U.S. patent application number 15/266653 was filed with the patent office on 2017-01-05 for adhesive, adhesive layer, and adhesive sheet.
This patent application is currently assigned to NITTO DENKO CORPORATION. The applicant listed for this patent is NITTO DENKO CORPORATION. Invention is credited to Masatsugu HIGASHI, Azusa ISEKI, Katsuhiko KAMIYA, Kiyoe SHIGETOMI, Koji SHITARA, Akiko TANAKA.
Application Number | 20170002235 15/266653 |
Document ID | / |
Family ID | 47995244 |
Filed Date | 2017-01-05 |
United States Patent
Application |
20170002235 |
Kind Code |
A1 |
HIGASHI; Masatsugu ; et
al. |
January 5, 2017 |
ADHESIVE, ADHESIVE LAYER, AND ADHESIVE SHEET
Abstract
A pressure-sensitive adhesive of the invention include a
(meth)acryl-based polymer obtained by polymerization of a monomer
component including 30 to 99.5% by weight of an alkyl
(meth)acrylate having an alkyl group of 10 to 18 carbon atoms at an
ester end and 0.5 to 50% by weight of a cyclic nitrogen-containing
monomer. The pressure-sensitive adhesive has a satisfactory level
of adhesive performance and can form a pressure-sensitive adhesive
layer with a lower dielectric constant and reliable moisture
resistance.
Inventors: |
HIGASHI; Masatsugu; (Osaka,
JP) ; SHIGETOMI; Kiyoe; (Osaka, JP) ; SHITARA;
Koji; (Osaka, JP) ; TANAKA; Akiko; (Osaka,
JP) ; KAMIYA; Katsuhiko; (Osaka, JP) ; ISEKI;
Azusa; (Osaka, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NITTO DENKO CORPORATION |
Osaka |
|
JP |
|
|
Assignee: |
NITTO DENKO CORPORATION
Osaka
JP
|
Family ID: |
47995244 |
Appl. No.: |
15/266653 |
Filed: |
September 15, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14348170 |
Mar 28, 2014 |
|
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PCT/JP2012/073354 |
Sep 12, 2012 |
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15266653 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 222/1006 20130101;
B32B 2457/202 20130101; H01B 5/002 20130101; C08F 220/1808
20200201; B32B 27/08 20130101; C09J 2203/318 20130101; C08G 2170/40
20130101; B32B 2457/204 20130101; C08F 220/18 20130101; G02F
2202/28 20130101; C09J 2467/006 20130101; C08F 226/06 20130101;
C08G 18/6266 20130101; C08F 220/20 20130101; C08F 226/10 20130101;
C08F 220/1811 20200201; C08F 226/06 20130101; C08F 220/20 20130101;
C08F 220/20 20130101; C08F 226/10 20130101; C08F 220/1811 20200201;
C08F 220/1811 20200201; C09J 133/14 20130101; Y10T 428/2891
20150115; B32B 2457/00 20130101; B32B 2307/516 20130101; B32B 27/36
20130101; C09J 2433/00 20130101; G02F 1/13338 20130101; B32B 27/306
20130101; C09J 175/04 20130101; B32B 2307/412 20130101; C08F
220/1808 20200201; C08G 18/8029 20130101; C08F 220/1811 20200201;
B32B 7/12 20130101; C08F 226/06 20130101; B32B 2307/202 20130101;
C09J 7/385 20180101; C08F 220/20 20130101 |
International
Class: |
C09J 7/02 20060101
C09J007/02; H01B 5/00 20060101 H01B005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 30, 2011 |
JP |
2011-217115 |
Apr 13, 2012 |
JP |
2012-092125 |
Claims
1.-19. (canceled)
20. A pressure-sensitive adhesive sheet, comprising a transparent
conductive film as a support and a pressure-sensitive adhesive
layer formed on at least one side of the transparent conductive
film, wherein the pressure-sensitive adhesive layer is obtained
from a pressure-sensitive adhesive composition, wherein the
pressure-sensitive adhesive composition comprises a
(meth)acryl-based polymer obtained by polymerization of a monomer
component including 30 to 99.5% by weight of an alkyl
(meth)acrylate having an alkyl group of 10 to 18 carbon atoms at an
ester end and 0.5 to 50% by weight of a cyclic nitrogen-containing
monomer.
21. The pressure-sensitive adhesive sheet according to claim 20,
wherein the alkyl group of the alkyl (meth)acrylate having the
alkyl group of 10 to 18 carbon atoms at the ester end is a branched
alkyl group.
22. The pressure-sensitive adhesive sheet according to claim 20,
wherein the alkyl (meth)acrylate having the alkyl group of 10 to 18
carbon atoms at the ester is an alkyl methacrylate having an alkyl
group of 10 to 18 carbon atoms at the ester end.
23. The pressure-sensitive adhesive sheet according to claim 20,
wherein the alkyl (meth)acrylate having the alkyl group of 10 to 18
carbon atoms at the ester is an alkyl acrylate having an alkyl
group of 10 to 18 carbon atoms at the ester end.
24. The pressure-sensitive adhesive sheet according to claim 20,
wherein the monomer component further includes 0.5% by weight or
more of at least one functional group-containing monomer selected
from a carboxyl group-containing monomer, a hydroxyl
group-containing monomer, and a cyclic ether group-containing
monomer.
25. The pressure-sensitive adhesive sheet according to claim 20,
wherein the monomer component further includes 0.5% or more by
weight of at least one selected from an alkyl (meth)acrylate having
an alkyl group of 1 to 9 carbon atoms at an ester end and an alkyl
(meth)acrylate having a cyclic alkyl group at an ester end.
26. The pressure-sensitive adhesive sheet according to claim 20,
wherein the monomer component further includes 3% or less by weight
of a polyfunctional monomer.
27. The pressure-sensitive adhesive sheet according to claim 20,
wherein the pressure-sensitive adhesive composition comprises 0.01
to 5 parts by weight of a crosslinking agent based on 100 parts by
weight of the (meth)acryl-based polymer.
28. The pressure-sensitive adhesive sheet according to claim 20,
wherein the pressure-sensitive adhesive layer has a relative
dielectric constant of 3.5 or less at a frequency of 100 kHz.
29. The pressure-sensitive adhesive sheet according to claim 20,
wherein the pressure-sensitive adhesive layer has a gel fraction of
20 to 98% by weight.
30. The pressure-sensitive adhesive sheet according to claim 20,
wherein the pressure-sensitive adhesive layer has a haze of 2% or
less when having a thickness of 25 .mu.m.
31. The pressure-sensitive adhesive sheet according to claim 20,
wherein the pressure-sensitive adhesive layer has a total light
transmittance of 90% or more.
32. The pressure-sensitive adhesive sheet according to claim 20,
which has an adhesive strength of 0.5 N/20 mm or more to alkali
glass at a peel angle of 90.degree. and a peel rate of 300
mm/minute.
Description
TECHNICAL FIELD
[0001] The invention relates to a pressure-sensitive adhesive
capable have a lower dielectric constant. The invention also
relates to a pressure-sensitive adhesive layer obtained from such a
pressure-sensitive adhesive and to a pressure-sensitive adhesive
sheet including a support and such a pressure-sensitive adhesive
layer provided on at least one side of the support.
[0002] The pressure-sensitive adhesive layer or the
pressure-sensitive adhesive sheet of the invention is suitable for
use in optical applications. For example, the pressure-sensitive
adhesive layer or the pressure-sensitive adhesive sheet of the
invention is suitable for use in the manufacture of image display
devices such as liquid crystal display devices, organic
electro-luminescent (EL) display devices, plasma display panels
(PDPs), and electronic paper, and is also suitable for use in the
manufacture of input devices such as touch panels including
optical, ultrasonic, capacitance, and resistive types. In
particular, the pressure-sensitive adhesive layer or the
pressure-sensitive adhesive sheet of the invention is
advantageously used in capacitance touch panels.
[0003] The pressure-sensitive adhesive sheet of the invention is
also useful as a pressure-sensitive adhesive optical member, in
which an optical member is used as the support. For example, when a
transparent conductive film is used as the optical member, the
pressure-sensitive adhesive optical member can be used as a
pressure-sensitive adhesive layer-carrying transparent conductive
film. Such a pressure-sensitive adhesive layer-carrying transparent
conductive film may be used as a transparent electrode in the image
display device or the touch panel mentioned above after it is
processed appropriately. In particular, the pressure-sensitive
adhesive layer-carrying transparent conductive film with a
patterned transparent conductive thin layer is advantageously used
as an electrode substrate for an input device of a capacitance
touch panel. Additionally, the pressure-sensitive adhesive
layer-carrying transparent conductive film can be used for
electromagnetic wave shielding or prevention of static buildup on
transparent products and to form liquid crystal dimming glass
products and transparent heaters.
[0004] When an optical film is used as the optical member, the
pressure-sensitive adhesive optical member can be used as a
pressure-sensitive adhesive layer-carrying optical film. The
pressure-sensitive adhesive layer-carrying optical film is used for
an image display device such as a liquid crystal display device and
an organic electroluminescence (EL) display device. The optical
film may be a polarizing plate, a retardation plate, an optical
compensation film, a brightness enhancement film, a laminate
thereof, or the like.
BACKGROUND ART
[0005] In recent years, input devices having a combination of a
touch panel and an image display device, such as cellular phones
and portable music players, have become popular. In particular,
capacitance touch panels have rapidly become popular because of
their functionality.
[0006] There are now many known transparent conductive films for
use in touch panels, which include a laminate of a transparent
plastic film substrate or a glass sheet and a transparent
conductive thin layer (ITO layer). A transparent conductive film
can be laminated on any other member with a pressure-sensitive
adhesive layer interposed therebetween. Various types of
pressure-sensitive adhesive layers are proposed (Patent Document 1
to 4).
[0007] When the transparent conductive film is used as an electrode
substrate for a capacitance touch panel, the transparent conductive
thin layer used is patterned. The transparent conductive film with
the patterned transparent conductive thin layer is laminated on
another transparent conductive film or any other component with a
pressure-sensitive adhesive layer interposed therebetween to form a
laminate to be used. These transparent conductive films are
advantageously used for a multi-touch input device, which can be
operated by touching it with two or more fingers at the same time.
Specifically, a capacitance touch panel is designed to achieve
sensing when the amount of change in output signal, which is
generated at a position where the touch panel is touched with a
finger or the like, exceeds a certain threshold value.
PRIOR ART DOCUMENTS
Patent Documents
[0008] Patent Document 1: JP-A-2003-238915
[0009] Patent Document 2: JP-A-2003-342542
[0010] Patent Document 3: JP-A-2004-231723
[0011] Patent Document 4: JP-A-2002-363530
[0012] Patent Document 5: WO 2010/147047
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0013] As mentioned above, the dielectric constant of a component
or film used to form a touch panel is an important value related to
the response of the touch panel. On the other hand, now, as touch
panels have become popular, they have been required to have higher
performance, and transparent conductive films or pressure-sensitive
adhesive layers to be used as components thereof also have been
required to have higher performance, in which a reduction in
thickness is one of the requirements. However, there is a problem
in that simply reducing the thickness of a pressure-sensitive
adhesive layer can change the designed capacitance. Thus, there is
a need to reduce the dielectric constant of a pressure-sensitive
adhesive layer without changing the capacitance value when the
pressure-sensitive adhesive layer is reduced in thickness. In some
cases, an air layer between a printed glass or film and an optical
film or an air layer above an LCD is filled with a
pressure-sensitive adhesive layer so that visibility can be
improved. On the other hand, however, such a pressure-sensitive
adhesive may cause a malfunction if having high dielectric
constant. To prevent such a malfunction, adhesive layers are
required to have lower dielectric constant. In addition, the
reduction in the dielectric constant of a pressure-sensitive
adhesive layer is also expected to improve the response speed or
sensitivity of a touch panel. There is also a problem in that when
a laminate including a transparent conductive film and a glass
sheet laminated with a pressure-sensitive adhesive layer interposed
therebetween is exposed to humid conditions, the pressure-sensitive
adhesive layer become clouded.
[0014] It is therefore an object of the invention to provide a
pressure-sensitive adhesive that has a satisfactory level of
adhesive performance and can form a pressure-sensitive adhesive
layer with a lower dielectric constant and reliable moisture
resistance.
[0015] It is another object of the invention to provide a
pressure-sensitive adhesive layer made from such a
pressure-sensitive adhesive and to provide a pressure-sensitive
adhesive sheet having such a pressure-sensitive adhesive layer.
Means for Solving the Problems
[0016] As a result of intense investigations to solve the problems,
the inventors have made the invention, based on the finding that
the objects are achieved with a pressure-sensitive adhesive
described below.
