U.S. patent application number 17/435893 was filed with the patent office on 2022-06-09 for polymer member/inorganic base composite, production method therefor, and polymer member therefor.
This patent application is currently assigned to TEIJIN LIMITED. The applicant listed for this patent is TEIJIN LIMITED. Invention is credited to Yoshinori IKEDA, Junshi SOEDA.
Application Number | 20220176684 17/435893 |
Document ID | / |
Family ID | 1000006209422 |
Filed Date | 2022-06-09 |
United States Patent
Application |
20220176684 |
Kind Code |
A1 |
SOEDA; Junshi ; et
al. |
June 9, 2022 |
POLYMER MEMBER/INORGANIC BASE COMPOSITE, PRODUCTION METHOD
THEREFOR, AND POLYMER MEMBER THEREFOR
Abstract
A composite of polymer member and inorganic substrate, a method
of manufacturing the same, and a polymer member therefor are
provided. A method for manufacturing a composite 210, 220 of
polymer member and inorganic substrate includes: providing a
composite 110, 120 of thermally modified polymer layer and
inorganic substrate in which one or more thermally modified polymer
layers 20, 21, 22 are adhered onto an inorganic substrate 10, and
bonding a polymer member 30, 31, 32 to the inorganic substrate via
the one or more thermally modified polymer layers 20, 21, 22.
Inventors: |
SOEDA; Junshi; (Osaka-shi,
JP) ; IKEDA; Yoshinori; (Osaka-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
TEIJIN LIMITED |
Osaka-shi, Osaka |
|
JP |
|
|
Assignee: |
TEIJIN LIMITED
Osaka-shi, Osaka
JP
|
Family ID: |
1000006209422 |
Appl. No.: |
17/435893 |
Filed: |
March 6, 2020 |
PCT Filed: |
March 6, 2020 |
PCT NO: |
PCT/JP2020/009831 |
371 Date: |
September 2, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 27/325 20130101;
B32B 7/04 20130101; B32B 9/045 20130101; B32B 15/085 20130101 |
International
Class: |
B32B 27/32 20060101
B32B027/32; B32B 7/04 20060101 B32B007/04; B32B 9/04 20060101
B32B009/04; B32B 15/085 20060101 B32B015/085 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 8, 2019 |
JP |
2019-043196 |
Dec 4, 2019 |
JP |
2019-219698 |
Claims
1. A method for manufacturing a composite of polymer member and
inorganic substrate, comprising: providing a composite of thermally
modified polymer layer and inorganic substrate in which one or more
thermally modified polymer layers are adhered onto an inorganic
substrate, and bonding a polymer member to the inorganic substrate
via the one or more thermally modified polymer layers, wherein the
polymer member at least comprises inorganic particles and a
polymer.
2. The method according to claim 1, wherein the polymer member
further comprises a coupling agent.
3. The method according to claim 1, wherein the polymer member is
in the form of a membrane or film.
4. The method according to claim 1, wherein the bonding of the
polymer member is performed by thermocompression bonding.
5. The method according to claim 1, wherein the one or more
thermally modified polymer layers are formed of an olefin polymer,
and the polymer of the polymer member is an olefin polymer.
6. The method according to claim 5, wherein the olefin polymer is a
cyclic olefin polymer.
7. The method according to claim 1, wherein the inorganic substrate
is selected from a group consisting of metals and metalloids, metal
oxides and metalloid oxides, metal nitrides and metalloid nitrides,
metal carbides and metalloid carbides, carbon materials, and
combinations thereof.
8. A composite of polymer member and inorganic substrate,
comprising: an inorganic substrate, one or more thermally modified
polymer layers adhered to the inorganic substrate, and a polymer
member adhered to the inorganic substrate via the one or more
thermally modified polymer layers, wherein the polymer member at
least comprises inorganic particles and a polymer.
9. The composite according to claim 8, wherein the polymer member
further comprises a coupling agent.
10. The composite according to claim 8, wherein the polymer member
is in the form of a membrane or film.
11. The composite according to claim 8, wherein the one or more
thermally modified polymer layers are formed of an olefin polymer,
and the polymer of the polymer member is an olefin polymer.
12. The composite according to claim 11, wherein the olefin polymer
is a cyclic olefin polymer.
13-21. (canceled)
Description
FIELD
[0001] The present invention relates to a composite of polymer
member and inorganic substrate, a method of manufacturing the same,
and a polymer member therefor.
