excellent luminance even after folding, while relaxing
stress caused by folding, are required for the adhesive
constituting the adhesive layer.
In addition, considering that the organic electronic device of the
present application has flexible characteristics, the substrate on
which the element is formed may be a flexible polymer base
material. Accordingly, in order to block moisture or oxygen
penetrating through the substrate, the adhesive layer may be
positioned on the opposite surface of one surface of the substrate
on which the element is formed. The organic electronic device
according to the present application can achieve endurance
reliability at high temperature and high humidity, prevention of
cracks in flexible organic electronic devices, and luminance
maintaining together with excellent moisture barrier
characteristics by forming the aforementioned adhesive layer on the
other surface of the substrate.
In this specification, the term "organic electronic device" means
an article or device having an element comprising an organic
material layer that generates alternate current of charges using
holes and electrons between a pair of electrodes opposing to each
other, and the example thereof may include, but is not limited to,
a photovoltaic device, a rectifier, a transmitter and an organic
light emitting diode (OLED), and the like. In one example of the
present invention, the organic electronic device may be an
OLED.
The term adhesive herein is a term encompassing not only a material
commonly referred to as an adhesive but also a layer formed by
using a material referred to as a so-called pressure-sensitive
adhesive or a material referred to as a so-called adhesive and
pressure-sensitive adhesive, and the like. The term adhesive layer
herein may be in a film or sheet shape, whereby the adhesive layer
may be used interchangeably with an adhesive film or an
adhesive.
In the present application, the term "polymer derived from
butylene" may mean that at least one of the polymerized units of
the polymer is composed of butylene. Since the polymer derived from
butylene has a very low polarity, is transparent, and has almost no
influence of corrosion, excellent moisture barrier characteristics
and endurance reliability can be realized when used as an
encapsulant or a sealing material.
In the present application, the polymer derived from butylene may
be also a homopolymer of a butylene monomer; a copolymer obtained
by copolymerizing another monomer polymerizable with a butylene
monomer; a reactive oligomer using a butylene monomer; or a mixture
thereof. In the present application, the derived polymer may mean
that the monomer forms a polymer in polymerized units. The butylene
monomer may include, for example, 1-butene, 2-butene or
isobutylene.
Another monomer polymerizable with the butylene monomer or a
derivative thereof may include, for example, an olefin-based
compound such as isoprene, styrene or butadiene. By using the
copolymer, physical properties such as processability and degree of
cross-linking can be maintained, whereby the heat resistance of the
adhesive itself can be ensured when applied to organic electronic
devices.
In addition, the reactive oligomer using the butylene monomer may
include a butylene polymer having a reactive functional group. The
butylene polymer may be associated with another polymer having a
reactive functional group. The other polymer may be, but is not
limited to, alkyl (meth)acrylate. The reactive functional group may
be a hydroxy group, a carboxyl group, an isocyanate group or a
nitrogen-containing group. In addition, the reactive oligomer and
the other polymer may be cross-linked by a multifunctional
cross-linking agent, and the multifunctional cross-linking agent
may be at least one selected from the group consisting of an
isocyanate cross-linking agent, an epoxy cross-linking agent, an
aziridine cross-linking agent and a metal chelate cross-linking
agent.
In one example, as the polymer, polyisobutylene, a copolymer of
isobutylene and isoprene, a copolymer of isoprene and styrene, a
copolymer of isobutylene and styrene, a copolymer of butadiene and
styrene, a copolymer of isoprene, butadiene and styrene,
polyisoprene, polybutadiene or a copolymer of isoprene and styrene,
a copolymer of butadiene and styrene, or a copolymer of isoprene,
butadiene and styrene can be exemplified.
In the present application, the polymer may have a weight average
molecular weight (MW) such an extent that the adhesive composition
can be formed into a film shape. For example, the polymer may have
a weight average molecular weight of about 10,000 to 2,000,000,
50,000 to 1,000,000, 80,000 to 500,000, or 100,000 to 300,000 or
so. In the present application, the term weight average molecular
weight means a value converted to standard polystyrene as measured
by GPC (Gel Permeation Chromatograph). However, the polymer does
not necessarily have the above-mentioned weight average molecular
weight, and for example, even when the molecular weight of the
polymer is not in such level to form a film, a separate binder
resin may be formulated into the adhesive composition.
As described above, the adhesive layer of the present application
may comprise a curable oligomer. The adhesive composition according
to the present application may optionally use the above-mentioned
curable oligomer instead of a tackifier to be described below. That
is, the adhesive layer according to the present application may
comprise no tackifier.
In one example, the curable oligomer may comprise at least one or
more curable functional groups. The curable functional group may be
one or more selected from, for example, a glycidyl group, an
isocyanate group, a hydroxy group, a carboxyl group, an amide
group, an epoxide group, a cyclic ether group, a sulfide group, an
acetal group and a lactone group.
In one example, the curable oligomer may have a weight average
molecular weight in a range of 400 to 10,000, 500 to 10,000, 800 to
10,000, 1,000 to 10,000, 2,000 to 9,000, or 3,000 to 8,000. Within
the above molecular weight range, the adhesive layer of the present
application may be cured to have excellent moisture barrier
characteristics and may be applied to flexible organic electronic
devices to realize excellent heat resistance and adhesion. Flexible
organic electronic devices can cause stress during the folding
process, whereby some portions can be peeled off, and be vulnerable
to high temperatures. However, the organic electronic device in
which the adhesive layer according to the present application is
formed can alleviate the stress, maintain excellent adhesive force
even under severe conditions, and achieve heat resistant durability
at high temperature and high humidity.
In one embodiment of the present application, the curable oligomer
may be a hydrogenated compound. The term hydrogenated compound
herein may mean a compound obtained by adding hydrogen to
unsaturated bonds in an organic compound, for example, a
carbon-carbon double bond or triple bond or a multiple bond such as
a carbonyl group. In an embodiment of the present application, the
hydrogenated compound may inhibit yellowing of the adhesive at high
temperatures.
In one example, the curable oligomer contains two or more
functional groups and may be an epoxy oligomer having an epoxy
equivalent of 100 g/eq to 1,500 g/eq, 150 g/eq to 1,400 g/eq, 200
g/eq to 1,200 g/eq, or 300 g/eq to 1,000 g/eq. The present
application can effectively maintain properties such as adhesion
performance and glass transition temperature of a cured product by
using an epoxy oligomer having an epoxy equivalent in the above
range.
In one example, the curable oligomer may have a cyclic structure
within the molecular structure. The cyclic structure may comprise,
for example, an aromatic group (e.g., a phenyl group). For example,
the curable oligomer of the present application may be a
hydrogenated aromatic epoxy compound. A specific example of the
aromatic group-containing curable oligomer that can be used in the
present application may be an oligomer type such as a biphenyl type
epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene
type epoxy resin, a dicyclopentadiene modified phenol type epoxy
resin, a cresol-based epoxy resin, a bisphenol-based epoxy resin, a
xylol-based epoxy resin, a multifunctional epoxy resin, a phenol
novolak epoxy resin, a triphenol methane type epoxy resin, and an
alkyl-modified triphenol methane epoxy resin, but is not limited
thereto.