[0017] The invention relates to a pressure-sensitive adhesive,
including a (meth)acryl-based polymer obtained by polymerization of
a monomer component including 30 to 99.5% by weight of an alkyl
(meth)acrylate having an alkyl group of 10 to 18 carbon atoms at an
ester end and 0.5 to 50% by weight of a cyclic nitrogen-containing
monomer. In the alkyl (meth)acrylate having the alkyl group of 10
to 18 carbon atoms at the ester, preferable alkyl group is a
branched alkyl group. The alkyl (meth)acrylate having the alkyl
group of 10 to 18 carbon atoms at the ester is also preferably an
alkyl methacrylate in view of a lower dielectric constant, and is
also preferably an alkyl methacrylate in view of productivity.
[0018] In the pressure-sensitive adhesive, the monomer component
may further include 0.5% by weight or more of at least one
functional group-containing monomer selected from a carboxyl
group-containing monomer, a hydroxyl group-containing monomer, and
a cyclic ether group-containing monomer.
[0019] In the pressure-sensitive adhesive, the monomer component
may further include 0.5% or more by weight of at least one selected
from an alkyl (meth)acrylate having an alkyl group of 1 to 9 carbon
atoms at an ester end and an alkyl (meth)acrylate having a cyclic
alkyl group at an ester end.
[0020] In the pressure-sensitive adhesive, the monomer component
may further contain 3% or less by weight or less of a
polyfunctional monomer.
[0021] In the pressure-sensitive adhesive, the pressure-sensitive
adhesive preferably further include 0.01 to 5 parts by weight of a
crosslinking agent based on 100 parts by weight of the
(meth)acryl-based polymer.
[0022] The pressure-sensitive adhesive is preferably for use on an
optical member.
[0023] The invention also relates to a pressure-sensitive adhesive
layer obtained from the above pressure-sensitive adhesive.
[0024] The pressure-sensitive adhesive layer preferably has a
relative dielectric constant of 3.5 or less at a frequency of 100
kHz.
[0025] The pressure-sensitive adhesive layer preferably has a gel
fraction of 20 to 98% by weight.
[0026] The pressure-sensitive adhesive layer preferably has a haze
of 2% or less when having a thickness of 25 .mu.m.
[0027] The pressure-sensitive adhesive layer preferably has a total
light transmittance of 90% or more.
[0028] The pressure-sensitive adhesive layer is preferably for use
on an optical member.
[0029] The invention also relates to a pressure-sensitive adhesive
sheet including: a support; and the above pressure-sensitive
adhesive layer formed on at least one side of the support.
[0030] The pressure-sensitive adhesive sheet preferably has an
adhesive strength of 0.5 N/20 mm or more to alkali glass at a peel
angle of 90.degree. and a peel rate of 300 mm/minute.
[0031] The pressure-sensitive adhesive sheet is preferably for use
on an optical member. The pressure-sensitive adhesive sheet is
preferably a pressure-sensitive adhesive optical member including
an optical member as the support and the pressure-sensitive
adhesive layer provided on at least one side of the optical
member.
Effect of the Invention
[0032] The (meth)acryl-based polymer as a main component of the
pressure-sensitive adhesive of the invention is obtained by
polymerization of a monomer component including a predetermined
amount of an alkyl (meth)acrylate having a relatively long chain
alkyl group and a cyclic nitrogen-containing monomer. The
relatively long chain alkyl group and a nitrogen atom-containing
cyclic structure in the pressure-sensitive adhesive of the
invention is effective in forming a pressure-sensitive adhesive
layer with a lower dielectric constant and a reliable moisture
resistance, and in providing a satisfactory level of adhesive
performance. Also when an air layer is filled with a
pressure-sensitive adhesive layer, malfunctions can be prevented
because of the low dielectric constant of the adhesive layer.
[0033] To lower the dielectric constant, it is said that the dipole
moment of the molecule may be reduced, and the molar volume of the
molecule may be increased, according to the Clausius-Mossotti
equation. The main monomer unit of the (meth)acryl-based polymer as
a main component of the pressure-sensitive adhesive of the
invention is derived from an alkyl (meth)acrylate having a
relatively long chain alkyl group. The (meth)acryl-based polymer
also has a copolymerized unit derived from a monomer having a
nitrogen atom-containing cyclic structure. These features are
considered to reduce the dielectric constant. The nitrogen
atom-containing cyclic structure can also produce cohesive and
hydrophilic effects, which are considered to provide reliable
moisture resistance.
[0034] For example, the pressure-sensitive adhesive layer of the
invention can have a relative dielectric constant as low as 3.5 or
less at a frequency of 100 kHz. This feature makes it possible to
design capacitance touch panels with no change in capacitance value
even when the pressure-sensitive adhesive layer of the invention is
reduced in thickness to form a transparent conductive film for use
in capacitance touch panels, and the pressure-sensitive adhesive
layer satisfies a reliable moisture resistance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] FIG. 1 is a view showing an example of a capacitance touch
panel produced using the pressure-sensitive adhesive layer or the
pressure-sensitive adhesive sheet of the invention.
MODE FOR CARRYING OUT THE INVENTION
[0036] The pressure-sensitive adhesive of the invention contains a
(meth)acryl-based polymer obtained by polymerization of a monomer
component including 30 to 99.5% by weight of an alkyl
(meth)acrylate having an alkyl group of 10 to 18 carbon atoms at an
ester end and 0.5 to 50% by weight of a cyclic nitrogen-containing
monomer. As used herein, the term "alkyl (meth)acrylate" refers to
alkyl acrylate and/or alkyl methacrylate, and "(meth)" is used in
the same meaning in the description.
[0037] The alkyl (meth)acrylate having an alkyl group of 10 to 18
carbon atoms at the ester end is preferably capable of forming a
homopolymer having a glass transition temperature (Tg) of -80 to
0.degree. C., more preferably -70 to -10.degree. C. If the Tg of
the homopolymer is -80.degree. C. or lower, the pressure-sensitive
adhesive may have too low an elastic modulus at normal temperature,
which is not preferred. If the Tg of the homopolymer is higher than
0.degree. C., the adhesive strength may be undesirably reduced. The
Tg of the homopolymer is the value measured using TG-DTA. To
achieve low dielectric constant and moderate elastic modulus, the
alkyl group has 10 to 18 carbon atoms. Based on this, an alkyl
(meth)acrylate having a suitable alkyl group can be selected as
needed depending on the method of producing the (meth)acryl-based
polymer. For example, when the (meth)acryl-based polymer is
produced by solution polymerization or the like, the alkyl group
preferably has preferably 10 to 16 carbon atoms, more preferably 10
to 14 carbon atoms. When the (meth)acryl-based polymer is produced
by radiation polymerization or the like, the alkyl group preferably
has 12 to 18 carbon atoms, more preferably 14 to 18 carbon atoms.
It should be noted that a straight-chain alkyl group or an alkyl
group of 9 or less carbon atoms is less effective in lowering the
dielectric constant of the pressure-sensitive adhesive layer even
though the homopolymer of the corresponding alkyl (meth)acrylate
has a Tg of -80 to 0.degree. C.
[0038] Although the alkyl group of 10 to 18 carbon atoms in the
alkyl (meth)acrylate to be used may be any of a linear chain and a
branched chain, the alkyl group is preferably a branched chain in
view of forming a pressure-sensitive adhesive layer with a lower
dielectric constant. It is conceivable that when the long chain
alkyl group of the alkyl methacrylate is a branched alkyl group, a
molar volume of a molecule of the long-chain alkyl group was
increased, and reduces a lower dipole moment so that it can form a
pressure-sensitive adhesive layer with a good balance between
them.
[0039] Examples of the alkyl (meth)acrylate having a branched-alkyl
group of 10 to 18 carbon atoms at the ester end include isodecyl
acrylate (10 carbons, homopolymer Tg=-60.degree. C., hereinafter,
simply abbreviated as Tg), isodecyl methacrylate (10 carbons,
homopolymer Tg=-41.degree. C.), isomyristyl acrylate (14 carbons,
homopolymer Tg=-56.degree. C.), isostearyl acrylate (18 carbons,
homopolymer Tg=-18.degree. C.), 2-propylheptylacrylate, isoundecyl
acrylate, isododecyl acrylate, isotridecyl acrylate, isopentadecyl
acrylate, isohexadecyl acrylate, isoheptadecyl acrylate, and
methacrylate monomers corresponding to the above acrylates. These
monomers may be used alone or in combination of two or more.
[0040] Of the branched alkyl group of 10 to 18 carbon atoms, those
having a t-butyl group are preferable in consideration of
particularly obtaining a pressure-sensitive adhesive with an
increased molar volume, a lowered dipole moment, and a balance of
both. An Example of the alkyl (meth)acrylate having a branched
alkyl group of 10 to 18 carbon atoms, the alkyl group having
t-butyl group, includes isostearyl acrylate represented by the
following formula:
##STR00001##
[0041] Also, as the alkyl (meth)acrylate having an alkyl group of
10 to 18 carbon atoms at the ester end, alkyl methacrylate is more
preferable than alkyl acrylates in view of the effects of the
pressure-sensitive adhesive layer lowering of dielectric constant
due to an increase in molar volume and a reduction in dipole
moment. It is conceivable that when the long chain alkyl group of
the alkyl methacrylate is a linear alkyl group, the alkyl
methacrylate can also have a higher molar volume and a lower dipole
moment so that it can form a pressure-sensitive adhesive layer with
a good balance between them. On the other hand, the alkyl acrylate
has higher compatibility with the cyclic nitrogen-containing
monomer than the alkyl methacrylate. The alkyl acrylate is
preferable in that it can form a (meth)acryl-based polymer with
good transparency, and the (meth)acryl-based polymer is preferable
in that it can produced with a shorter polymerization time and
higher productivity. Particularly when the (meth)acryl-based
polymer is produced by radiation polymerization, the alkyl acrylate
is preferred.
[0042] Examples of the alkyl methacrylate having an alkyl group of
10 to 18 carbon atoms at the ester end include lauryl methacrylate
(12 carbon atoms, Tg=-65.degree. C.), tridecyl methacrylate (13
carbon atoms, Tg=-40.degree. C.), stearyl methacrylate (18 carbon
atoms, Tg=38.degree. C.), isodecyl methacrylate (10 carbon atoms,
Tg=-41.degree. C.), undecyl methacrylate (11 carbon atoms),
tetradecyl methacrylate (14 carbon atoms), pentadecyl methacrylate
(15 carbon atoms), hexadecyl methacrylate (16 carbon atoms),
heptadecyl methacrylate (17 carbon atoms), etc. These may be used
singly or in combination of two or more.
[0043] As will be appreciated from the foregoing, the alkyl
(meth)acrylate having an alkyl group of 10 to 18 carbon atoms at
the ester end is preferably an alkyl methacrylate having a branched
alkyl group of 10 to 18 carbon atoms at the ester end.
[0044] The content of the alkyl (meth)acrylate having an alkyl
group of 10 to 18 carbon atoms at the ester end is 30 to 99.5% by
weight, preferably 32 to 99.5% by weight, more preferably 35 to
99.5% by weight, furthermore preferably 40 to 99.5% by weight,
furthermore preferably 45 to 96% by weight, and furthermore
preferably 65 to 95% by weight, based on the total weight of the
monomer component used to form the (meth)acryl-based polymer. Use
of 30% by weight or more of the alkyl (meth)acrylate is preferable
in view of lowering of dielectric constant, and use of 99.5% by
weight or less thereof is preferable in view of maintaining
adhesive strength.
[0045] Any monomer having a cyclic nitrogen structure and an
unsaturated double bond-containing polymerizable functional group
such as a (meth)acryloyl group or a vinyl group may be used without
restriction as the cyclic nitrogen-containing monomer. The cyclic
nitrogen structure preferably has a nitrogen atom in the cyclic
structure. Examples of the cyclic nitrogen-containing monomer
include vinyl lactam monomers such as N-vinylpyrrolidone,
N-vinyl-.epsilon.-caprolactam, and methylvinylpyrrolidone; and
nitrogen-containing heterocyclic vinyl monomers such as
vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine,
vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, and
vinylmorpholine. The cyclic nitrogen-containing monomer may also be
a (meth)acrylic monomer having a heterocyclic ring such as a
morpholine ring, a piperidine ring, a pyrrolidine ring, or a
piperazine ring. Examples include N-acryloyl morpholine,
N-acryloylpiperidine, N-methacryloyl piperidine, and N-acryloyl
pyrrolidine. Among them, vinyl lactam monomers are preferred, and
N-vinylpyrrolidone is particularly preferred, in view of dielectric
constant and cohesiveness.
[0046] In the invention, the content of the cyclic
nitrogen-containing monomer is from 0.5 to 50% by weight,
preferably from 0.5 to 40% by weight, more preferably from 0.5 to
30% by weight, based on the total weight of the monomer component
used to form the (meth)acryl-based polymer. A cyclic
nitrogen-containing monomer content of 0.5% by weight or more is
preferred in terms of lower dielectric constant and reliable
moisture resistance. A cyclic nitrogen-containing monomer content
of 50% by weight or less is preferred in terms of adhering strength
improvement.