BACKGROUND OF THE INVENTION
[0002] A polymer member, for example a polyolefin-based polymer
such as polypropylene, polyethylene, and cyclic olefin, has been
widely used in molded articles such as resin films, nonwoven
fabrics, automotive parts, electronic equipment parts, and camera
lenses because of their excellent lightness, mechanical strength,
chemical resistance, and the like. In contrast, inorganic materials
such as metals, semiconductors, or oxides thereof have different
mechanical, thermal, optical, and chemical properties than the
polymer member.
[0003] Accordingly, it has been studied to bond the polymer member
to the inorganic substrate in order to utilize their different
properties in a preferable manner.
[0004] In this regard, for example, in Patent Document 1, an
inorganic material and a polyolefin-based resin material are
integrated without using an adhesive to provide a composite
material useful for a microchip, a liquid crystal protective film
for TV, and the like. Specifically, this Patent Document 1 proposes
a method for producing a composite material comprising an inorganic
material and a polyolefin-based resin material, in which a thin
film having a thickness of 1 to 50 nm consisting of an organic
material with a hydrophilic group is formed on a surface of an
inorganic material, and the inorganic material on which the thin
film has been formed and a polyolefin-based resin material are
irradiated with ultraviolet rays having a wavelength of 100 to 200
nm, respectively, and then the polyolefin-based resin material is
laminated on the thin film of the inorganic material to integrate
the inorganic material and the polyolefin-based resin material.
RELATED ART
Patent Literature
[0005] [Patent Document 1] JP-A-2013-103456
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0006] As described above, it may be preferable to bond a polymer
member to an inorganic substrate without using an adhesive.
Accordingly, in the present invention, there is provided a method
useful for bonding a polymer member to an inorganic substrate
without using an adhesive, as well as a polymer member or the like
used therefor.
Solution to the Problem
[0007] The present invention may include the following
embodiments.
Embodiment 1
[0008] A method for manufacturing a composite of polymer member and
inorganic substrate, comprising:
[0009] providing a composite of thermally modified polymer layer
and inorganic substrate in which one or more thermally modified
polymer layers are adhered onto an inorganic substrate, and
[0010] bonding a polymer member to the inorganic substrate via the
one or more thermally modified polymer layers,
wherein the polymer member at least comprises inorganic particles
and a polymer.
Embodiment 2
[0011] The method according to embodiment 1, wherein the polymer
member further comprises a coupling agent.
Embodiment 3
[0012] The method according to embodiment 1 or 2, wherein the
polymer member is in the form of a membrane or film.
Embodiment 4
[0013] The method according to any one of embodiments 1 to 3,
wherein the bonding of the polymer member is performed by
thermocompression bonding.
Embodiment 5
[0014] The method according to any one of embodiments 1 to 4,
wherein the one or more thermally modified polymer layers are
formed of an olefin polymer, and the polymer of the polymer member
is an olefin polymer.
Embodiment 6
[0015] The method according to embodiment 5, wherein the olefin
polymer is a cyclic olefin polymer.
Embodiment 7
[0016] The method according to any one of embodiments 1 to 6,
wherein the inorganic substrate is selected from a group consisting
of metals and metalloids, metal oxides and metalloid oxides, metal
nitrides and metalloid nitrides, metal carbides and metalloid
carbides, carbon materials, and combinations thereof.
Embodiment 8
[0017] A composite of polymer member and inorganic substrate,
comprising:
[0018] an inorganic substrate,
[0019] one or more thermally modified polymer layers adhered to the
inorganic substrate, and
[0020] a polymer member adhered to the inorganic substrate via the
one or more thermally modified polymer layers
wherein the polymer member at least comprises inorganic particles
and a polymer.
Embodiment 9
[0021] The composite according to embodiment 8, wherein the polymer
member further comprises a coupling agent.
Embodiment 10
[0022] The composite according to embodiment 8 or 9, wherein the
polymer member is in the form of a membrane or film.
Embodiment 11
[0023] The composite according to any one of embodiments 8 to 10,
wherein the one or more thermally modified polymer layers are
formed of an olefin polymer, and the polymer of the polymer member
is an olefin polymer.
Embodiment 12
[0024] The composite according to embodiment 11, wherein the olefin
polymer is a cyclic olefin polymer.
Embodiment 13
[0025] A polymer member at least comprising inorganic particles, a
polymer, and a coupling agent.
Embodiment 14
[0026] The polymer member according to embodiment 13, which is in
the form of a membrane or film.
Embodiment 15
[0027] The polymer member according to embodiment 13 or 14, wherein
the average primary particle diameter of the inorganic particles is
from 1 to 500 nm.