In one example, the curable oligomer may be an oligomer shape such
as 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate
(EEC) and derivatives, dicyclopentadiene dioxide and derivatives,
3-ethyl-3-oxetane methanol and derivatives, diglycidyl
tetrahydrophthalate and derivatives, diglycidyl hexahydrophthalate
and derivatives, 1,2-ethanediglycidyl ether and derivatives,
1,3-propanediglycidyl ether and derivatives, 1,4-butanediol
diglycidyl ether and derivatives, higher 1,n-alkane diglycidyl
ether and derivatives, bis[(3,4-epoxycyclohexyl)methyl]adipate and
derivatives, vinylcyclohexyldioxide and derivatives,
1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate) and
derivatives, diglycidyl 4,5-epoxytetrahydrophthalate and
derivatives, bis[1-ethyl(3-oxetanyl)methyl]ether and derivatives,
pentaerythrityl tetraglycidyl ether and derivatives, bisphenol A
diglycidyl ether (DGEBA), hydrogenated bisphenol A diglycidyl
ether, bisphenol F diglycidyl ether, hydrogenated bisphenol F
diglycidyl ether, epoxy phenol novolak, hydrogenated epoxy phenol
novolak, epoxy cresol novolac, hydrogenated epoxy cresol novolak,
2-(7-oxabicyclospiro(1,3-dioxane-5,3'-(7-oxabicylco[4.1.0]heptane))
or 1,4-bis((2,3-epoxypropoxy)-methyl)cyclohexane. An example of the
curable oligomer may include, as a commercially available product,
ST-3000 and ST-5000 from Kukdo Chemical, and YX-8000 and YX-8034
from Mitsubishi.
The curable oligomer may be included in an amount of 15 to 100
parts by weight, 20 to 80 parts by weight, or 20 to 70 parts by
weight relative to 100 parts by weight of the polymer derived from
butylene. Within the above weight range, the present application
can achieve endurance reliability at high temperature and high
humidity, prevention of cracks in flexible organic electronic
devices, and luminance maintaining together with excellent moisture
barrier characteristics by applying the adhesive layer to the
organic electronic element.
In one example, the adhesive layer may further comprise a curable
monomer. The curable monomer can be distinguished from the curable
oligomer in that it is not in the oligomeric form. The curable
monomer may be a cationic initiating monomer. An exemplary curable
monomer may have a weight average molecular weight in a range of
less than 400, 50 to 390, or 100 to 350.
In one example, the curable monomer may comprise at least one or
more curable functional groups. The curable functional group may be
one or more selected from, for example, a glycidyl group, an
isocyanate group, a hydroxy group, a carboxyl group, an amide
group, an epoxide group, a cyclic ether group, a sulfide group, an
acetal group and a lactone group.
In one embodiment of the present application, as the curable
monomer containing two or more functional groups, an epoxy compound
having an epoxy equivalent of 10 g/eq to 200 g/eq, 50 g/eq to 180
g/eq, or 100 g/eq to 150 g/eq may be used. By using the epoxy
compound having an epoxy equivalent in the above range, properties
such as adhesion performance and glass transition temperature of
the cured product can be effectively maintained.
In one example, as the curable monomer, a compound having a cyclic
structure in which the ring constituent atoms in the molecular
structure are in the range of 3 to 10, 4 to 9, or 5 to 8 may be
used, but is not limited thereto. In one example, the curable
monomer may be an alicyclic epoxy compound having the cyclic
structure.
An example of the curable monomer is 3,4-epoxycyclohexylmethyl
3',4'-epoxycyclohexanecarboxylate (EEC) and derivatives,
dicyclopentadiene dioxide and derivatives, 3-ethyl-3-oxetane
methanol and derivatives, diglycidyl tetrahydrophthalate and
derivatives, diglycidyl hexahydrophthalate and derivatives,
1,2-ethanediglycidyl ether and derivatives, 1,3-propanediglycidyl
ether and derivatives, 1,4-butanediol diglycidyl ether and
derivatives, higher 1,n-alkane diglycidyl ether and derivatives,
bis[(3,4-epoxycyclohexyl)methyl]adipate and derivatives,
vinylcyclohexyldioxide and derivatives, 1,4-cyclohexanedimethanol
bis(3,4-epoxycyclohexanecarboxylate) and derivatives, diglycidyl
4,5-epoxytetrahydrophthalate and derivatives,
bis[1-ethyl(3-oxetanyl)methyl]ether and derivatives,
pentaerythrityl tetraglycidyl ether and derivatives, bisphenol A
diglycidyl ether (DGEBA), hydrogenated bisphenol A diglycidyl
ether, bisphenol F diglycidyl ether, hydrogenated bisphenol F
diglycidyl ether, epoxy phenol novolak, hydrogenated epoxy phenol
novolak, epoxy cresol novolac, hydrogenated epoxy cresol novolak,
2-(7-oxabicyclospiro(1,3-dioxane-5,3'-(7-oxabicylco[4.1.0]heptane))
or 1,4-bis((2,3-epoxypropoxy)-methyl)cyclohexane.
The curable monomer may be included in an amount of 20 to 80 parts
by weight, 30 to 70 parts by weight, or 35 to 60 parts by weight
relative to 100 parts by weight of the polymer derived from
butylene. Within the above weight range, excellent moisture barrier
characteristics and adhesiveness can be realized.
In one example, when the adhesive layer comprises the curable
monomer and the curable oligomer together, the curable monomer and
the curable oligomer may be included in the aforementioned adhesive
layer in ratios of 10 to 50 parts by weight and 20 to 70 parts by
weight, or 20 to 45 parts by weight and 25 to 60 parts by weight,
respectively. In another embodiment, the adhesive layer may
comprise the polymer derived from butylene, the curable monomer and
the curable oligomer in ratios of 40 to 100 parts by weight, 10 to
50 parts by weight and 20 to 70 parts by weight, respectively.
Within the above weight range, the present application can achieve
endurance reliability at high temperature and high humidity,
together with excellent moisture barrier characteristics by
applying the adhesive layer to the organic electronic device, and
excellent heat resistance holding ability, adhesion and prevention
of cracks and luminance maintaining by applying the adhesive layer
to the flexible organic electronic device.
In one example, if necessary, the adhesive layer may further
comprise a tackifier, which may be a hydrogenated cyclic
olefin-based polymer. As the tackifier, for example, a hydrogenated
petroleum resin obtained by hydrogenating a petroleum resin can be
used. The hydrogenated petroleum resin may be partially or fully
hydrogenated and may be a mixture of such resins. As such a
tackifier, one having excellent moisture barrier characteristics,
while having good compatibility with the adhesive composition, and
having low organic volatile components, can be selected. A specific
example of the hydrogenated petroleum resin may include a
hydrogenated terpene resin, a hydrogenated ester resin or a
hydrogenated dicyclopentadiene resin, and the like. The tackifier
may have a weight average molecular weight of about 200 to 5,000.
The content of the tackifier can be appropriately adjusted as
necessary. For example, the content of the tackifier may be
included in a weight ratio of 5 parts by weight to 100 parts by
weight or 20 to 40 parts by weight, relative to 100 parts by weight
of the solid content of the adhesive composition.
In an embodiment of the present application, the adhesive layer may
further comprise a curing agent or an initiator depending on the
kind of the polymer, the curable oligomer or the curable monomer.
For example, a curing agent capable of reacting with the polymer,
the curable oligomer or the curable monomer, as described above, to
form a cross-linked structure or the like, or a cationic initiator
or a radical initiator, capable of initiating the curing reaction
may be further included. As the cationic initiator, a cationic
photopolymerization initiator or a cationic thermal initiator may
be used.
As an exemplary curing agent, which is an epoxy curing agent known
in the art, for example, one or two or more of an amine curing
agent, an imidazole curing agent, a phenol curing agent, a
phosphorus curing agent, an acid anhydride curing agent, and the
like can be used, without being limited thereto.
In one example, as the curing agent, an imidazole compound which is
solid at room temperature and has a melting point or a
decomposition temperature of 80.degree. C. or higher can be used.
Such a compound can be exemplified by, for example,
2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole,
2-phenyl-4-methylimidazole or 1-cyanoethyl-2-phenylimidazole, and
the like, but is not limited thereto.