[0047] The monomer component used to form the (meth)acryl-based
polymer according to the invention may further include at least one
functional group-containing monomer selected from a carboxyl
group-containing monomer, a hydroxyl group-containing monomer, and
a cyclic ether group-containing monomer.
[0048] Any monomer having a carboxyl group and an unsaturated
double bond-containing polymerizable functional group such as a
(meth)acryloyl group or a vinyl group may be used without
restriction as the carboxyl group-containing monomer. Examples of
the carboxyl group-containing monomer include (meth)acrylic acid,
carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic
acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic
acid. These may be used alone or in any combination. Itaconic acid
or maleic acid can be used in the form of an anhydride. Among
these, acrylic acid and methacrylic acid are preferred, and acrylic
acid is particularly preferred. In the invention, a carboxyl
group-containing monomer may be or may not be used as an optional
monomer to produce the (meth)acryl-based polymer. An adhesive
containing a (meth)acryl-based polymer obtained from a monomer
composition free of any carboxyl group-containing monomer can form
a pressure-sensitive adhesive layer with reduced ability to corrode
metals, because the ability to corrode metals would be due to any
carboxyl group.
[0049] Any monomer having a hydroxyl group and an unsaturated
double bond-containing polymerizable functional group such as a
(meth)acryloyl group or a vinyl group may be used without
restriction as the hydroxyl group-containing monomer. Examples of
the hydroxyl group-containing monomer include hydroxyalkyl
(meth)acrylate such as 2-hydroxybutyl (meth)acrylate,
3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate,
6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate,
10-hydroxydecyl (meth)acrylate, or 12-hydroxylauryl (meth)acrylate;
and hydroxyalkylcycloalkane (meth)acrylate such as
(4-hydroxymethylcyclohexyl)methyl (meth)acrylate. Other examples
include hydroxyethyl(meth)acrylamide, allyl alcohol, 2-hydroxyethyl
vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol
monovinyl ether. These may be used alone or in any combination.
Among them, hydroxyalkyl (meth)acrylate is preferred.
[0050] Any monomer having a cyclic ether group such as an epoxy
group or an oxetane group and an unsaturated double bond-containing
polymerizable functional group such as a (meth)acryloyl group or a
vinyl group may be used without restriction as the cyclic ether
group-containing monomer. Examples of the epoxy group-containing
monomer include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl
(meth)acrylate, and 4-hydroxybutyl(meth)acrylate glycidyl ether.
Examples of the oxetane group-containing monomer include
3-oxetanylmethyl (meth)acrylate, 3-methyl-oxetanylmethyl
(meth)acrylate, 3-ethyl-oxetanylmethyl (meth)acrylate,
3-butyl-oxetanylmethyl (meth)acrylate, and 3-hexyl-oxetanylmethyl
(meth)acrylate. These monomers may be used alone or in any
combination.
[0051] In the invention, the content of the functional
group-containing monomer is preferably 0.5% or more, further
preferably 0.8% or more used to form the (meth)acryl-based polymer
so that adhesive strength and cohesive strength can be increased.
If the content of the functional group-containing monomer is too
high, a hard pressure-sensitive adhesive layer with a lower
adhesive strength may be formed, and the pressure-sensitive
adhesive may have too high a viscosity or may form a gel. Thus, the
content of the functional group-containing monomer is preferably
30% by weight or less, more preferably 27% by weight or less, even
more preferably 25% by weight or less based on the total weight of
the monomer component used to form the (meth)acryl-based
polymer.
[0052] The monomer component used to form the (meth)acryl-based
polymer according to the invention may further include a
copolymerizable monomer other than the functional group-containing
monomer. For example, a copolymerizable monomer other than those
described above may be an alkyl (meth)acrylate represented by the
formula CH.sub.2.dbd.C(R.sup.1) COOR.sup.2, wherein R.sup.1
represents hydrogen or a methyl group, and R.sup.2 represents a
substituted or unsubstituted alkyl group of 1 to 9 carbon
atoms.
[0053] The substituted or unsubstituted alkyl group of 1 to 9
carbon atoms represented by R.sup.2 may be a linear or branched
alkyl group or cyclic alkyl group. Specifically, R.sup.2 represents
a branched alkyl of group of 3 to 9 carbon atoms. The substituted
alkyl group preferably has an aryl group of 3 to 8 carbon atoms or
an aryloxy group of 3 to 8 carbon atoms as a substituent. The aryl
group is preferably, but not limited to, a phenyl group. Concerning
this alkyl (meth)acrylate, the alkyl methacrylate is more preferred
than the alkyl acrylate in order to lower dielectric constant by
increasing molar volume and reducing dipole moment.
[0054] Examples of the monomer represented by
CH.sub.2.dbd.C(R.sup.1) COOR.sup.2 include methyl (meth)acrylate,
ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl
(meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate,
n-pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl
(meth)acrylate, heptyl (meth)acrylate, isoamyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl
(meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate,
phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl
(meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, and
isobornyl (meth)acrylate. These monomers may be used alone or in
any combination.
[0055] In the invention, the content of the (meth)acrylate
represented by CH.sub.2.dbd.C(R.sup.1)COOR.sup.2 may be 69.5% by
weight or less, preferably 65% by weight or less, more preferably
59.5% by weight or less, even more preferably 55% by weight or
less, even more preferably 50% by weight or less, even more
preferably 40% by weight or less, even more preferably 30% by
weight or less, based on the total weight of the monomer component
used to form the (meth)acryl-based polymer. To maintain the level
of adhesive strength, the (meth)acrylate represented by
CH.sub.2.dbd.C(R.sup.1)COOR.sup.2 is preferably used in an amount
of 5% by weight or more, more preferably 10% by weight or more.
[0056] The preferred content of the (meth)acrylate represented by
CH.sub.2.dbd.C(R.sup.1)COOR.sup.2, which can be used in the amount
mentioned above, may be selected as needed depending on the method
of producing the (meth)acryl-based polymer. For example, when the
(meth)acryl-based polymer is produced by radiation polymerization
or the like, the content of the (meth)acrylate represented by
CH.sub.2.dbd.C(R.sup.1)COOR.sup.2 is preferably more than 0% by
weight to 55% by weight, more preferably from 20 to 50% by weight,
based on the total weight of all monomers, in view of adhesive
properties. In this case, the content of the alkyl (meth)acrylate
having an alkyl group of 10 to 18 carbon atoms at the ester end is
preferably from 30 to 80% by weight, more preferably from 30 to 70%
by weight, based on the total weight of all monomers.
[0057] Other copolymerizable monomers that may also be used include
vinyl monomers such as vinyl acetate, vinyl propionate, styrene,
.alpha.-methylstyrene; glycol acrylic ester monomers such as
polyethylene glycol (meth)acrylate, polypropylene glycol
(meth)acrylate, methoxyethylene glycol (meth)acrylate, and
methoxypolypropylene glycol (meth)acrylate; and acrylate ester
monomers such as tetrahydrofurfuryl (meth)acrylate,
fluoro(meth)acrylate, silicone (meth)acrylate, and 2-methoxyethyl
acrylate; amide group-containing monomers, amino group-containing
monomers, imide group-containing monomers, N-acryloyl morpholine,
and vinyl ether monomers. Cyclic structure-containing monomers such
as terpene (meth)acrylate and dicyclopentanyl (meth)acrylate may
also be used as copolymerizable monomers.
[0058] Besides the above, a silicon atom-containing silane monomer
may be exemplified as the copolymerizable monomer. Examples of the
silane monomers include 3-acryloxypropyltriethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane,
4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane,
8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane,
10-methacryloyloxydecyltrimethoxysilane,
10-acryloyloxydecyltrimethoxysilane,
10-methacryloyloxydecyltriethoxysilane, and
10-acryloyloxydecyltriethoxysilane.
[0059] In the invention, if necessary, the monomer component used
to form the (meth)acryl-based polymer may contain a polyfunctional
monomer for controlling the cohesive strength of the
pressure-sensitive adhesive in addition to the monofunctional
monomers listed above.
[0060] The polyfunctional monomer is a monomer having at least two
polymerizable functional groups with an unsaturated double bond
such as (meth)acryloyl group or vinyl group, and examples thereof
include ester compounds of a polyhydric alcohol with (meth)acrylic
acid such as (poly)ethylene glycol di(meth)acrylate,
(poly)propylene glycol di(meth)acrylate, neopentyl glycol
di(meth)acrylate, pentaerythritol di(meth)acrylate,
pentaerythritoltri(meth)acrylate, dipentaerythritol
hexa(meth)acrylate, 1,2-ethyleneglycol di(meth)acrylate,
1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol
di(meth)acrylate, trimethylolpropane tri(meth)acrylate,
tetramethylolmethane tri(meth)acrylate; allyl (meth)acrylate, vinyl
(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate,
urethane acrylate, butanediol di(meth)acrylate, hexanediol
di(meth)acrylate, and the like. Among them, trimethylolpropane
tri(meth)acrylate, hexanediol di(meth)acrylate, and
dipentaerythritol hexa (meth)acrylate can be preferably used. The
polyfunctional monomer can be used alone or in combination of two
or more.
[0061] The content of the polyfunctional monomer, if used, is
preferably 3% by weigh or less, more preferably 2% by weight or
less, even more preferably 1% by weight or less, based on the total
weight of the monomer component used to form the (meth)acryl-based
polymer, although it varies with the molecular weight of the
monomer, the number of the functional groups, or other conditions.
When the polyfunctional monomer is used in a content of more than
3% by weight, the pressure-sensitive adhesive may have too high
cohesive strength and thus have lower adhesive strength.
[0062] The (meth)acryl-based polymer described above can be
produced using a method appropriately selected from known
production methods, such as solution polymerization, radiation
polymerization such as UV polymerization, bulk polymerization, and
various radical polymerization methods including emulsion
polymerization. The resultant (meth)acryl-based polymer may be any
of a random copolymer, a block copolymer, a graft copolymer, or any
other form.
[0063] Any appropriate polymerization initiator, chain transfer
agent, emulsifying agent and so on may be selected and used for
radical polymerization. The (meth)acrylic polymer may be controlled
by the reaction conditions including the amount of addition of the
polymerization initiator or the chain transfer agent. The amount of
the addition may be controlled as appropriate depending on the type
of these materials.
[0064] In a solution polymerization process and so on, for example,
ethyl acetate, toluene or the like is used as a polymerization
solvent. In a specific solution polymerization process, for
example, the reaction is performed under a stream of inert gas such
as nitrogen at a temperature of about 50 to about 70.degree. C. for
about 5 to about 30 hours in the presence of a polymerization
initiator.
[0065] Examples of the thermal polymerization initiator used for
the solution polymerization process include, but are not limited
to, azo initiators such as 2,2'-azobisisobutyronitrile,
2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionic
acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid,
azobisisovaleronitrile,
2,2'-azobis(2-amidinopropane)dihydrochloride,
2,2'-azobis[2-(5-methyl-2-imidazoline-2-yl)propane]dihydrochlorid
e, 2,2'-azobis(2-methylpropionamidine)disulfate,
2,2'-azobis(N,N'-dimethyleneisobutylamidine), and
2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate
(VA-057, manufactured by Wako Pure Chemical Industries, Ltd.);
persulfates such as potassium persulfate and ammonium persulfate;
peroxide initiators such as di(2-ethylhexyl)peroxydicarbonate,
di(4-tert-butylcyclohexyl)peroxydicarbonate,
di-sec-butylperoxydicarbonate, tert-butylperoxyneodecanoate,
tert-hexylperoxypivalate, tert-butylperoxypivalate, dilauroyl
peroxide, di-n-octanoyl peroxide,
1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate,
di(4-methylbenzoyl) peroxide, dibenzoyl peroxide,
tert-butylperoxyisobutylate, 1,1-di(tert-hexylperoxy)cyclohexane,
tert-butylhydroperoxide, and hydrogen peroxide; and redox system
initiators of a combination of a peroxide and a reducing agent,
such as a combination of a persulfate and sodium hydrogen sulfite
and a combination of a peroxide and sodium ascorbate.
[0066] One of the above polymerization initiators may be used
alone, or two or more thereof may be used in a mixture. The content
of the polymerization initiator is preferably from about 0.005 to 1
part by weight, even more preferably from about 0.02 to about 0.5
parts by weight, based on 100 parts by total weight of the monomer
component.
[0067] For example, when 2,2'-azobisisobutyronitrile is used as a
polymerization initiator for the production of the
(meth)acryl-based polymer with the above weight average molecular
weight, the polymerization initiator is preferably used in a
content of about 0.2 parts by weight or less, more preferably of
from about 0.06 to about 0.2 parts by weight, further more
preferably of from about 0.08 to about 0.175 parts by weight, based
on 100 parts by total weight of the monomer component.
[0068] Examples of the chain transfer agent include lauryl
mercaptan, glycidyl mercaptan, mercaptoacetic acid,
2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate
and 2,3-dimercapto-1-propanol. One of these chain transfer agents
may be used alone, or two or more thereof may be used in a mixture.
The total content of the chain transfer agent is preferably about
0.1 parts by weight or less, based on 100 parts by total weight of
the monomer component.
[0069] Examples of the emulsifier used in emulsion polymerization
include anionic emulsifiers such as sodium lauryl sulfate, ammonium
lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium
polyoxyethylene alkyl ether sulfate, and sodium polyoxyethylene
alkyl phenyl ether sulfate; and nonionic emulsifiers such as
polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether,
polyoxyethylene fatty acid ester, and
polyoxyethylene-polyoxypropylene block polymers. These emulsifiers
may be used alone, or two or more thereof may be used in
combination.
[0070] The emulsifier may be a reactive emulsifier. Examples of
such an emulsifier having an introduced radical-polymerizable
functional group such as a propenyl group and an allyl ether group
include Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, and BC-20 (each
manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and Adekaria Soap
SE10N (manufactured by ADEKA COORPORATION). The reactive emulsifier
is preferred, because after polymerization, it can be incorporated
into a polymer chain to improve water resistance. Based on 100
parts by total weight of the monomer component, the emulsifier is
preferably used in a content of 0.3 to 5 parts by weight, more
preferably of 0.5 to 1 part by weight, in view of polymerization
stability or mechanical stability.
[0071] The (meth)acryl-based polymer can also be produced by
radiation polymerization, in which radiation, such as electron
beams or UV rays, is applied to the monomer component. When
electron beams are used in the radiation polymerization, there is
no particular need to add a photopolymerization initiator to the
monomer component. When UV polymerization is used as the radiation
polymerization, however, a photopolymerization initiator may be
added to the monomer component, which is advantageous particularly
in that the polymerization time can be reduced. Any of the
photopolymerization initiators may be used alone or in combination
of two or more.
[0072] The photopolymerization initiator is not particularly
limited as long as it can initiate photopolymerization, and
photopolymerization initiators that are usually used can be
employed. Examples thereof that can be used include benzoin
ether-based photopolymerization initiator, acetophenone-based
photopolymerization initiator, .alpha.-ketol-based
photopolymerization initiator, aromatic sulfonyl chloride-based
photopolymerization initiator, photoactive oxime-based
photopolymerization initiator, benzoin-based photopolymerization
initiator, benzyl-based photopolymerization initiator,
benzophenone-based photopolymerization initiator, ketal-based
photopolymerization initiator, thioxanthone-based
photopolymerization initiator, acylphosphine oxide-based
photopolymerization initiator, and the like.
[0073] Specific examples of the benzoin ether-based
photopolymerization initiator include benzoin methyl ether, benzoin
ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin
isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name:
IRGACURE 651, manufactured by BASF), anisoin methyl ether, and the
like. Examples of the acetophenone-based photopolymerization
initiator include 1-hydroxycyclohexyl phenyl ketone (trade name:
IRGACURE 184, manufactured by BASF), 4-phenoxydichloroacetophenone,
4-t-butyl-dichloroacetophenone,
1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one
(trade name: IRGACURE 2959, manufactured by BASF),
2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: DAROCUR 1173,
manufactured by BASF), methoxyacetophenone, and the like. Examples
of the .alpha.-ketol-based photopolymerization initiator include
2-methyl-2-hydroxypropiophenone,
1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one, and
the like. Examples of the aromatic sulfonyl chloride-based
photopolymerization initiator include 2-naphthalene sulfonyl
chloride and the like. Examples of the photoactive oxime-based
photopolymerization initiator include
1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl)-oxime, and the
like.
[0074] Examples of the benzoin-based photopolymerization initiator
include benzoin and the like. Examples of the benzyl-based
photopolymerization initiator include benzyl and the like. Examples
of the benzophenone-based photopolymerization initiators include
benzophenone, benzoylbenzoic acid,
3,3'-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone,
.alpha.-hydroxycyclohexyl phenyl ketone, and the like. Examples of
the ketal-based photopolymerization initiator include benzyl
dimethyl ketal and the like. Examples of the thioxanthone-based
photopolymerization initiator include thioxanthone,
2-chlorothioxanthone, 2-methylthioxanthone,
2,4-dimethylthioxanthone, isopropylthioxanthone,
2,4-dichlorothioxanthone, 2,4-diethylthioxanthone,
isopropylthioxanthone, 2,4-diisopropylthioxanthone,
dodecylthioxanthone and the like.
[0075] Examples of the acylphosphine oxide-based
photopolymerization initiator include
bis(2,6-dimethoxybenzoyl)phenylphosphine oxide,
bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide,
bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide,
bis(2,6-dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide,
bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide,
bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide,
bis(2,6-dimethoxybenzoyl)octylphosphine oxide,
bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide,
bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide,
bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide,
bis(2,6-diethoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide,
bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide,
bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide,
bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide,
bis(2,6-dimethoxybenzoyl)benzylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide,
bis(2,6-dimethoxybenzoyl)benzylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide,
2,6-dimethoxybenzoyl benzylbutylphosphine oxide,
2,6-dimethoxybenzoyl benzyloctylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine
oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine
oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,
6-dimethoxybenzoyl-2, 4, 6-trimethylbenzoyl-n-butylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide,
1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane,
tri(2-methylbenzoyl)phosphine oxide, and the like.
[0076] The content of the photopolymerization initiator is not
particularly limited, but is preferably 0.01 to 5 parts by weight,
more preferably 0.05 to 3 parts by weight, furthermore preferably
0.05 to 1.5 parts by weight, and particularly preferably 0.1 to 1
part by weight, based on 100 parts by total weight of the monomer
component.
[0077] If the photopolymerization initiator is used in an amount of
less than 0.01 parts by weight, the polymerization reaction may be
insufficient. If the photopolymerization initiator is used in an
amount of more than 5 parts by weight, the photopolymerization
initiator may absorb ultraviolet rays, so that ultraviolet rays may
fail to reach the inside of the pressure-sensitive adhesive layer.
In this case, the degree of polymerization may decrease, or a
polymer with a lower molecular weight may be produced. This may
cause the resulting pressure-sensitive adhesive layer to have lower
cohesive strength, so that in the process of peeling off the
pressure-sensitive adhesive layer from a film, the
pressure-sensitive adhesive layer may partially remain on the film,
which may make it impossible to reuse the film. The
photopolymerization initiators may be used singly or in combination
of two or more.
[0078] In the invention, the (meth)acryl-based polymer preferably
has a weight average molecular weight of 400,000 to 2,500,000, more
preferably 600,000 to 2,200,000. When the weight average molecular
weight is more than 400,000, the pressure-sensitive adhesive layer
can have satisfactory durability and can have a cohesive strength
small enough to suppress adhesive residue. On the other hand, if
the weight average molecular weight is more than 2,500,000, bonding
ability or adhesive strength may tend to be lower. In this case,
the pressure-sensitive adhesive may form a solution with too high a
viscosity, which may be difficult to apply. As used herein, the
term "weight average molecular weight" refers to a
polystyrene-equivalent weight average molecular weight, which is
determined using gel permeation chromatography (GPC). It should be
noted that the molecular weight of the (meth)acryl-based polymer
obtained by radiation polymerization would be difficult to
measure.
<Measurement of Weight Average Molecular Weight>
[0079] The weight average molecular weight of the obtained
(meth)acryl-based polymer was measured by gel permeation
chromatography (GPC) as follows. The polymer sample was dissolved
in tetrahydrofuran to form a 0.1% by weight solution. After allowed
to stand overnight, the solution was filtered through a 0.45 .mu.m
membrane filter, and the filtrate was used for the measurement.
Analyzer: HLC-8120GPC manufactured by TOSOH CORPORATION Columns:
(meth)acryl-based polymer, GM7000H.sub.XL+GMH.sub.XL+GMH.sub.XL,
manufactured by TOSOH CORPORATION, aromatic-based polymer,
G3000HXL+2000HXL+G1000HXL, manufactured by TOSOH CORPORATION Column
size: each 7.8 mm.phi..times.30 cm, 90 cm in total Eluent:
tetrahydrofuran (concentration 0.1% by weight) Flow rate: 0.8
ml/minute Inlet pressure: 1.6 MPa Detector: differential
refractometer (RI) Column temperature: 40.degree. C. Injection
volume: 100 .mu.l Standard sample: polystyrene
[0080] The pressure-sensitive adhesive of the invention may contain
a crosslinking agent. Examples of the crosslinking agents include
an isocyanate crosslinking agent, an epoxy crosslinking agent, a
silicone crosslinking agent, an oxazoline crosslinking agent, an
aziridine crosslinking agent, a silane crosslinking agent, an alkyl
etherified melamine crosslinking agent, a metallic chelate
crosslinking agent and a peroxide. Such crosslinking agents may be
used alone or in combination of two or more. An isocyanate
crosslinking agent or an epoxy crosslinking agent is preferably
used as the crosslinking agent.
[0081] These crosslinking agents may be used alone or in a mixture
of two or more. The total content of the crosslinking agent(s) is
preferably 5 parts by weight or less, more preferably 0.01 to 5
parts by weight, even more preferably 0.01 to 4 parts by weight,
still more preferably 0.02 to 3 parts by weight, based on 100 parts
by weight of the (meth)acryl-based polymer.
[0082] The term "isocyanate crosslinking agent" refers to a
compound having two or more isocyanate groups (which may include
functional groups that are temporarily protected with an isocyanate
blocking agent or by oligomerization and are convertible to
isocyanate groups) per molecule.
[0083] Isocyanate crosslinking agents include aromatic isocyanates
such as tolylene diisocyanate and xylene diisocyanate, alicyclic
isocyanates such as isophorone diisocyanate, and aliphatic
isocyanates such as hexamethylene diisocyanate.
[0084] More specifically, examples of isocyanate crosslinking
agents include lower aliphatic polyisocyanates such as butylene
diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates
such as cyclopentylene diisocyanate, cyclohexylene diisocyanate,
and isophorone diisocyanate; aromatic diisocyanates such as 2,
4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
xylylene diisocyanate, and polymethylene polyphenyl isocyanate;
isocyanate adducts such as a trimethylolpropane-tolylene
diisocyanate trimer adduct (trade name: CORONATE L, manufactured by
NIPPON POLYURETHANE INDUSTRY CO., LTD.), a
trimethylolpropane-hexamethylene diisocyanate trimer adduct (trade
name: CORONATE HL, manufactured by NIPPON POLYURETHANE INDUSTRY
CO., LTD.), and an isocyanurate of hexamethylene diisocyanate
(trade name: CORONATE HX, manufactured by NIPPON POLYURETHANE
INDUSTRY CO., LTD.); a trimethylolpropane adduct of xylylene
diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals,
Inc.) and a trimethylolpropane adduct of hexamethylene diisocyanate
(trade name: D160N, manufactured by Mitsui Chemicals, Inc.);
polyether polyisocyanate and polyester polyisocyanate; adducts
thereof with various polyols; and polyisocyanates
polyfunctionalized with an isocyanurate bond, a biuret bond, an
allophanate bond, or the like. In particular, aliphatic isocyanates
are preferably used because of their high reaction speed.
[0085] These isocyanate crosslinking agents may be used alone or in
a mixture of two or more. The total content of the isocyanate
crosslinking agent(s) is preferably 0.01 to 5 parts by weight, more
preferably 0.01 to 4 parts by weight, further more preferably 0.02
to 3 parts by weight, based on 100 parts by weight of the
(meth)acryl-based polymer. The content may be appropriately
determined taking into account cohesive strength, the ability to
prevent delamination in a durability test, or other properties.
[0086] When an aqueous dispersion of a modified (meth)acryl-based
polymer produced by emulsion polymerization is used, the isocyanate
crosslinking agent does not have to be used. If necessary, however,
a blocked isocyanate crosslinking agent may also be used in such a
case, because the isocyanate crosslinking agent itself can easily
react with water.
[0087] The term "epoxy crosslinking agent" refers to a
polyfunctional epoxy compound having two or more epoxy groups per
molecule. Examples of the epoxy crosslinking agent include
bisphenol A, epichlorohydrin-type epoxy resin, ethylene glycol
diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylenediamine,
diglycidylaniline, N,N-diamino glycidyl amine,
1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol
diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene
glycol diglycidyl ether, propylene glycol diglycidyl ether,
polyethylene glycol diglycidyl ether, polypropylene glycol
diglycidyl ether, sorbitol polyglycidyl ether, glycerol
polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerine
diglycidyl ether, glycerine triglycidyl ether, polyglycerol
polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane
polyglycidyl ether, diglycidyl adipate, diglycidyl o-phthalate,
triglycidyl tris(2-hydroxyethyl)isocyanurate, resorcin diglycidyl
ether, bisphenol-S diglycidyl ether, and epoxy resins having two or
more epoxy groups in the molecule. The epoxy crosslinking agent may
also be a commercially available product such as TETRAD-C (trade
name) or TETRAD-X (trade name) manufactured by MITSUBISHI GAS
CHEMICAL COMPANY, INC.