The content of the curing agent may be selected depending on
composition of the composition, for example, the type and ratio of
the polymer, the curable oligomer or the curable monomer. For
example, the curing agent may be included in an amount of 0.01 to
20 parts by weight, 0.1 to 10 parts by weight or 1 to 5 parts by
weight, relative to 100 parts by weight of the solid content of the
adhesive composition. However, the weight ratio may be changed
depending on the type and ratio of the functional group of the
curable oligomer or the curable monomer or the compound, the
cross-linking density to be achieved, and the like.
In one example, as the cationic photopolymerization initiator, an
ionized cationic initiator of onium salt or organometallic salt
series or a non-ionized cationic photopolymerization initiator of
organic silane or latent sulfonic acid series may be used. As the
initiator of onium salt series, diaryliodonium salt,
triarylsulfonium salt or aryldiazonium salt, and the like can be
exemplified, as the initiator of organometallic salt series, iron
arene and the like can be exemplified, as the initiator of
organosilane series, o-nitrobenzyl triaryl silyl ether, triaryl
silyl peroxide or acyl silane, and the like can be exemplified, and
as the initiator of latent sulfuric acid series,
.alpha.-sulfonyloxy ketone or .alpha.-hydroxymethylbenzoin
sulfonate, and the like can be exemplified, without being limited
thereto.
In one example, the initiator may be included in an amount of 0.01
parts by weight to 20 parts by weight, 0.1 parts by weight to 10
parts by weight or 1 part by weight to 5 parts by weight, relative
to 100 parts by weight of the solid content of the adhesive
composition.
The adhesive layer of the present application may further comprise
a high molecular weight resin. The high molecular weight resin can
play a role of improving moldability, when the adhesive layer of
the present application is molded into a film or sheet shape. In
addition, it can serve as a high-temperature viscosity controlling
agent for controlling flowability.
The type of the high molecular weight resin that can be used in the
present application is not particularly limited as long as it is
compatible with other components such as the polymer. A specific
example of the high molecular weight resin that can be used may
include, as a resin having a weight average molecular weight of
20,000 or more, one or a mixture of two or more of a phenoxy resin,
an acrylate resin, a high molecular weight epoxy resin, a ultrahigh
molecular weight epoxy resin, a high polar functional
group-containing rubber and a high polar functional
group-containing reactive rubber, and the like, but is not limited
thereto.
When the high molecular weight resin is included in the adhesive
layer of the present application, the content thereof is not
particularly limited as it is controlled depending on the intended
physical properties. For example, in the present application, the
high molecular weight resin may be included in an amount of up to
about 200 parts by weight, preferably up to 150 parts by weight,
more preferably up to about 100 parts by weight, relative to 100
parts by weight of the polymer derived from butylene, and the lower
limit is not particularly limited, but may be 30 parts by weight or
more, or 50 parts by weight or more. In the present application, by
controlling the content of the high molecular weight resin to 200
parts by weight or less, compatibility with each component of the
resin composition can be effectively maintained.
The adhesive layer of the present application may comprise a
moisture adsorbent, if necessary. The term "moisture adsorbent" can
be used generically to refer to components capable of adsorbing or
removing moisture or humidity introduced from the outside through
physical or chemical reactions or the like. That is, it means a
moisture-reactive adsorbent or a physical adsorbent, and a mixture
thereof can be also used.
The moisture-reactive adsorbent chemically reacts with humidity,
moisture or oxygen, and the like introduced into the adhesive to
adsorb moisture or humidity. The physical adsorbent can lengthen a
moving route of moisture or humidity penetrating into the
encapsulation structure to suppress the permeation, and can
maximize the barrier characteristics against moisture and humidity
through interaction with the matrix structure of the adhesive resin
and the moisture-reactive adsorbent.
The specific kind of the moisture adsorbent which can be used in
the present application is not particularly limited, and for
example, the moisture-reactive adsorbent may include one or a
mixture of two or more of a metal powder such as alumina, a metal
oxide, a metal salt or phosphorus pentoxide (P.sub.2O.sub.5), and
the like, and the physical adsorbent may include silica, zeolite,
titania, zirconia or montmorillonite, and the like.
Here, a specific example of the metal oxide may include alumina,
lithium oxide (Li.sub.2O), sodium oxide (Na.sub.2O), barium oxide
(BaO), calcium oxide (CaO) or magnesium oxide (MgO), and the like,
and an example of the metal salt may include a sulfate salt such as
lithium sulfate (Li.sub.2SO.sub.4), sodium sulfate
(Na.sub.2SO.sub.4), calcium sulfate (CaSO.sub.4), magnesium sulfate
(MgSO.sub.4), cobalt sulfate (CoSO.sub.4), gallium sulfate
(Ga.sub.2(SO.sub.4).sub.3), titanium sulfate (Ti(SO.sub.4).sub.2)
or nickel sulfate (NiSO.sub.4), a metal halide such as calcium
chloride (CaCl.sub.2), magnesium chloride (MgCl.sub.2), strontium
chloride (SrCl.sub.2), yttrium chloride (YCl.sub.3), copper
chloride (CuCl.sub.2), cesium fluoride (CsF), tantalum fluoride
(TaF.sub.5), niobium fluoride (NbF.sub.5), lithium bromide (LiBr),
calcium bromide (CaBr.sub.2), cesium bromide (CeBr.sub.3), selenium
bromide (SeBr.sub.4), vanadium bromide (VBr.sub.3), magnesium
bromide (MgBr.sub.2), barium iodide (BaI.sub.2) or magnesium iodide
(MgI.sub.2); or a metal chlorate such as barium perchlorate
(Ba(ClO.sub.4).sub.2) or magnesium perchlorate
(Mg(ClO.sub.4).sub.2), and the like, without being limited
thereto.
In the present application, the moisture adsorbent such as the
metal oxide can be formulated into the composition in a properly
processed state. For example, an adhesive made of the
above-mentioned adhesive composition in the form of a film can be
formed into a thin film having a thickness of 30 .mu.m or less
depending on the kind of the organic electronic device to be
applied, where a process of pulverizing the moisture adsorbent may
be required. For pulverizing the moisture adsorbent, a process such
as three roll mill, bead mill or ball mill may be used.
The adhesive layer of the present application may comprise the
moisture adsorbent in an amount of 0 parts by weight to 100 parts
by weight, 1 to 90 parts by weight, 5 parts by weight to 80 parts
by weight, or 10 to 60 parts by weight, relative to 100 parts by
weight of the polymer derived from butylene. The moisture adsorbent
may not be included as an optional component, but preferably by
controlling the content of the moisture adsorbent to 5 parts by
weight or more, the cured product may exhibit excellent moisture
and humidity barrier characteristics. In addition, by controlling
the content of the moisture adsorbent to 100 parts by weight or
less, it may exhibit excellent moisture barrier characteristics,
while forming a thin film encapsulation structure.
In this specification, unless otherwise specified, the unit "part
by weight" means a weight ratio between the respective
components.
The adhesive layer of the present application may optionally
comprise a filler, preferably an inorganic filler. The filler can
lengthen the moving route of moisture or humidity penetrating into
the encapsulation structure to suppress the penetration, and can
maximize the barrier characteristics against moisture and humidity
through the interaction with the matrix structure of the resin
component and the moisture adsorbent. The specific kind of the
filler that can be used in the present application is not
particularly limited, and for example, one or a mixture of two or
more of clay, or talc, and the like may be used.
In the present application, in order to increase the bonding
efficiency between the filler and the organic binder, a product
surface-treated with an organic material may be used as the filler,
or an additional coupling agent may be added thereto and used.
The adhesive layer of the present application may comprise 0 to 50
parts by weight, 1 to 40 parts by weight, or 1 to 20 parts by
weight of the filler, relative to 100 parts by weight of the
polymer derived from butylene. In the present application, the
filler may not be included in the adhesive as an optional
component, but preferably by controlling it to 1 part by weight or
more, an encapsulation structure having excellent moisture or
humidity barrier characteristics and mechanical properties may be
provided. In addition, by controlling the filler content to 50
parts by weight or less in the present application, it is possible
to provide a cured product which can be produced in the form of a
film and exhibits excellent moisture barrier characteristics even
when formed into a thin film.