[0088] These epoxy crosslinking agents may be used alone or in a
mixture of two or more. The total content of the epoxy crosslinking
agent(s) is preferably 0.01 to 5 parts by weight, more preferably
0.01 to 4 parts by weight, further more preferably 0.02 to 3 parts
by weight, based on 100 parts by weight of the (meth)acryl-based
polymer. The content may be appropriately determined taking into
account cohesive strength, the ability to prevent delamination in a
durability test, or other properties.
[0089] Any peroxide crosslinking agents capable of generating
active radical species by heating and promoting the crosslinking of
the base polymer in the pressure-sensitive adhesive may be
appropriately used. In view of workability and stability, a
peroxide with a one-minute half-life temperature of 80.degree. C.
to 160.degree. C. is preferably used, and a peroxide with a
one-minute half-life temperature of 90.degree. C. to 140.degree. C.
is more preferably used.
[0090] Examples of the peroxide for use in the invention include
di(2-ethylhexyl) peroxydicarbonate (one-minute half-life
temperature: 90.6.degree. C.), di(4-tert-butylcyclohexyl)
peroxydicarbonate (one-minute half-life temperature: 92.1.degree.
C.), di-sec-butyl peroxydicarbonate (one-minute half-life
temperature: 92.4.degree. C.), tert-butyl peroxyneodecanoate
(one-minute half-life temperature: 103.5.degree. C.), tert-hexyl
peroxypivalate (one-minute half-life temperature: 109.1.degree.
C.), tert-butyl peroxypivalate (one-minute half-life temperature:
110.3.degree. C.), dilauroyl peroxide (one-minute half-life
temperature: 116.4.degree. C.), di-n-octanoylperoxide (one-minute
half-life temperature: 117.4.degree. C.),
1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate (one-minute
half-life temperature: 124.3.degree. C.), di(4-methylbenzoyl)
peroxide (one-minute half-life temperature: 128.2.degree. C.),
dibenzoyl peroxide (one-minute half-life temperature: 130.0.degree.
C.), tert-butyl peroxyisobutylate (one-minute half-life
temperature: 136.1.degree. C.), and
1,1-di(tert-hexylperoxy)cyclohexane (one-minute half-life
temperature: 149.2.degree. C.). In particular,
di(4-tert-butylcyclohexyl) peroxydicarbonate (one-minute half-life
temperature: 92.1.degree. C.), dilauroyl peroxide (one-minute
half-life temperature: 116.4.degree. C.), dibenzoyl peroxide
(one-minute half-life temperature: 130.0.degree. C.), or the like
is preferably used, because they can provide high crosslinking
reaction efficiency.
[0091] The half life of the peroxide is an indicator of how fast
the peroxide can be decomposed and refers to the time required for
the amount of the peroxide to reach one half of its original value.
The decomposition temperature required for a certain half life and
the half life time obtained at a certain temperature are shown in
catalogs furnished by manufacturers, such as "Organic Peroxide
Catalog, 9th Edition, May, 2003" furnished by NOF CORPORATION.
[0092] One of the peroxide crosslinking agents may be used alone,
or a mixture of two or more of the peroxide crosslinking agent may
be used. The total content of the peroxide(s) is preferably from
0.02 to 2 parts by weight, more preferably from 0.05 to 1 part by
weight, based on 100 parts by weight of the (meth)acrylic polymer.
The content of the peroxide (s) may be appropriately selected in
this range in order to control the workability, reworkability,
crosslink stability or peeling properties.
[0093] The amount of decomposition of the peroxide may be
determined by measuring the peroxide residue after the reaction
process by high performance liquid chromatography (HPLC).
[0094] More specifically, for example, after the reaction process,
about 0.2 g of each pressure-sensitive adhesive composition is
taken out, immersed in 10 ml of ethyl acetate, subjected to shaking
extraction at 25.degree. C. and 120 rpm for 3 hours in a shaker,
and then allowed to stand at room temperature for 3 days.
Thereafter, 10 ml of acetonitrile is added, and the mixture is
shaken at 25.degree. C. and 120 rpm for 30 minutes. About 10 .mu.l
of the liquid extract obtained by filtration through a membrane
filter (0.45 .mu.m) is subjected to HPLC by injection and analyzed
so that the amount of the peroxide after the reaction process is
determined.
[0095] As the crosslinking agent, a polyfunctional metal chelate
may also be used in combination with an organic crosslinking agent.
Examples of the polyfunctional metal chelate may include a
polyvalent metal and an organic compound that is covalently or
coordinately bonded to the metal. Examples of the polyvalent metal
atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y,
Ce, Sr, Ba, Mo, La, Sn, and Ti. The organic compound has a covalent
or coordinate bond-forming atom such as an oxygen atom. Examples of
the organic compound include alkyl esters, alcohol compounds,
carboxylic acid compounds, ether compounds, and ketone
compounds.
[0096] The pressure-sensitive adhesive of the invention may contain
a (meth)acryl-based oligomer in view of improving adhesive
strength. The (meth)acryl-based oligomer is preferably a polymer
having a Tg higher than that of the (meth)acryl-based polymer
according to the invention and having a weight average molecular
weight lower than that of the (meth)acryl-based polymer according
to the invention. The (meth)acryl-based oligomer functions as a
tackifying resin and is advantageous in increasing adhesive
strength without raising dielectric constant.
[0097] The (meth)acryl-based oligomer may have a Tg of from about
0.degree. C. to about 300.degree. C., preferably from about
20.degree. C. to about 300.degree. C., more preferably from about
40.degree. C. to about 300.degree. C. When the Tg falls within the
range, the adhesive strength can be improved. Like the Tg of the
(meth)acryl-based polymer, the Tg of the (meth)acryl-based oligomer
is the theoretical value calculated from the Fox equation.
[0098] The (meth)acryl-based oligomer may have a weight average
molecular weight of 1,000 to less than 30,000, preferably 1,500 to
less than 20,000, more preferably 2,000 to less than 10,000. If the
oligomer has a weight average molecular weight of 30,000 or more,
the effect of improving adhesive strength cannot be sufficiently
obtained in some cases. The oligomer with a weight average
molecular weight of less than 1,000 may lower the adhesive strength
or holding performance because of its relatively low molecular
weight. In the invention, the weight average molecular weight of
the (meth)acryl-based oligomer can be determined as a
polystyrene-equivalent weight average molecular weight by GPC
method. More specifically, the weight average molecular weight can
be determined using HPLC 8020 with two TSKgel GMH-H (20) columns
manufactured by TOSOH CORPORATION under the conditions of a solvent
of tetrahydrofuran and a flow rate of about 0.5 ml/minute.
[0099] Examples of monomers that may be used to form the
(meth)acryl-based oligomer include alkyl (meth)acrylate such as
methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,
isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl
(meth)acrylate, sec-butyl (meth)acrylate, tert-butyl
(meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate,
hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl
(meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate,
nonyl (meth)acrylate, isononyl (meth)acrylate, decyl
(meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, or
dodecyl (meth)acrylate; an ester of (meth)acrylic acid and an
alicyclic alcohol, such as cyclohexyl (meth)acrylate or isobornyl
(meth)acrylate; aryl (meth)acrylate such as phenyl (meth)acrylate
or benzyl (meth)acrylate; and a (meth)acrylate derived from a
terpene compound derivative alcohol. These (meth)acrylates may be
used alone or in combination of two or more.
[0100] The (meth)acryl-based oligomer preferably contains, as a
monomer unit, an acrylic monomer having a relatively bulky
structure, typified by an alkyl (meth)acrylate whose alkyl group
has a branched structure, such as isobutyl (meth)acrylate or
tert-butyl (meth)acrylate; an ester of (meth)acrylic acid and an
alicyclic alcohol, such as cyclohexyl (meth)acrylate or isobornyl
(meth)acrylate; or aryl (meth)acrylate such as phenyl
(meth)acrylate or benzyl (meth)acrylate, or any other cyclic
structure-containing (meth)acrylate. The use of a (meth)acryl-based
oligomer with such a bulky structure can further improve the
tackiness of the pressure-sensitive adhesive layer. In terms of
bulkiness, cyclic structure-containing oligomers are highly
effective, and oligomers having two or more rings are more
effective. When ultraviolet (UV) light is used in the process of
synthesizing the (meth)acryl-based oligomer or forming the
pressure-sensitive adhesive layer, a saturated oligomer is
preferred because such an oligomer is less likely to inhibit
polymerization, and an alkyl (meth)acrylate whose alkyl group has a
branched structure or an ester of an alicyclic alcohol and
(meth)acrylic acid is preferably used as a monomer to form the
(meth)acryl-based oligomer.
[0101] From these points of view, preferred examples of the
(meth)acryl-based oligomer include a copolymer of cyclohexyl
methacrylate (CHMA) and isobutyl methacrylate (IBMA), a copolymer
of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate
(IBXMA), a copolymer of cyclohexyl methacrylate (CHMA) and acryloyl
morpholine (ACMO), a copolymer of cyclohexyl methacrylate (CHMA)
and diethylacrylamide (DEAA), a copolymer of 1-adamanthyl acrylate
(ADA) and methyl methacrylate (MMA), a copolymer of dicyclopentanyl
methacrylate (DCPMA) and isobornyl methacrylate (IBXMA), and a
homopolymer of each of dicyclopentanyl methacrylate (DCPMA),
cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA),
isobornyl acrylate (IBXA), a copolymer of dicyclopentanyl
methacrylate (DCPMA) and methyl methacrylate (MMA), dicyclopentanyl
acrylate (DCPA), 1-adamanthyl methacrylate (ADMA), and 1-adamanthyl
acrylate (ADA). In particular, an oligomer composed mainly of CHMA
is preferred.
[0102] In the pressure-sensitive adhesive of the invention, the
content of the (meth)acryl-based oligomer is preferably, but not
limited to, 70 parts by weight or less, more preferably from 1 to
70 parts by weight, even more preferably from 2 to 50 parts by
weight, still more preferably from 3 to 40 parts by weight, based
on 100 parts by weight of the (meth)acryl-based polymer. If the
content of the (meth)acryl-based oligomer is more than 70 parts by
weight, a problem may occur such as an increase in elastic modulus
or a decrease in tackiness at low temperature. Adding 1 part by
weight or more of the (meth)acryl-based oligomer is effective in
improving adhesive strength.
[0103] The pressure-sensitive adhesive of the invention may further
contain a silane coupling agent for improving water resistance at
the interface between the pressure-sensitive adhesive layer and a
hydrophilic adherend, such as glass, bonded thereto. The content of
the silane coupling agent is preferably 1 part by weight or less,
more preferably from 0.01 to 1 part by weight, even more preferably
from 0.02 to 0.6 parts by weight, based on 100 parts by weight of
the (meth)acryl-based polymer. If the content of the silane
coupling agent is too high, the adhesive may have a higher adhesive
strength to glass so that it may be less removable from glass. If
the content of the silane coupling agent is too low, the durability
of the adhesive may undesirably decrease.
[0104] Examples of silane coupling agent preferably can be used
include epoxy group-containing silane coupling agents such as
3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane,
3-glycidoxypropylmethyldiethoxysilane, and
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; amino
group-containing silane coupling agents such as
3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine and
N-phenyl-.gamma.-aminopropyltrimethoxysilane; (meth)acrylic
group-containing silane coupling agents such as
3-acryloxypropyltrimethoxysilane and
3-methacryloxypropyltriethoxysilane; and isocyanate
group-containing silane coupling agents such as
3-isocyanatepropyltriethoxysilane.
[0105] The pressure-sensitive adhesive composition of the invention
may also contain any other known additive. For example, a powder
such as a colorant and a pigment, a dye, a surfactant, a
plasticizer, a tackifier, a surface lubricant, a leveling agent, a
softening agent, an antioxidant, an age resister, a light
stabilizer, an ultraviolet absorbing agent, a polymerization
inhibitor, an inorganic or organic filler, a metal powder, or a
particle- or foil-shaped material may be added as appropriate
depending on the intended use.
[0106] The pressure-sensitive adhesive layer of the invention is
made from the pressure-sensitive adhesive described above. The
thickness of the pressure-sensitive adhesive layer is typically,
but not limited to, about 1 to about 400 .mu.m. The preferred range
of the thickness of the pressure-sensitive adhesive layer may be
appropriately determined depending on the method of producing the
(meth)acryl-based polymer used to form the pressure-sensitive
adhesive. For example, when the (meth)acryl-based polymer is
produced by solution polymerization or the like, the thickness of
the pressure-sensitive adhesive layer is preferably from 1 to 100
.mu.m, more preferably from 2 to 50 .mu.m, even more preferably
from 2 to 40 .mu.m, still more preferably from 5 to 35 .mu.m. When
the (meth)acryl-based polymer is produced by radiation
polymerization or the like, the thickness of the pressure-sensitive
adhesive layer is preferably from 50 to 400 .mu.m, more preferably
from 75 to 300 .mu.m, even more preferably from 100 to 200
.mu.m.
[0107] The pressure-sensitive adhesive layer of the invention
preferably has a relative dielectric constant of 3.5 or less, more
preferably 3.3 or less, even more preferably 3.2 or less, still
more preferably 3.0 or less at a frequency of 100 kHz.
[0108] The pressure-sensitive adhesive layer of the invention
preferably has a gel fraction of 20 to 98% by weight. The gel
fraction of the pressure-sensitive adhesive layer is more
preferably from 30 to 98% by weight, even more preferably from 40
to 95% by weight. When the pressure-sensitive adhesive contains a
crosslinking agent, the gel fraction can be controlled by adjusting
the total amount of the crosslinking agent (s) added, taking
carefully into account the effect of the crosslinking treatment
temperature and the crosslinking treatment time. As the gel
fraction decreases, the cohesive strength may decrease. As the gel
fraction excessively increases, the adhesive strength may degrade.
The pressure-sensitive adhesive layer having a gel fraction in such
a range is characterized in that it shows only a very small
increase in adhesive strength after bonded to an adherend and that
it can be easily removed from the adherend without leaving adhesive
residue even after bonded thereto for a long period of time.
[0109] The pressure-sensitive adhesive layer of the invention
preferably has a haze value of 2% or less when having a thickness
of 25 .mu.m. The pressure-sensitive adhesive layer with a haze
value of 2% or less can satisfy the requirements for transparency
when it is used on optical members. The haze value is preferably
from 0 to 1.5%, more preferably from 0 to 1%. A haze value of 2% or
less is a satisfactory level for optical applications. If the haze
value is more than 2%, cloudiness may occur, which is not preferred
for optical film applications.
[0110] The transparency of the pressure-sensitive adhesive layer is
considered to depend on the total content of the hydroxyl
group-containing monomer and the cyclic nitrogen-containing monomer
based on the total amount of the monomer component. If the total
content is high, the transparency can be high, but too high a total
content may have an adverse effect on other properties. Therefore,
for example, when the content of the cyclic nitrogen-containing
monomer is low, the transparency can be controlled using the
hydroxyl group-containing monomer.
[0111] For example, the pressure-sensitive adhesive layer may be
formed by a method including applying the pressure-sensitive
adhesive to a support, removing the polymerization solvent and so
on by drying to form a pressure-sensitive adhesive sheet. Before
the pressure-sensitive adhesive is applied, appropriately at least
one solvent other than the polymerization solvent may be added to
the pressure-sensitive adhesive.
[0112] Various methods may be used to apply the pressure-sensitive
adhesive layer. Specific examples of such methods include roll
coating, kiss roll coating, gravure coating, reverse coating, roll
brush coating, spray coating, dip roll coating, bar coating, knife
coating, air knife coating, curtain coating, lip coating, and
extrusion coating with a die coater or the like.
[0113] The heat drying temperature is preferably from 40.degree. C.
to 200.degree. C., more preferably from 50.degree. C. to
180.degree. C., in particular, preferably from 70.degree. C. to
170.degree. C. Setting the heating temperature within the above
range makes it possible to obtain a pressure-sensitive adhesive
layer having good adhesive properties. The drying time may be any
appropriate period of time. The drying time is preferably from 5
seconds to 20 minutes, more preferably from 5 seconds to 10
minutes, in particular, preferably from 10 seconds to 5
minutes.
[0114] When the (meth)acryl-based polymer according to the
invention is produced by ultraviolet irradiation of the monomer
component to be polymerized, the pressure-sensitive adhesive layer
may be formed while the (meth)acryl-based polymer is produced from
the monomer component. Appropriate materials such as a crosslinking
agent and other materials that may be added to the
pressure-sensitive adhesive may also be mixed with the monomer
component. Before the ultraviolet irradiation, the monomer
component may be partially polymerized to form a syrup before use.
The ultraviolet irradiation may be performed using a high-pressure
mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or
the like.
[0115] For example, a release-treated sheet may be used as the
support. A silicone release liner is preferably used as the
release-treated sheet.
[0116] In the pressure-sensitive adhesive sheet include the layer
pressure-sensitive adhesive layer formed on the release-treated
sheet, when the pressure-sensitive adhesive layer is exposed, the
pressure-sensitive adhesive layer may be protected with the
release-treated sheet (a separator) before practical use. The
release-treated sheet is peeled off before actual use.
[0117] Examples of the material for forming the separator include a
plastic film such as a polyethylene, polypropylene, polyethylene
terephthalate, or polyester film, a porous material such as paper,
cloth and nonwoven fabric, and an appropriate thin material such as
a net, a foamed sheet, a metal foil, and a laminate thereof. In
particular, a plastic film is preferably used, because of its good
surface smoothness.
[0118] The plastic film may be any film capable of protecting the
pressure-sensitive adhesive layer, and examples thereof include a
polyethylene film, a polypropylene film, a polybutene film, a
polybutadiene film, a polymethylpentene film, a polyvinyl chloride
film, a vinyl chloride copolymer film, a polyethylene terephthalate
film, a polybutylene terephthalate film, a polyurethane film, and
an ethylene-vinyl acetate copolymer film.
[0119] The thickness of the separator is generally from about 5 to
about 200 .mu.m, preferably from about 5 to about 100 .mu.m. If
necessary, the separator may be treated with a release agent such
as a silicone, fluorine, long-chain alkyl, or fatty acid amide
release agent, or may be subjected to release and antifouling
treatment with silica powder or to antistatic treatment of coating
type, kneading and mixing type, vapor-deposition type, or the like.
In particular, if the surface of the separator is appropriately
subjected to release treatment such as silicone treatment,
long-chain alkyl treatment, and fluorine treatment, the
releasability from the pressure-sensitive adhesive layer can be
further increased.
[0120] The pressure-sensitive adhesive layer and the
pressure-sensitive adhesive sheet of the invention are suitable for
use on optical members, and particularly in optical applications,
they are preferably used and bonded to metal thin layers or metal
electrodes. Metal thin layers include thin layers of metal, metal
oxide, or a mixture of metal and metal oxide, and examples of metal
thin layers include, but are not limited to, thin layers of ITO
(indium tin oxide), ZnO, SnO, and CTO (cadmium tin oxide). The
thickness of metal thin layers is typically, but not limited to,
about 10 to 200 nm. Usually, for example, a metal thin layer such
as an ITO layer is provided on a transparent plastic film substrate
such as a polyethylene terephthalate film (specifically, a PET
film) to form a transparent conductive film for use. When the
pressure-sensitive adhesive sheet of the invention is bonded to a
metal thin layer, the surface of the pressure-sensitive adhesive
layer is preferably used as a bonding surface to the metal thin
layer.
[0121] The metal electrodes may be made of metal, metal oxide, or a
mixture of metal and metal oxide, and examples include, but are not
limited to, ITO, silver, copper, and carbon nanotube (CNT)
electrodes.
[0122] A specific example of the use of the pressure-sensitive
adhesive sheet of the invention is a touch panel-forming
pressure-sensitive adhesive sheet, which is used in the manufacture
of a touch panel. For example, the touch panel-forming
pressure-sensitive adhesive sheet is used in the manufacture of a
capacitance touch panel, where it is used to bond a transparent
conductive film having a metal thin layer such as an ITO layer to a
poly (methyl methacrylate) (PMMA) resin sheet, a hard-coated film,
a glass lens, or any other material. Applications of the touch
panel include, but are not limited to, cellular phones, tablet
computers, and personal digital assistances.
[0123] FIG. 1 shows a more specific example of the use of the
pressure-sensitive adhesive layer or the pressure-sensitive
adhesive sheet of the invention, which is an example of a
capacitance touch panel. FIG. 1 shows a capacitance touch panel 1
including a decorative panel 11, pressure-sensitive adhesive layers
or pressure-sensitive adhesive sheets 12, ITO films 13, and a hard
coated film 14. The decorative panel 11 is preferably a glass plate
or a transparent acrylic plate (PMMA plate). Each ITO films 13
preferably includes a glass sheet or a transparent plastic film
(specifically, a PET film) and an ITO layer provided thereon. The
hard coated film 14 is preferably a hard coated transparent plastic
film such as a hard coated PET film. The capacitance touch panel 1
having the pressure-sensitive adhesive layer or the
pressure-sensitive adhesive sheet of the invention can be made
thinner and more stable in operation. The capacitance touch panel 1
also has a good appearance and good visibility.
[0124] An optical member may be used as the support of the
pressure-sensitive adhesive sheet of the invention. The
pressure-sensitive adhesive layer can be formed by a process
including applying the pressure-sensitive adhesive directly to an
optical member and drying the adhesive to remove the polymerization
solvent and the like, so that the pressure-sensitive adhesive layer
is formed on the optical member. Alternatively, the
pressure-sensitive adhesive layer may be formed on a
release-treated separator and then transferred to an optical member
as needed to form a pressure-sensitive adhesive optical member.
[0125] The release-treated sheet used in the preparation of the
pressure-sensitive adhesive optical member may be used by itself as
a separator for the pressure-sensitive adhesive optical member, so
that the process can be simplified.
[0126] The process for forming the pressure-sensitive adhesive
layer for the pressure-sensitive adhesive optical member may
further include forming an anchor layer on the surface of the
optical member or performing any adhesion-facilitating treatment
such as a corona treatment or a plasma treatment before forming the
pressure-sensitive adhesive layer. The surface of the
pressure-sensitive adhesive layer may also be subjected to an
adhesion-facilitating treatment.
[0127] The pressure-sensitive adhesive optical member of the
invention may be used as a pressure-sensitive adhesive
layer-carrying transparent conductive film, which is produced using
a transparent conductive film as an optical member. The transparent
conductive film includes a transparent plastic film substrate and a
transparent conductive thin layer that is formed of a metal thin
layer such as the ITO layer on one surface of the substrate. The
pressure-sensitive adhesive layer of the invention is provided on
the other surface of the transparent plastic film substrate. The
transparent conductive thin layer may be provided on the
transparent plastic film substrate with an undercoat layer
interposed therebetween. Two or more undercoat layers may be
provided. An oligomer migration-preventing layer may be provided
between the transparent plastic film substrate and the
pressure-sensitive adhesive layer.
[0128] The transparent plastic film substrate to be used may be,
but not limited to, various transparent plastic films. The plastic
film is generally formed of a monolayer film. Examples of the
material for the transparent plastic film substrate include
polyester resins such as polyethylene terephthalate and
polyethylene naphthalate, acetate resins, polyethersulfone resins,
polycarbonate resins, polyamide resins, polyimide resins,
polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins,
polyvinylidene chloride resins, polystyrene resins, polyvinyl
alcohol resins, polyarylate resins, and polyphenylene sulfide
resins. In particular, polyester resins, polyimide resins, and
polyethersulfone resins are preferred. The film substrate
preferably has a thickness of 15 to 200 .mu.m.
[0129] The surface of the film substrate may be previously subject
to sputtering, corona discharge treatment, flame treatment,
ultraviolet irradiation, electron beam irradiation, chemical
treatment, etching treatment such as oxidation, or undercoating
treatment such that the adhesion of the transparent conductive thin
layer or the undercoat layer formed thereon to the transparent
plastic film substrate can be improved. If necessary, the film
substrate may also be subjected to dust removing or cleaning by
solvent cleaning, ultrasonic cleaning or the like, before the
transparent conductive thin layer or the undercoat layer is
formed.
[0130] The material and thickness of the transparent conductive
thin layer are not restricted and may be those described for the
metal thin layer. The undercoat layer may be made of an inorganic
material, an organic material or a mixture of an inorganic material
and an organic material. Examples of the inorganic material include
NaF (1.3), Na.sub.3AlF.sub.6 (1.35), LiF (1.36), MgF.sub.2 (1.38),
CaF.sub.2 (1.4), BaF.sub.2 (1.3), SiO.sub.2 (1.46), LaF.sub.3
(1.55), CeF.sub.3 (1.63), and Al.sub.2O.sub.3 (1.63), wherein each
number inside the parentheses is the refractive index of each
material. In particular, SiO.sub.2, MgF.sub.2, Al.sub.2O.sub.3, or
the like is preferably used. In particular, SiO.sub.2 is preferred.
Besides the above, a complex oxide containing about 10 to about 40
parts by weight of cerium oxide and about 0 to about 20 parts by
weight of tin oxide based on 100 parts by weight of the indium
oxide may also be used.