Furthermore, in one example, the adhesive layer may further
comprise a dispersing agent so that a moisture adsorbent or the
like can be uniformly dispersed. As the dispersing agent that can
be used here, for example, a nonionic surfactant having affinity
with the surface of the moisture adsorbent and good compatibility
with the adhesive resin, and the like can be used.
The adhesive layer according to the present application may
comprise, in addition to the above-described configurations,
various additives in accordance with applications, the type of the
resin component and the manufacturing process of the adhesive layer
described below, within the range that the above-described effect
of invention is not affected. For example, the adhesive layer may
comprise a coupling agent, a cross-linking agent, a curable
material, an ultraviolet stabilizer or an antioxidant, and the like
in an appropriate range of content depending on the desired
physical properties.
In one example, the adhesive layer may have, in a graph (X-axis:
temperature, Y-axis: storage elastic modulus) of storage elastic
moduli depending on temperatures, where the X-axis is a temperature
and the Y-axis is a storage elastic modulus, an absolute value of
the slope of the storage elastic modulus with respect to the
temperature before curing, greater than an absolute value of the
slope of the storage elastic modulus with respect to the
temperature after curing. Here, the storage elastic modulus may be
measured at a temperature range of 25.degree. C. to 65.degree. C.
under conditions of a strain of 5% and a frequency of 1 Hz.
Otherwise, a ratio (A/B) of the absolute value (A) of the slope of
the storage elastic modulus with respect to the temperature after
curing to the absolute value (B) of the storage elastic modulus
with respect to the temperature before curing may be in a range of
0.001 to 0.9 or 0.001 to 0.8. Generally, as the temperature
increases, the polymer has a lower storage elastic modulus, where
the adhesive layer of the present application can realize excellent
step filling property in a vacuum heat cohesion condition applied
to a substrate by maintaining the large absolute value of the slope
before curing to have a low storage elastic modulus at a high
temperature. In addition, the present application also maintains a
high storage elastic modulus at a high temperature by keeping the
slope small after curing, and thus can realize heat resistant
durability at high temperature and high humidity by being applied
to a flexible organic electronic device.
In one example, the adhesive layer may have a viscosity measured
depending on shear stress in conditions of a temperature at any one
point of 50.degree. C. to 70.degree. C., a strain of 5% and a
frequency of 1 Hz before curing in a range of 100 Pas to 10.sup.4
Pas, or 500 Pas to 8,000 Pas. In the application of the organic
electronic device, the adhesive satisfying the above viscosity
range can realize excellent step filling property in the vacuum
heat cohesion condition.
In one example, the adhesive layer may be a multi-layer structure.
For example, the adhesive layer may have a structure of two or more
layers, and the composition of the two adhesive layers may be the
same or different.
In an embodiment of the present application, the adhesive layer may
have a storage elastic modulus, as measured in conditions of a
temperature of 25.degree. C., a strain of 5% and a frequency of 1
Hz after curing, in a range of 10.sup.5 to 10.sup.9 Pa, 0.5 MPa to
800 MPa or 0.8 MPa to 500 MPa. By controlling the physical
properties of the adhesive layer within the above elastic modulus
range, the present application can effectively suppress the stress
in each layer constituting the flexible organic electronic device,
and suppress the luminance change rate according to Equation 1
described below to provide a reliable organic electronic
device.
In one example, the organic electronic device of the present
application may further comprise an encapsulating layer (4)
covering the entire surface of the organic electronic element (2),
as shown in FIG. 1 or 2. The encapsulation layer may be an
adhesive, a pressure-sensitive adhesive, or an adhesive and
pressure-sensitive adhesive, and the composition may be the same as
or different from the above-mentioned adhesive layer. For example,
the encapsulating layer may comprise one or more of the polymer
derived from butylene, the curable oligomer and the curable
monomer, as described above.
In an embodiment of the present application, the organic electronic
device may further comprise a cover substrate (5) formed on the
encapsulation layer (4). The surface of the substrate, where the
organic electronic element is present, and the cover substrate may
be adhered by the encapsulation layer.
The specific kind of the substrate or the cover substrate is not
particularly limited. As the substrate or the cover substrate in
the present application, for example, a general polymer film in
this field can be used. In the present application, for example, as
the substrate or the cover substrate, a polyethylene terephthalate
film, a polytetrafluoroethylene film, a polyethylene film, a
polypropylene film, a polybutene film, a polybutadiene film, a
vinyl chloride copolymer film, a polyurethane film, an
ethylene-vinyl acetate film, an ethylene-propylene copolymer film,
an ethylene-ethyl acrylate copolymer film, an ethylene-methyl
acrylate copolymer film or a polyimide film, and the like can be
used.
In the present application, the thickness of the substrate or the
cover substrate as above is not particularly limited and can be
appropriately selected depending on the applied applications. For
example, in the present application, the substrate or the cover
substrate may have a thickness of 10 .mu.m to 500 .mu.m, preferably
20 .mu.m to 200 .mu.m or so. If the thickness is less than 10
.mu.m, the substrate may be easily deformed during the
manufacturing process, whereas if the thickness exceeds 500 .mu.m,
the economical efficiency is lowered.
The thickness of the adhesive layer of the present application is
not particularly limited and can be appropriately selected in
accordance with the following conditions in consideration of the
application to which the adhesive layer is applied. The adhesive
layer included in the adhesive film of the present application may
have 5 .mu.m to 200 .mu.m, preferably 10 .mu.m to 150 .mu.m or
so.
Furthermore, in one example, the organic electronic device may
comprise one or more folding portions. For example, FIG. 2
illustrates the organic electronic device having one folding
portion, in which the folding portion is folded with a curvature
radius of 1 R. Also, the folding portion may satisfy Equation 1
below. X.ltoreq.10% [Equation 1]
In Equation 1, X is a luminance change rate before and after a
folding test in which a process of folding the folding portion of
the organic electronic device to a curvature radius of 1 R (1 mm)
at a temperature at any one point of 15.degree. C. to 35.degree.
C., for example, a temperature of 25.degree. C. and the humidity at
any one point of 30% to 80%, for example, a relative humidity of
50%, is repeated 100,000 times. The folding test is not limited to
the above, and can be carried out by folding it 10,000 to 200,000
times with any one radius of 0.1 R to 3 R. Here, the change rate of
luminance can be measured by measuring luminance A of the folding
portion before the folding test and luminance B after the folding
test, using the DISPLAY COLOR ANALYZER (CA-210, KONICA MINOLTA)
equipment as a luminance meter, and calculating the change rate
|(A-B)/A|.times.100. In Equation 1 above, X may be 8% or less or 5%
or less, and the lower limit is not particularly limited, but may
be 0%. The organic electronic device according to the present
application has flexible characteristics and can effectively
suppress cracks that may occur in the organic electronic device,
despite the folding process of 100,000 times or more as described
above, and can maintain excellent luminance.
The term "folding portion" herein may mean any one portion of an
organic electronic device that can be folded such that the organic
electronic device has a curvature radius of 0.1 R to 3 R. The
folding portion can be seen as a straight line when the organic
electronic device is viewed in a plan view, but is not limited
thereto. The unit R can be used in the same manner as mm, which is
a length unit, and 1 R can mean that the curvature radius is 1 mm,
when the folding portion has been folded. Furthermore, the folding
process may mean a process of folding the folding portion. As
described above, the organic electronic device of the present
application may have one folding portion, but is not limited
thereto, and for example, two or more folding portions. Also, the
flexible organic electronic device of the present application can
be folded without limitation to any region, by having folding
portions on all the entire surface of the device.