[0131] Examples of the organic material include acrylic resins,
urethane resins, melamine resins, alkyd resins, siloxane polymers,
and organosilane-based condensates. At least one of these organic
materials may be used. In particular, a thermosetting resin
including a mixture composed of a melamine resin, an alkyd resin
and an organosilane condensate is preferably used as the organic
material.
[0132] The thickness of the undercoat layer is generally, but not
limited to, from about 1 to about 300 nm, preferably from 5 to 300
nm, in view of optical design and the effect of preventing the
release of an oligomer from the film substrate.
[0133] The pressure-sensitive adhesive layer-carrying transparent
conductive film can be used to form various devices such as touch
panels and liquid crystal display devices. In particular, the
pressure-sensitive adhesive layer-carrying transparent conductive
film is preferably used as a touch panel-forming electrode sheet.
The touch panel is suitable for use in different types of detection
(such as resistive and capacitance types).
[0134] A capacitance touch panel usually includes a transparent
conductive film that has a transparent conductive thin layer in a
specific pattern and is formed over the surface of a display unit.
The pressure-sensitive adhesive layer-carrying transparent
conductive film is a laminate in which the pressure-sensitive
adhesive layer and the patterned transparent conductive thin layer
are appropriately stacked facing each other.
[0135] The pressure-sensitive adhesive optical member of the
invention may be used as a pressure-sensitive adhesive
layer-carrying optical film, which is produced using an image
display-forming optical film as the optical member.
[0136] The optical film may be of any type for use in forming image
display devices such as liquid crystal display devices and organic
electro-luminescent (EL) display devices. For example, a polarizing
plate is exemplified as the optical film. A polarizing plate
including a polarizer and a transparent protective film provided on
one or both sides of the polarizer is generally used.
[0137] A polarizer is not limited especially but various kinds of
polarizer may be used. As a polarizer, for example, a film that is
uniaxially stretched after having dichromatic substances, such as
iodine and dichromatic dye, absorbed to hydrophilic high molecular
weight polymer films, such as polyvinyl alcohol type film,
partially formalized polyvinyl alcohol type film, and
ethylene-vinyl acetate copolymer type partially saponified film;
poly-ene type alignment films, such as dehydrated polyvinyl alcohol
and dehydrochlorinated polyvinyl chloride, etc. may be mentioned.
In these, a polyvinyl alcohol type film on which dichromatic
materials such as iodine, is absorbed and aligned after stretched
is suitably used. Although thickness of polarizer is not especially
limited, the thickness of about 5 to 80 .mu.m is commonly
adopted.
[0138] A polarizer that is uniaxially stretched after a polyvinyl
alcohol type film dyed with iodine is obtained by stretching a
polyvinyl alcohol film by 3 to 7 times the original length, after
dipped and dyed in aqueous solution of iodine. If needed the film
may also be dipped in aqueous solutions, such as boric acid and
potassium iodide, which may include zinc sulfate, zinc chloride.
Furthermore, before dyeing, the polyvinyl alcohol type film may be
dipped in water and rinsed if needed. By rinsing polyvinyl alcohol
type film with water, effect of preventing un-uniformity, such as
unevenness of dyeing, is expected by making polyvinyl alcohol type
film swelled in addition that also soils and blocking inhibitors on
the polyvinyl alcohol type film surface may be washed off.
Stretching may be applied after dyed with iodine or may be applied
concurrently, or conversely dyeing with iodine may be applied after
stretching. Stretching is applicable in aqueous solutions, such as
boric acid and potassium iodide, and in water bath.
[0139] A thermoplastic resin with a high level of transparency,
mechanical strength, thermal stability, moisture blocking
properties, isotropy, and the like may be used as a material for
forming the transparent protective film. Examples of such a
thermoplastic resin include cellulose resins such as
triacetylcellulose, polyester resins, polyethersulfone resins,
polysulfone resins, polycarbonate resins, polyamide resins,
polyimide resins, polyolefin resins, (meth)acrylic resins, cyclic
olefin polymer resins (norbornene resins), polyarylate resins,
polystyrene resins, polyvinyl alcohol resins, and any mixture
thereof. The transparent protective film is generally laminated to
one side of the polarizer with the adhesive layer, but
thermosetting resins or ultraviolet curing resins such as
(meth)acrylic, urethane, acrylic urethane, epoxy, or silicone
resins may be used to other side of the polarizer for the
transparent protective film. The transparent protective film may
also contain at least one type of any appropriate additive.
Examples of the additive include an ultraviolet absorbing agent, an
antioxidant, a lubricant, a plasticizer, a release agent, an
anti-discoloration agent, a flame retardant, a nucleating agent, an
antistatic agent, a pigment, and a colorant. The content of the
thermoplastic resin in the transparent protective film is
preferably from 50 to 100% by weight, more preferably from 50 to
99% by weight, still more preferably from 60 to 98% by weight,
particularly preferably from 70 to 97% by weight. If the content of
the thermoplastic resin in the transparent protective film is 50%
by weight or less, high transparency and other properties inherent
in the thermoplastic resin can fail to be sufficiently
exhibited.
[0140] Further an optical film of the invention may be used as
other optical layers, such as a reflective plate, a transflective
plate, a retardation plate (a half wavelength plate and a quarter
wavelength plate included), an optical compensation film and a
viewing angle compensation film, which may be used for formation of
a liquid crystal display device etc. These are used in practice as
an optical film, or as one layer or two layers or more of optical
layers laminated with polarizing plate.
[0141] Although an optical film with the above described optical
layer laminated to the polarizing plate may be formed by a method
in which laminating is separately carried out sequentially in
manufacturing process of a liquid crystal display device etc., an
optical film in a form of being laminated beforehand has an
outstanding advantage that it has excellent stability in quality
and assembly workability, etc., and thus manufacturing processes
ability of a liquid crystal display device etc. may be raised.
Proper adhesion means, such as a pressure-sensitive adhesive layer,
may be used for laminating. On the occasion of adhesion of the
above described polarizing plate and other optical layers, the
optical axis may be set as a suitable configuration angle according
to the target retardation characteristics etc.
[0142] The pressure-sensitive adhesive layer-carrying optical film
of the invention is preferably used to form various types of image
display devices such as liquid crystal display devices. Liquid
crystal display devices may be formed according to conventional
techniques. Specifically, liquid crystal display devices are
generally formed by appropriately assembling a liquid crystal cell
and the pressure-sensitive adhesive layer-carrying optical film and
optionally other component such as a lighting system and
incorporating a driving circuit according to any conventional
technique, except that the pressure-sensitive layer-carrying
adhesive optical film of the invention is used. Any type of liquid
crystal cell may also be used such as a TN type, an STN type, a
.PI. type a VA type and IPS type.
[0143] Suitable liquid crystal display devices, such as liquid
crystal display device with which the pressure-sensitive adhesive
layer-carrying optical film has been located at one side or both
sides of the liquid crystal cell, and with which a backlight or a
reflective plate is used for a lighting system may be manufactured.
In this case, the optical film may be installed in one side or both
sides of the liquid crystal cell. When installing the optical films
in both sides, they may be of the same type or of different type.
Furthermore, in assembling a liquid crystal display device,
suitable parts, such as diffusion plate, anti-glare layer,
antireflection film, protective plate, prism array, lens array
sheet, optical diffusion plate, and backlight, may be installed in
suitable position in one layer or two or more layers.
EXAMPLES
[0144] The invention is more specifically described by the examples
below, which are not intended to limit the scope of the invention.
The measurements described below were performed for the evaluation
items in the examples and so on.
Example 1
Preparation of (Meth)acryl-Based Polymer
[0145] To a four-neck flask equipped with a stirring blade, a
thermometer, a nitrogen gas introducing tube, and a condenser were
added 80 parts by weight of isodecyl methacrylate (IDM), 20 parts
by weight of N-vinyl-.epsilon.-caprolactam (NVP), 10 parts by
weight of 2-hydroxybutyl acrylate (HEA), 0.1 parts by weight of
2,2'-azobisisobutyronitrile as a polymerization initiator, and 150
parts by weight of ethyl acetate. Nitrogen gas was introduced for 1
hour to replace the air while the mixture was gently stirred, and
then a polymerization reaction was performed for 15 hours while the
temperature of the liquid in the flask was kept at about 55 to
about 60.degree. C. to obtain (meth)acryl-based polymer
solution.
[0146] To the resulting (meth)acryl-based polymer solution were
added 0.5 parts by weight of a trimethylolpropane adduct of
xylylene diisocyanate (D110N (trade name) manufactured by Mitsui
Chemicals, Inc.) as a crosslinking agent based on 100 parts by
weight of the polymer solid, so that a pressure-sensitive adhesive
solution was obtained.
[0147] The resulting pressure-sensitive adhesive solution was then
applied to one side of a silicone-treated, 75-.mu.m-thick,
polyethylene terephthalate (PET) film (TORAY ADVANCED FILM Co.,
LTD., CERAPEEL) so that a 25-.mu.m-thick pressure-sensitive
adhesive layer could be formed after drying. The coating was dried
at 130.degree. C. for 3 minutes to form a pressure-sensitive
adhesive layer, so that a pressure-sensitive adhesive sheet was
obtained.
Examples 2 to 13 and Comparative Examples 1 to 11
[0148] Pressure-sensitive adhesive sheets were prepared using the
process of Example 1, except that the type and ratio of the
monomers used to form the (meth)acryl-based polymer and the type
and content of the crosslinking agent were changed as shown in
Table 1.
Example 14
Preparation of Monomer Component for Use in UV Polymerization
[0149] To a four-neck flask were added 39 parts by weight of
2-ethylhexyl acrylate (2EHA), 39 parts of isostearyl acrylate
(ISA), 18 parts of N-vinyl-2-pyrrolidone (NVP), 4 parts by weight
of 4-hydroxybutyl acrylate (HBA), 0.05 parts by weight of each of
two photopolymerization initiators (IRGACURE 184 (trade name)
manufactured by BASF and IRGACURE 651 (trade name) manufactured by
BASF), so that a monomer mixture was obtained. Subsequently, the
monomer mixture was partially photo-polymerized by being exposed to
ultraviolet rays in a nitrogen atmosphere, so that a partial
polymer (acryl-based polymer syrup) was obtained with a conversion
of about 10% by weight.
[0150] To 100 parts by weight of the above acryl-based polymer
syrup) were added 0.035 parts by weight of trimethylolpropane
triacrylate. Subsequently, these materials were uniformly mixed to
form a monomer component.
<Production of Pressure-Sensitive Adhesive Layer Using UV
Polymerization>
[0151] Subsequently, a 38-.mu.m-thick polyester film (Diafoil MRF
(trade name) manufactured by Mitsubishi Plastics, Inc.) with its
one side release-treated with silicone was provided, and the
monomer component prepared as described above was applied to the
release-treated surface of the polyester film so that a coating
layer with a final thickness of 100 .mu.m could be formed.
Subsequently, a 38-.mu.m-thick polyester film (Diafoil MRE (trade
name) manufactured by Mitsubishi Plastics, Inc.) with its one side
release-treated with silicone was provided, and the surface of the
applied monomer component was covered with the polyester film in
such a manner that the release-treated surface of the film faced
the coating layer. As a result, the coating layer of the monomer
component was shielded from oxygen. The sheet having the coating
layer obtained as described above was irradiated with ultraviolet
rays from a chemical light lamp (manufactured by TOSHIBA
CORPORATION) at an irradiance of 5 mW/cm.sup.2 (as measured using
TOPCON UVR-T1 having a maximum sensitivity at about 350 nm) for 360
seconds, so that the coating layer was cured to form a
pressure-sensitive adhesive layer, and thus a pressure-sensitive
adhesive sheet was formed. The polyester films placed over both
sides of the pressure-sensitive adhesive layer function as release
liners.
Example 15 to 24
[0152] Pressure-sensitive adhesive sheets were prepared using the
same process as Example 14, except that the type and ratio of the
monofunctional monomer, the type and content of the polyfunctional
monomer used for the preparation of monomer component, the
thickness of the pressure-sensitive adhesive layer were changed as
shown in Table 2.
[0153] The pressure-sensitive adhesive sheets (samples) obtained in
the examples and the comparative examples were evaluated as
described below. Tables 1 and 2 show the evaluation results.
<Measurement of Gel Fraction>
[0154] A predetermined amount (initial weight W1) was sampled from
the pressure-sensitive adhesive layer of the pressure-sensitive
adhesive sheet. The sample was immersed and stored in an ethyl
acetate solution at room temperature for 1 week. The insoluble
matter was then taken out and measured for dry weight (W2). The gel
fraction of the sample was determined from the following formula:
gel fraction=(W2/W1).times.100.