In one example, if the physical properties of the adhesive film
measured herein are physical properties varying by the temperature,
they may be physical properties measured at room temperature,
unless otherwise specified. The room temperature herein may mean a
natural temperature that the temperature is not increased nor
reduced, and for example, the temperature at any one point of about
15.degree. C. to 35.degree. C., the temperature at any one point of
20.degree. C. to 25.degree. C. or about 25.degree. C.
In one example, the adhesive layer of the present application may
have a peel force (peeling speed: 0.3 m/min, peeling angle:
180.degree.) to the substrate of 1000 gf/in or more. Since the
organic electronic device of the present application has folding
portions, interface peeling may occur between the respective layers
constituting the organic electronic device due to several folding,
but by controlling the peeling force of the adhesive layer as
above, defects due to the interface peeling can be suppressed.
Furthermore, in one example, the adhesive layer may have a
coefficient of thermal expansion of less than 80 .mu.m/m.degree. C.
The coefficient of thermal expansion can be measured in conditions
of a temperature at any one point of 30.degree. C. to 100.degree.
C., 0.1 N and 10.degree. C./min. By controlling the coefficient of
thermal expansion within the above range, the present application
can prevent interface peeling or cracks caused by folding the
flexible organic electronic device, and consequently, control the
luminance change rate.
Also, in one example, the adhesive may have a moisture permeability
of 50 g/m.sup.2day or less, 30 g/m.sup.2day or less, 20
g/m.sup.2day or less, or less than 15 g/m.sup.2day. In the present
application, the moisture permeability is a moisture permeability
measured in the thickness direction of a cross-linked product or a
cured product under 100.degree. F. and a relative humidity of 100%,
where the cross-linked product or the cured product is obtained
after cross-linking or curing an adhesive described below and
making the cross-linked product or cured product into a film shape
having a thickness of 100 .mu.m. In addition, the moisture
permeability is measured according to ASTM F1249. In the present
application, as the adhesive has the lower value of moisture
permeability, the encapsulation structure exhibit more excellent
performance, where the lower limit is not particularly limited, and
for example may be 0 g/m.sup.2day, 1 g/m.sup.2day or 3
g/m.sup.2day. Also, in one example, the adhesive may have a
moisture content of 0.05% or less, relative to the adhesive mass,
as measured according to Kal-Fischer titration. The moisture
content may be a moisture content (the measurement conditions are a
nitrogen gas temperature of 240.degree. C. and a flow rate of 250
ml/min, and the measurement time is measured until the moisture
measurement amount reaches 0.17 .mu.g/s) for about 1 g of the
adhesive sample by using VA-236S equipment from Mitsubishi after
performing nitrogen purging for about 1 hour in the equipment and
the container storage chamber, but is not limited thereto. By
controlling the moisture permeability to the above range or
controlling the moisture content to the above range, permeation of
moisture, humidity or oxygen, and the like into the organic
electronic device can be effectively suppressed.
Furthermore, in one example, the adhesive may have a dielectric
constant of 4 F/m or less, or 3 F/m or less. The dielectric
constant can be measured by a method known in the art, and for
example, can be measured at 1 MHz by preparing an adhesive sample
in a thickness of 100 .mu.m, laminating the sample with a size of 2
cm.times.2 cm between copper foils, and then using an Agilent 4294A
Precision Impedance Analyzer, but is not limited thereto. It is
preferred that the dielectric constant does not exceed 4 F/m with
respect to the response speed of the touch sensor, considering that
the organic electronic device described above is applied to a
display device or the like.
Also, in one example, the adhesive layer may have excellent light
transmittance with respect to the visible light region. For
example, the light transmittance may be measured at 550 nm using a
UV-Vis spectrometer. In one example, the adhesive layer of the
present application may exhibit a light transmittance of 90% or
more with respect to the visible light region. Furthermore, the
adhesive layer of the present application can exhibit low haze with
excellent light transmittance. In one example, the adhesive layer
may exhibit a haze of 3% or less, 2% or less, 1% or less, 0.8% or
less, 0.5% or less, or 0.3% or less. The adhesive layer of the
present application can realize excellent optical characteristics
by being applied to an organic electronic device. The light
transmittance or haze in the present application may be measured in
accordance with JIS K7105 standard test method.
In one example, the organic electronic device of the present
application can satisfy Equation 2 below. Y.ltoreq.10% [Equation
2]
In Equation 2, Y is a light transmittance change rate before and
after a folding test in which a process of folding the folding
portion of the organic electronic device to a curvature radius of 1
R (1 mm) at a temperature at any one point of 15.degree. C. to
35.degree. C., for example, a temperature of 25.degree. C. and the
humidity at any one point of 30% to 80%, for example, a relative
humidity of 50%, is repeated 100,000 times. The folding test is not
limited to the above, and can be carried out by folding it 10,000
to 200,000 times with any one radius of 0.1 R to 3 R. The light
transmittance can be measured at a wavelength of 550 nm using a
UV-Vis spectrometer.
Furthermore, in one example, the organic electronic device of the
present application can satisfy Equation 3 below. Z.ltoreq.10%
[Equation 3]
In Equation 3, Z is a haze change rate before and after a folding
test in which a process of folding the folding portion of the
organic electronic device to a curvature radius of 1 R (1 mm) at a
temperature at any one point of 15.degree. C. to 35.degree. C., for
example, a temperature of 25.degree. C. and the humidity at any one
point of 30% to 80%, for example, a relative humidity of 50%, is
repeated 100,000 times. The folding test is not limited to the
above, and can be carried out by folding it 10,000 to 200,000 times
with any one radius of 0.1 R to 3 R. The haze can be measured
according to the JIS K7105 standard test method. In Equation 3
above, Z may be 8% or less or 5% or less.
As described above, when the adhesive composition is cured to form
an adhesive layer and the adhesive layer is applied to the flexible
organic electronic device, the components constituting the adhesive
composition and the contents of the respective components can be
controlled in order to realize the above-described physical
properties.
The organic electronic device according to the present application
may comprise an organic electronic element, as described above.
The organic electronic element present on the top of the substrate
region may comprise a first electrode layer and a second electrode
layer, and may also comprise an organic layer present between the
first and second electrode layers. The first and second electrode
layers may be a hole-injection or electron-injection electrode
layer commonly used in organic electronic devices. Any one of the
first and second electrode layers may be formed of a hole-injection
electrode layer and the other may be formed of an
electron-injection electrode layer. Any one of the first and second
electrode layers may be formed of a transparent electrode layer and
the other may be formed of a reflective electrode layer. The
hole-injection electrode layer may be formed using, for example, a
material having a relatively high work function, and if necessary,
may be formed using a transparent or reflective material. For
example, the hole-injection electrode layer may comprise a metal,
an alloy, an electrically conductive compound or a mixture of two
or more thereof, having a work function of about 4.0 eV or more. As
such a material, a metal such as gold, CuI, an oxide material such
as ITO (indium tin oxide), IZO (indium zinc oxide), ZTO (zinc tin
oxide), zinc oxide doped with aluminum or indium, magnesium indium
oxide, nickel tungsten oxide, ZnO, SnO.sub.2 or In.sub.2O.sub.3, a
metal nitride such as gallium nitride, a metal selenide such as
zinc selenide or a metal sulfide such as zinc sulfide, and the like
can be exemplified. The transparent hole-injection electrode layer
can also be formed by using a laminate of a metal thin film such as
Au, Ag or Cu and a high refractive index transparent material such
as ZnS, TiO.sub.2 or ITO.
The hole-injection electrode layer may be formed by any means such
as vapor deposition, sputtering, chemical vapor deposition or
electrochemical means. In addition, if necessary, the formed
electrode layer may be patterned through a process using known
photolithography, shadow mask, or the like.
The electron-injection electrode layer can be formed using, for
example, a material having a relatively low work function, and for
example, can be formed using a suitable transparent or reflective
material of materials used for forming the hole-injection electrode
layer, without being limited thereto. The electron-injection
electrode layer can also be formed using, for example, a vapor
deposition method or a sputtering method, and the like, and if
necessary, can be suitably patterned.
The electrode layer may be formed to have a thickness of, for
example, about 90 nm to 200 nm, 90 nm to 180 nm, or about 90 nm to
150 nm or so.
An organic layer exists between the first and second electrode
layers. The organic layer may comprise at least two light emitting
units. In such a structure, light emitted from the light emitting
unit can be emitted toward the transparent electrode layer through
a process of being reflected by the reflective electrode layer.
The material constituting the light emitting unit is not
particularly limited. Fluorescent or phosphorescent organic
materials having various luminescent center wavelengths are known
in the art, and the light emitting unit can be formed by selecting
a suitable type of such known materials. As the material of the
light emitting unit, a material of Alq series such as
tris(4-methyl-8-quinolinolate)aluminum (III) (Alg3), 4-MAlq3 or
Gaq3, a cyclopentadiene derivative such as C-545T
(C.sub.26H.sub.26N.sub.2O.sub.2S), DSA-amine, TBSA, BTP, PAP-NPA,
Spiro-FPA, Ph.sub.3Si (PhTDAOXD) or PPCP
(1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene), DPVBi
(4,4'-bis(2,2'-diphenylyinyl)-1,1'-biphenyl), distyrylbenzene or a
derivative thereof, or
DCJTB-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-e-
nyl)-4H-pyran), DDP, AAAP, NPAMLI; or a phosphorescent material
such as Firpic, m-Firpic, N-Firpic, bon.sub.2Ir(acac),
(C.sub.6).sub.2Ir(acac), bt.sub.2Ir(acac), dp.sub.2Ir(acac),
bzq.sub.2Ir(acac), bo.sub.2Ir(acac), F.sub.2Ir(bpy),
F.sub.2Ir(acac), op.sub.2Ir(acac), ppy.sub.2Ir(acac),
tpy.sub.2Ir(acac),
FIrppy(fac-tris[2-(4,5'-difluorophenyl)pyridine-C'2,N]
iridium(III)) or
Btp.sub.2Ir(acac)(bis(2-(2'-benzo[4,5-a]thienyl)pyridinato-N,C3')
iridium(acetylactonate)), and the like can be exemplified, but is
not limited thereto. The light emitting unit may also have a
host-dopant system which includes the above material as a host and
also includes perylene, distyrylbiphenyl, DPT, quinacridone,
rubrene, BTX, ABTX or DCJTB and the like as a dopant.
The light emitting unit may also be formed by appropriately
employing a kind that exhibits light emission characteristics among
the electron-accepting organic compounds or electron-donating
organic compounds as described below.
As long as the organic layer comprises the light emitting unit, it
may be formed with various structures further comprising a variety
of other functional layers known in the art. As the layer that can
be included in the organic layer, an electron injecting layer, a
hole blocking layer, an electron transporting layer, a hole
transporting layer and a hole injecting layer, and the like can be
exemplified.
The electron injecting layer or the electron transporting layer can
be formed using, for example, an electron accepting organic
compound. Here, as the electron-accepting organic compound, any
known compound can be used without any particular limitation. As
such an organic compound, a polycyclic compound or a derivative
thereof such as p-terphenyl or quaterphenyl, a polycyclic
hydrocarbon compound or a derivative thereof such as naphthalene,
tetracene, pyrene, coronene, chrysene, anthracene,
diphenylanthracene, naphthacene or phenanthrene, a heterocyclic
compound or a derivative thereof such as phenanthroline,
bathophenanthroline, phenanthridine, acridine, quinoline,
quinoxaline or phenazine, and the like can be exemplified.
Fluoroceine, perylene, phthaloperylene, naphthaloperylene,
perynone, phthaloperynone, naphthaloperynone, diphenylbutadiene,
tetraphenylbutadiene, oxadiazole, aldazine, bisbenzoxazoline,
bisstyryl, pyrazine, cyclopentadiene, oxine, aminoquinoline, imine,
diphenylethylene, vinyl anthracene, diaminocarbazole, pyrane,
thiopyrane, polymethine, merocyanine, quinacridone or rubrene, and
the like or derivatives thereof, metal chelate complex compounds
disclosed in Japanese Laid-Open Patent Publication No. 1988-295695,
Japanese Laid-Open Patent Publication No. 1996-22557, Japanese
Laid-Open Patent Publication No. 1996-81472, Japanese Laid-Open
Patent Publication No. 1993-009470 or Japanese Laid-Open Patent
Publication No. 1993-017764, and the like, for example, metal
complexes having at least one 8-quinolinolato or derivative thereof
as a ligand, such as tris(8-quinolinolato)aluminum,
bis(8-quinolinolato)aluminum, bis[benzo(f)-8-quinolinolato]zinc,
bis(2-methyl-8-quinolinolato)aluminum, tris(8-quinolinolato)indium,
tris (5-methyl-8-quinolinolato)aluminum, 8-quinolinolatolithium,
tris(5-chloro-8-quinolinolato)gallium or
bis(5-chloro-8-quinolinolato)calcium, which is a metal chelated
oxanoid compound, oxadiazole compounds disclosed in Japanese
Laid-Open Patent Publication No. 1993-202011, Japanese Laid-Open
Patent Publication No. 1995-179394, Japanese Laid-Open Patent
Publication No. 1995-278124 or Japanese Laid-Open Patent
Publication No. 1995-228579, and the like, triazine compounds
disclosed in Japanese Laid-Open Patent Publication No. 1995-15473,
and the like, stilbene derivatives or distyrylarylene derivatives,
disclosed in Japanese Laid-Open Patent Publication No. 1994-203963,
and the like, styryl derivatives disclosed in Japanese Laid-Open
Patent Publication No. 1994-132080 or Japanese Laid-Open Patent
Publication No. 1994-88072, and the like, diolefin derivatives
disclosed in Japanese Laid-Open Patent Publication No. 1994-100857
or Japanese Laid-Open Patent Publication No. 1994-207170, and the
like; fluorescent brightening agents such as benzooxazole
compounds, benzothiazole compounds or benzoimidazole compounds;
distyrylbenzene compounds such as 1,4-bis(2-methylstyryl)benzene,
1,4-bis(3-methylstyryl)benzene, 1,4-bis(4-methylstyryl)benzene,
distyrylbenzene, 1,4-bis(2-ethylstyryl)benzene,
1,4-bis(3-ethylstyryl)benzene,
1,4-bis(2-methylstyryl)-2-methylbenzene or
1,4-bis(2-methylstyryl)-2-ethylbenzene; distyrylpyrazine compounds
such as 2,5-bis(4-methylstyryl)pyrazine,
2,5-bis(4-ethylstyryl)pyrazine,
2,5-bis[2-(1-naphthyl)vinyl]pyrazine,
2,5-bis(4-methoxystyryl)pyrazine,
2,5-bis[2-(4-biphenyl)vinyl]pyrazine or
2,5-bis[2-(1-pyrenyl)vinyl]pyrazine, dimethylidine compounds or
derivatives thereof such as 1,4-phenylenedimethylidine,
4,4'-phenylenedimethylidine, 2,5-xylenedimethylidine,
2,6-naphthylenedimethylidine, 1,4-biphenylenedimethylidine,
1,4-para-terephenylenedimethylidine,
9,10-anthracenediyldimethylidine,
4,4'-(2,2-di-t-butylphenylvinyl)biphenyl or
4,4'-(2,2-diphenylvinyl)biphenyl, silanamine derivatives disclosed
in Japanese Laid-Open Patent Publication No. 1994-49079 or Japanese
Laid-Open Patent Publication No. 1994-293778, and the like,
multifunctional styryl compounds disclosed in Japanese Laid-Open
Patent Publication No. 1994-279322 or Japanese Laid-Open Patent
Publication No. 1994-279323, and the like, oxadiazole derivatives
disclosed in Japanese Laid-Open Patent Publication No. 1994-107648
or Japanese Laid-Open Patent Publication No. 1994-092947, and the
like, anthracene compounds disclosed in Japanese Laid-Open Patent
Publication No. 1994-206865, and the like, oxynate derivatives
disclosed in Japanese Laid-Open Patent Publication No. 1994-145146,
and the like, tetraphenylbutadiene compounds disclosed in Japanese
Laid-Open Patent Publication No. 1992-96990, organic trifunctional
compounds disclosed in Japanese Laid-Open Patent Publication No.