<Dielectric Constant>
[0155] Pressure-sensitive adhesive layers (each obtained by peeling
off the silicone-treated PET film from the pressure-sensitive
adhesive sheet) were stacked to form an about 100-.mu.m-thick
laminate of the pressure-sensitive adhesive layers. The
100-.mu.m-thick and 175-.mu.m-thick samples obtained by UV
Polymerization in Examples 14 to 24 were used without laminating.
The laminate of the pressure-sensitive adhesive layers (or the
pressure-sensitive adhesive layer) was sandwiched between a copper
foil and an electrode and then measured for relative dielectric
constant at a frequency of 100 kHz using the instrument shown
below. Three samples were prepared, and the average of the
measurements for the three samples was determined as the dielectric
constant of the samples. The relative dielectric constant of the
pressure-sensitive adhesive layer at a frequency of 100 kHz was
measured under the following conditions according to JIS K
6911.
[0156] Measurement method: capacitance method (instrument: 4294A
Precision Impedance Analyzer, Agilent Technologies)
[0157] Electrode structure: 12.1 mm.phi., 0.5 mm thick aluminum
plate
[0158] Counter electrode: 3 oz copper plate
[0159] Measurement environment: 23.+-.1.degree. C., 52.+-.1% RH
<Adhesive Strength>
[0160] A 25-.mu.m-thick, PET film (Toray industries Inc., Lumirror
S10) was bonded to the pressure-sensitive adhesive surface of the
sample obtained in each of the examples and the comparative
examples to form an evaluation sample. The evaluation sample was
cut into a piece of 20 mm in width and about 100 mm in length. The
PET film was then peeled off from the sample piece. The resulting
pressure-sensitive adhesive layer was bonded to a 0.5 mm thick
non-alkali glass plate (1737, manufactured by Corning Incorporated)
by a reciprocating motion of a 2 kg roller. After allowed to stand
at room temperature (23.degree. C.) for 1 hour, the
pressure-sensitive adhesive layer was measured for peel adhesive
strength at a peel angle of 90.degree. and a peel rate of 300
mm/minute.
<Measurement of Haze and Total Light Transmittance>
[0161] The pressure-sensitive adhesive sheet obtained in each of
the examples and the comparative examples was bonded to one side of
a non-alkali glass plate with a total light transmittance of 93.3%
and a haze of 0.1%. The haze and the total light transmittance of
the resulting laminate were measured with a haze meter (MR-100
manufactured by MURAKAMI COLOR RESEARCH LABORATORY). For the
measurement with the haze meter, the pressure-sensitive adhesive
sheet was placed on the light source side. The haze value of the
non-alkali glass, 0.1%, was subtracted from the measured value when
the haze value of the pressure-sensitive adhesive sheet was
determined. The measured value was used as the total light
transmittance (%) of the pressure-sensitive adhesive sheet.
<Change in Haze after Humidification>
[0162] A transparent conductive film (a film composed of a
50-.mu.m-thick PET film and ITO vapor-deposited thereon) was
provided. The pressure-sensitive adhesive layer (obtained by
peeling off the silicone-treated PET film from the
pressure-sensitive adhesive sheet) was bonded to the surface of the
transparent conductive film opposite to its surface where the ITO
was vapor-deposited. The resulting pressure-sensitive adhesive
layer-carrying transparent conductive film was bonded to an alkali
glass plate with a haze of 0.2% and then held in an autoclave at
50.degree. C. and 5 atm for 15 minutes. Subsequently, the haze (H1)
of the pressure-sensitive adhesive layer-carrying transparent
conductive film was measured in such an arrangement that the ITO
side of the film was placed on the light source side. After the
measurement of the haze, the pressure-sensitive adhesive
layer-carrying transparent conductive film was placed in a
humidifying oven at 60.degree. C. and 95% R.H. and stored for 250
hours. After the storage, the film was taken out of the oven and
allowed to stand at room temperature (23.degree. C.) for 3 hours.
The haze (H2) of the pressure-sensitive adhesive layer-carrying
transparent conductive film was then measured under the same
conditions. A change in haze was calculated by subtracting the haze
(H1) from the haze (H2). The results are shown in Tables 1 and 2.
The change in haze is preferably less than 1.5%, more preferably
1.4% or less, even more preferably 1.3% or less.
TABLE-US-00001 TABLE 1 Pressure-sensitive adhesive composition
(Meth)acryl- Pressure-sensitive Evaluations based polymer
Crosslinking adhesive layer Total light Change in Monomer type and
agent Thick- Gel Adhesive transmit- haze after component ratio
Content ness fraction Dielectric strength tance humidifi- (weight
ratio) Type (weight parts) (.mu.m) (%) constant (N/20 mm) Haze (%)
cation Example 1 IDM/NVC/HEA = D110N 0.50 25 84.7 2.66 7.50 0.3
92.4 0.6 80/20/10 Example 2 IDM/NVC/HEA = D110N 0.20 25 75.4 2.75
7.00 0.3 92.2 0.5 80/20/15 Example 3 IDM/NVC/HEA = D110N 0.20 25
81.2 2.90 6.80 0.3 92 0.3 80/20/20 Example 4 IDM/NVC/HEA = D110N
0.55 25 83.0 2.50 6.88 0.2 92.3 1.1 85/15/10 Example 5 IDM/NVC/HEA
= D110N 0.30 25 83.7 2.90 7.50 0.2 92.9 0.9 85/15/15 Example 6
IDM/NVC/HEA = D110N 0.50 25 81.3 3.05 8.02 0.2 92.9 0.8 85/15/20
Example 7 IDM/NVC/HEA = D110N 0.15 25 69.6 3.28 12.20 0.2 92.8 0.6
85/15/25 Example 8 IDM/NVC/HBA = D110N 0.75 25 77.0 2.36 8.11 0.3
91.9 0.4 80/20/1 Example 9 IDM/NVC/HBA = D110N 0.20 25 81.5 2.65
8.80 0.3 92.7 0.2 80/20/10 Example 10 IDM/NVC/HBA = D110N 0.20 25
84.3 2.89 10.20 0.3 92.7 0.0 80/20/20 Example 11 IDM/NVP/HBA =
D110N 0.20 25 80.2 2.75 7.90 0.3 92.9 1.0 90/10/10 Example 12
LMA/NVC/HBA = D110N 0.50 25 70.0 2.55 6.90 0.4 92.5 0.6 80/20/10
Example 13 TDMA/NVC/HBA = D110N 0.35 25 70.0 2.47 5.80 0.4 92.1 0.5
70/30/10 Comparative BA/HBA = D110N 0.50 25 87.9 5.30 3.21 0.2 93.6
2.0 Example 1 100/3 Comparative i-OA/HBA = D110N 0.50 25 76.9 3.57
3.00 0.6 93.5 -- Example 2 100/1 Comparative i-AA/HBA = D110N 0.50
25 88.7 4.00 3.65 0.4 93.0 -- Example 3 100/1 Comparative i-NA/HBA
= D110N 0.50 25 81.9 3.55 2.25 0.8 92.7 2.1 Example 4 100/1
Comparative 2EHA/HBA = D110N 0.50 25 79.0 3.70 2.81 0.2 93.0 1.9
Example 5 100/1 Comparative BA/LA/HBA = D110N 0.50 25 85.7 3.95
1.02 0.6 93.1 -- Example 6 60/40/1 Comparative BA/STA/HBA = D110N
0.50 25 80.9 4.01 1.15 0.8 93.2 -- Example 7 60/40/1 Comparative
OA/DA/HBA = D110N 0.50 25 71.1 3.74 0.50 1.0 93.3 -- Example 8
50/50/1 Comparative BA/STA/HBA = D110N 0.50 25 80.9 4.01 1.18 0.8
93.2 -- Example 9 60/40/1 Comparative 2EHA/LA/HBA = D110N 0.50 25
77.6 3.57 1.33 1.0 92.8 -- Example 10 55/45/1 Comparative
2EHA/NVP/HBA = D110N 0.50 25 82.0 3.21 7.89 2.0 92.1 1.7 Example 11
70/30/1
TABLE-US-00002 TABLE 2 Pressure-sensitive adhesive composition
Monofunctional Pressure-sensitive Evaluations monomer
Polyfunctional adhesive layer Total light Change in Monomer type
and monomer Thick- Gel Adhesive transmit- haze after component
ratio Content ness fraction Dielectric strength tance humidifi-
(weight ratio) Type (weight parts) (.mu.m) (%) constant (N/20 mm)
Haze (%) cation Example 14 2EHA/ISTA/NVP/HBA = TMPTA 0.035 100 86.8
2.93 8.2 0.7 92.3 0.1 39/39/18/4 Example 15 2EHA/ISTA/NVP/HBA =
TMPTA 0.01 100 87.0 3.10 33.0 0.6 92.4 1.2 38/38/14/10 Example 16
2EHA/ISTA/NVP/HBA = TMPTA 0.035 175 85.7 3.10 17.1 0.6 92.4 0.4
49/32/18/1 Example 17 i-NA/ISTA/NVP/HBA = TMPTA 0.01 100 78.0 3.11
35.2 0.8 92.2 0.1 47/31/18/4 Example 18 2EHA/ISTA/NVC/HBA = TMPTA
0.035 100 86.1 2.89 6.1 0.5 92.3 1.3 39/39/18/4 Example 19
2EHA/ISTA/NVP/HBA = TMPTA 0.035 100 89.5 2.90 25.2 0.6 92.4 1.0
39/39/18/4 Example 20 i-NA/ISTA/NVP/HBA = TMPTA 0.035 100 90.1 2.94
28.8 0.6 92.3 1.1 39/39/18/4 Example 21 2EHA/IDA/NVC/HBA = TMPTA
0.15 100 97.8 3.34 6.5 0.8 92.2 0.3 39/39/18/4 Example 22
2EHA/ISTA/NVP = TMPTA 0.035 175 83.8 2.88 18.8 0.7 92.3 0.7
41/41/18 Example 23 2EHA/ISTA/NVP/HBA = TMPTA 0.035 175 87.3 2.90
20.3 0.6 92.4 0.6 40.5/40.5/18/1 Example 24 2EHA/ISTA/NVP/HBA =
TMPTA 0 175 51.9 2.97 22.2 0.8 92.3 0.2 39/39/18/4
[0163] In Tables 1 and 2, IDM represents isodecyl methacrylate
(manufactured by Kyoeisha Chemical Co., Ltd., homopolymer
Tg=-41.degree. C.);
[0164] LMA represents lauryl methacrylate (manufactured by Kyoeisha
Chemical Co., Ltd., homopolymer Tg=-65.degree. C.);
[0165] TDMA represents tridecyl methacrylate (manufactured by
Sartomer, homopolymer Tg=-40.degree. C.);
[0166] ISTA represents isostearyl acrylate (manufactured by Osaka
Organic Chemical Industry Ltd., homopolymer Tg=-18.degree. C.);
[0167] IDA represents isodecyl acrylate (manufactured by Sartomer,
homopolymer Tg=-60.degree. C.);
[0168] NVC represents N-vinyl-.epsilon.-caprolactam (manufactured
by BASF);
[0169] NVP represents N-vinyl-2-pyrrolidone (manufactured by NIPPON
SHOKUBAI CO., LTD.);
[0170] TMPTA represents trimethylolpropane triacrylate;
[0171] i-OA represents isooctyl acrylate (manufactured by Osaka
Organic Chemical Industry Ltd., homopolymer Tg=-58.degree. C.);
[0172] i-AA represents isoamyl acrylate (manufactured by Kyoeisha
Chemical Co., Ltd., homopolymer Tg=-45.degree. C.);
[0173] i-NA represents isononyl acrylate (manufactured by Osaka
Organic Chemical Industry Ltd., homopolymer Tg=-58.degree. C.);
[0174] 2EHA represents 2-ethylhexyl acrylate (manufactured by
TOAGOSEI CO., LTD., homopolymer Tg=-70.degree. C.);
[0175] LA represents lauryl acrylate (manufactured by Kyoeisha
Chemical Co., Ltd., homopolymer Tg=-3.degree. C.);
[0176] STA represents stearyl acrylate (manufactured by Osaka
Organic Chemical Industry Ltd., homopolymer Tg=30.degree. C.);
[0177] HEA represents 2-hydroxyethyl acrylate;
[0178] HBA represents 4-hydroxybutyl acrylate;
[0179] BA represents butyl acrylate;
[0180] OA represents octyl acrylate;
[0181] and DA represents decyl acrylate.
[0182] D110N represents a trimethylolpropane adduct of xylylene
diisocyanate (D110N (trade name) manufactured by Mitsui Chemicals,
Inc.).
DESCRIPTION OF REFERENCE SIGNS
[0183] Reference sign 1 represents a capacitance touch panel;
[0184] 11 represents a decorative panel; [0185] 12 represents an
adhesive layer or an adhesive sheet; [0186] 13 represents an ITO
film; [0187] and 14 represents a hard coated film.
* * * * *