1991-296595, and the like, coumarin derivatives disclosed in
Japanese Laid-Open Patent Publication No. 1990-191694, and the
like, perylene derivatives disclosed in Japanese Laid-Open Patent
Publication No. 1990-196885, and the like, naphthalene derivatives
disclosed in Japanese Laid-Open Patent Publication No. 1990-255789,
and the like, phthaloperynone derivatives disclosed in Japanese
Laid-Open Patent Publication No. 1990-289676 or Japanese Laid-Open
Patent Publication No. 1990-88689, and the like, or styrylamine
derivatives disclosed in Japanese Laid-Open Patent Publication No.
1990-25029, and the like can be also used as an electron-accepting
organic compound included in the low refractive layer. In addition,
the electron injecting layer can be also formed using a material
such as LiF or CsF.
The hole blocking layer is a layer capable of improving the
lifetime and efficiency of the element by preventing the injected
holes from entering into the electron-injection electrode layer via
the light emitting unit, and if necessary, can be formed in an
appropriate portion between the light emitting unit and the
electron-injection electrode layer by using a known material.
The hole injecting layer or the hole transporting layer may
comprise, for example, an electron donating organic compound. As
the electron donating organic compound, arylamine compounds such as
N,N',N'-tetraphenyl-4,4'-diaminophenyl,
N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diaminobiphenyl,
2,2-bis(4-di-p-tolylaminophenyl)propane,
N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl,
bis(4-di-p-tolylaminophenyl)phenylmethane,
N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl,
N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether,
4,4'-bis(diphenylamino)quadriphenyl,
4-N,N-diphenylamino-(2-diphenylvinyl)benzene,
3-methoxy-4'-N,N-diphenylaminostylbenzene, N-phenylcarbazole,
1,1-bis(4-di-p-triaminophenyl)cyclohexane,
1,1-bis(4-di-p-triaminophenyl)-4-phenylcyclohexane,
bis(4-dimethylamino-2-methylphenyl)phenylmethane,
N,N,N-tri(p-tolyl)amine,
4-(di-p-tolylamono)-4'-[4-(di-p-tolylamino)styryl]stilbene,
N,N,N',N'-tetraphenyl-4,4'-diaminobiphenyl-N-phenylcarbozole,
4,4'-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl,
4,4''-bis[N-(1-naphthyl)-N-phenylamino]-p-terphenyl,
4,4'-bis[N-(2-naphthyl)-N-phenylamino]biphenyl,
4,4'-bis[N-(3-acenaphthenyl)-N-phenylamino]biphenyl,
1,5-bis[N-(1-naphthyl)-N-phenylamino]naphthalene,
4,4'-bis[N-(9-anthryl)-N-phenylamino]biphenylphenylamino]biphenyl,
4,4''-bis[N-(1-anthryl)-N-phenylamino]-p-terphenyl,
4,4'-bis[N-(2-phenanthryl)-N-phenylamino]biphenyl,
4,4'-bis[N-(8-fluoranthenyl)-N-phenylamino]biphenyl,
4,4'-bis[N-(2-pyrenyl)-N-phenylamino]biphenyl,
4,4'-bis[N-(2-perylenyl)-N-phenylamino]biphenyl,
4,4'-bis[N-(1-coronenyl)-N-phenylamino]biphenyl,
2,6-bis(di-p-tolylamino)naphthalene,
2,6-bis[di-(1-naphthyl)amino]naphthalene,
2,6-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]naphthalene,
4,4''-bis[N,N-di(2-naphthyl)amino]terphenyl, 4,4'-bis
{N-phenyl-N-[4-(1-naphthyl)phenyl]amino}biphenyl,
4,4'-bis[N-phenyl-N-(2-pyrenyl)amino]biphenyl,
2,6-bis[N,N-di-(2-naphthyl)amino]fluorene or
4,4''-bis(N,N-di-p-tolylamino)terphenyl, and
bis(N-1-naphthyl)(N-2-naphthyl)amine can be representatively
exemplified, without being limited thereto.
The hole injecting layer or the hole transporting layer may be
formed by dispersing an organic compound in a polymer, or by using
a polymer derived from the organic compound. Furthermore, so-called
.pi.-conjugated polymers such as polyparaphenylenevinylene and
derivatives thereof, hole-transporting non-conjugated polymers such
as poly(N-vinylcarbazole) or .alpha.-conjugated polymers such as
polysilanes, and the like may also be used.
The hole injecting layer may be formed by using metal
phthalocyanine such as copper phthalocyanine or nonmetal
phthalocyanine, or electrically conductive polymers such as a
carbon film and polyaniline, or by reacting the arylamine compound
as an oxidizing agent with a Lewis acid.
The specific structure of the organic layer is not particularly
limited. In this field, various materials for forming a hole or
electron injecting electrode layer and an organic layer, for
example, a light emitting unit, an electron injecting or
transporting layer, a hole injecting or transporting layer, and
forming methods thereof are known, and all the above methods may be
applied to manufacture the organic electronic device.
Furthermore, the organic electronic element of the present
application may comprise a protective layer. The protective layer
can prevent damage to the electrode, be composed of typical
materials in this technical field, and for example, comprise SiNx
or Al.sub.2O.sub.3, and the like as an inorganic material.
The present application also relates to a method for manufacturing
the organic electronic device.
The manufacturing method may comprise steps of forming an adhesive
layer comprising a polymer derived from butylene and a curable
oligomer on the other surface of a substrate, one surface of which
an organic electronic element is present on, and curing the
adhesive layer.
The term "curing" herein may mean that the adhesive composition of
the present invention forms a cross-linked structure through
heating or UV irradiation processes to be produced in the form of
an adhesive.
Specifically, an organic electronic element may be formed by
forming an electrode on a polymer film used as a substrate with a
method such as vacuum deposition or sputtering, forming a
luminescent organic material layer composed of, for example, a hole
transporting layer, a light emitting layer and an electron
transporting layer, and the like on the electrode and then further
forming an electrode layer on the top. Subsequently, in the
substrate performed by the above process, the above-described
adhesive layer is placed on the opposite side of the surface on
which the element is formed. Subsequently, the adhesive layer may
be formed by heating the adhesive layer and pressing it in a state
where fluidity is imparted thereto, with a laminator or the like,
and cross-linking the resin in the adhesive layer.
The method for manufacturing the organic electronic device
according to the present application may also comprise positioning
an encapsulation layer to cover the entire surface of the organic
electronic element. Subsequently, the encapsulation layer may be
formed by heating the encapsulation layer and pressing it in a
state where fluidity is imparted thereto, with a laminator or the
like, and cross-linking the resin in the encapsulation layer.
In one example, the encapsulation layer positioned to cover the
entire surface of the organic electronic element may be previously
transferred to the cover substrate. The transfer of the
encapsulation layer to the cover substrate can be also carried out,
for example, by peeling the encapsulation layer and then heating
the encapsulation layer in contact with the cover substrate using a
vacuum press or a vacuum laminator and the like. If the adhesive
contains a thermosetting curable polymer, there is a concern that
the curing reaction is excessively performed in the above process
and sticking force or adhesiveness of the encapsulation layer is
reduced, and thus it is possible to control the process temperature
to about 100.degree. C. or less and the process time within 5
minutes.
The encapsulation layer may be formed by positioning the cover
substrate onto which the encapsulation layer is transferred on the
organic electronic element, and performing the hot pressing
process.
Although one example of the method for manufacturing the organic
electronic device has been mentioned above, the organic electronic
device may be manufactured in other ways as well. For example, the
device is manufactured in the same manner as described above, but
the order or conditions of the process may be changed.
The present application also relates to a use of the organic
electronic device, for example, an organic light emitting device.
The organic light emitting device may be effectively applied to a
backlight of a liquid crystal display (LCD), an illumination, a
light source of various sensors, a printer, a copy machine, a
vehicle instrument light source, a signal lamp, an indicating lamp,
a display device, a light source of a planar light emitter, a
display, a decoration, or various lights, and the like. In one
example, the present application relates to a lighting apparatus
comprising the flexible organic electronic device. In addition, the
present application relates to a display device comprising the
flexible organic electronic device as a light source. When the
organic electronic element is applied to the lighting apparatus or
other uses, other components constituting the device or the like,
or the methods for constituting the device are not particularly
limited, and as long as the organic electronic element is used, any
material or method known in the relevant field may be employed.
Advantageous Effects
The present application provides a flexible organic electronic
device that does not only realize excellent moisture barrier
characteristics, but also has excellent endurance reliability under
high temperature and high humidity conditions while having flexible
characteristics.
BRIEF DESCRIPTION OF DRAWINGS
FIGS. 1 and 2 are cross-sectional views illustrating exemplary
organic electronic devices.
EXPLANATION OF REFERENCE NUMERALS
1: substrate 2: organic electronic element 3: adhesive layer or
adhesive film 4: encapsulation layer 5: cover substrate
BEST MODE
Hereinafter, the present invention will be described in more detail
with reference to Examples complying with the present invention and
Comparative Examples not complying with the present invention, but
the scope of the present invention is not limited by the following
examples.
Example 1
A styrene-isobutylene copolymer (SIBS 102T, Mw: 100,000, Kaneka) as
a polymer derived from butylene, a hydrogenated bisphenol A epoxy
resin (YX8000, epoxy equivalent: 201 g/eq, Mitsubishi Chemical) as
a curable oligomer, and a silane-modified epoxy resin (KSR-177,
Kukdo Chemical) as a curable monomer were introduced into a
reaction vessel at a weight ratio of 60:15:25 (SIBS 102T: YX8000:
KSR-177), respectively, and Irgacure290 (Ciba) as a cationic
photoinitiator was added thereto in an amount of 0.1 parts by
weight, relative to 100 parts by weight of the polymer, and then
diluted with toluene to a solid content of about 15% by weight to
prepare an adhesive composition coating solution.
An adhesive film was produced by coating the prepared solution on
the releasing surface of the releasing PET and drying it in an oven
at 100.degree. C. for 15 minutes to form an adhesive layer having a
thickness of 50 .mu.m.
Example 2
An adhesive composition and an adhesive film were produced in the
same manner as in Example 1, except that a styrene-isobutylene
copolymer (SIBS 102T, Mw: 100,000, Kaneka) as a polymer derived
from butylene, a hydrogenated bisphenol A epoxy resin (YX8000,
epoxy equivalent: 201 g/eq, Mitsubishi Chemical) as a curable
oligomer, and an alicyclic epoxy compound (Celloxide 2021P, Mw:
250, Daicel corporation) as a curable monomer were introduced into
a reaction vessel at a weight ratio of 60:15:25 (SIBS 102T: YX8000:
Celloxide 2021P), respectively.
Comparative Example 1
Polyisobutylene (B50, BASF) as a polymer derived from butylene, a
hydrogenated petroleum resin (SU90, Kolon), and 1,6-hexandediol
diacrylate (M200, Miwon Commercial Co., Ltd.) were introduced into
a reaction vessel at a weight ratio of 60:30:10 (B50: SU90: M200),
respectively, and Irgacure651 (Ciba) as a radical initiator was
added thereto in an amount of 0.1 parts by weight, relative to 100
parts by weight of the polymer, and then diluted with toluene to a
solid content of about 15% by weight to prepare an adhesive
composition coating solution.
An adhesive film was produced by coating the prepared solution on
the releasing surface of the releasing PET and drying it in an oven
at 100.degree. C. for 15 minutes to form an adhesive layer having a
thickness of 50 .mu.m.
Comparative Example 2
An adhesive composition and an adhesive film were produced in the
same manner as in Comparative Example 1, except that
polyisobutylene (B50, BASF) as a polymer derived from butylene, a
hydrogenated petroleum resin (SU90, Kolon), and 1,6-hexandediol
diacrylate (M200, Miwon Commercial Co., Ltd.) were introduced into
a reaction vessel at a weight ratio of 50:40:10 (B50: SU90: M200),
respectively.
Comparative Example 3
An adhesive composition and an adhesive film were produced in the
same manner as in Example 1, except that a styrene-isobutylene
copolymer (SIBS 062M, Kaneka) as a polymer derived from butylene, a
hydrogenated petroleum resin (SU90, Kolon), and an alicyclic epoxy
compound (Celloxide 2021P, Mw: 250, Daicel corporation) were
introduced into a reaction vessel at a weight ratio of 50:30:20
(SIBS 062M: SU90: Celloxide 2021P), respectively.
Experimental Example 1--Storage Elastic Modulus after Curing
After curing the adhesive film prepared in Examples and Comparative
Examples with a UV dose of 1000 mJ/cm.sup.2 or at 110.degree. C.
for 1 hour, the film was laminated to a thickness of 600 .mu.m, and
physical properties were measured using ARES equipment as
follows.
The storage elastic modulus was measured in conditions of a
temperature of 25.degree. C., a strain of 5% and a frequency of 1
Hz.
Experimental Example 2--Viscosity Before Curing
Before curing the adhesive film prepared in Examples and
Comparative Examples, the film was laminated to a thickness of 600
.mu.m, and physical properties were measured using ARES equipment
as follows. The viscosity was measured depending on shear stress in
conditions of a temperature of 65.degree. C., a strain of 5% and a
frequency of 1 Hz.
Experimental Example 3--Step Filling Property
In a simple substrate on which steps of 10 .mu.m are formed, the
adhesive film prepared in Examples and Comparative Examples was
adhered to the center portion by using a roll laminator. A glass
having the same size as the prepared specimen is pressed in the
vertical direction and bonded together by applying a vacuum of 100
pa and a pressure of 0.5 MPa under a temperature condition of
65.degree. C. with a vacuum bonding machine. The cohesiveness was
determined depending on looseness of the step forming region in the
front side of the adhesive and classified as 0 when the loosed
portion of the step formation region is 10% or less of the total
area, A when it is 30% or less and X when it is 50% or more.
Experimental Example 4--Heat Resistance Holding Ability
A sample in which the pressure-sensitive adhesive layer prepared in
Examples and Comparative Examples was formed to a thickness of 50
.mu.m on one surface of a polyimide substrate was attached to a
glass with an adhesion area of 1 cm.times.1 cm, and the holding
ability of the pressure-sensitive adhesive layer was measured, when
a load of 1 kg was applied to the substrate in the direction of
gravitational force at 80.degree. C. for 24 hours.
It was classified as O when the pressure-sensitive adhesive layer
is adhered to the glass for 12 hours or more and X when it
falls.
TABLE-US-00001 TABLE 1 Storage elastic Viscosity modulus at
65.degree. C. Step after curing before curing filling Heat
resistance (MPa) (Pa s) property holding ability Example 1 2.1 5000
.DELTA. .largecircle. Example 2 2.0 4000 .DELTA. .largecircle. C.
Example 1 0.3 20000 X X C. Example 2 0.1 15000 X X C. Example 3 1.0
1500 .largecircle. X (C. Example: Comparative Example)
* * * * *