Embodiment 16
[0028] A composite polymer member, comprising:
[0029] a polymer member at least comprising inorganic particles and
a polymer; and
[0030] an additional polymer member at least comprising a
polymer.
Embodiment 17
[0031] The composite polymer member according to embodiment 16,
which is in the form of a membrane or film.
Embodiment 18
[0032] The composite polymer member according to embodiment 16 or
17, wherein the inorganic particles have the average primary
particle diameter of 1 to 500 nm.
Embodiment 19
[0033] The composite polymer member according to any one of
embodiments 16 to 18, wherein at least one of the polymer member
and the additional polymer member further comprises a coupling
agent.
Embodiment 20
[0034] The composite polymer member according to embodiment 19,
wherein the polymer member is in the form of a film and further
comprises a coupling agent, the additional polymer member is in the
form of a film, further comprises inorganic particles, and does not
comprise a coupling agent, and
the composite polymer member is in the form of a film.
Embodiment 21
[0035] The polymer member according to any one of embodiments 13 to
15 and the composite polymer member according to any one of
embodiments 16 to 20, which are for optical use.
Advantageous Effects of Invention
[0036] According to the present disclosure, it is possible to
provide a method which is beneficial for bonding a polymer member
to an inorganic substrate without using an adhesive, and a polymer
member or the like used therefor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1A is a schematic cross-sectional view of a composite
of polymer member and inorganic substrate according to the present
invention;
[0038] FIG. 1B is a schematic cross-sectional view of a composite
of polymer member and inorganic substrate according to the present
invention;
DETAILED DESCRIPTION OF THE EMBODIMENTS
<<Method for Manufacturing a Composite of Polymer Member and
Inorganic Substrate>>
[0039] The method for manufacturing a composite of polymer member
and inorganic substrate according to the present invention
comprises:
[0040] providing a composite of thermally modified polymer layer
and inorganic substrate, in which one or more thermally modified
polymer layers are adhered onto an inorganic substrate, and
[0041] bonding a polymer member to the inorganic substrate via the
one or more thermally modified polymer layers.
[0042] Without wishing to be bound by theory, it is believed that
according to the method of the present invention for manufacturing
a composite of polymer member and inorganic substrate, by bonding
the polymer member to the inorganic substrate via the one or more
thermally modified polymer layers, it is possible to improve the
adhesion of the polymer member to the inorganic substrate. With
respect to the bonding of the polymer member and the inorganic
substrate via the one or more thermally modified polymer layers,
the polymer member can be bonded directly to the one or more
thermally modified polymer layers, or to a thermally unmodified
polymer layer on the one or more thermally modified polymer
layers.
[0043] A method for manufacturing a composite of thermally modified
polymer layer and inorganic substrate in which one or more
thermally modified polymer layers are adhered onto an inorganic
substrate may include forming a first polymer layer on an inorganic
substrate and then heating the first polymer layer to form a first
thermally modified polymer layer, in order to adhere the first
thermally modified polymer layer onto the inorganic substrate.
[0044] Note that, in the composite of polymer member and inorganic
substrate according to the present invention, the polymer member at
least comprises inorganic particles and a polymer, and in
particular at least comprises inorganic particles and a cyclic
olefin polymer.
[0045] When the polymer member comprises inorganic particles, it is
possible to adjust the physical properties, such as the refractive
index, of the polymer member.
[0046] In a preferred embodiment of the composite of polymer member
and inorganic substrate according to the present disclosure, the
polymer member at least comprises inorganic particles, a polymer,
and a coupling agent, and in particular at least comprises
inorganic particles, a cyclic olefin polymer, and a silane coupling
agent.
[0047] When the polymer member further comprises the coupling
agent, the adhesion of the polymer member to the thermally modified
polymer layer can be further improved. In particular, the adhesion
of the polymer member to the thermally modified polymer layer can
be further improved, when the adhesion of the polymer member to the
thermally modified polymer layer is reduced due to the inclusion of
the inorganic particles.
[0048] Without wishing to be bound by theory, it is believed that
this is because the coupling agent, in particular the coupling
agent adhered to the surface of the inorganic particles, improves
the dispersibility of the inorganic particles in the polymer
member, and the remaining coupling agent improves the adhesion of
the polymer member to the thermally modified polymer layer.
<Inorganic Substrate>
[0049] The inorganic substrate used in the method of the present
invention may be any inorganic substrate, and may be selected from
the group consisting of, for example, metals and metalloids, oxides
of metals and metalloids, nitrides of metals and metalloids,
carbides of metals and metalloids, carbon materials, and
combinations thereof. Specifically, examples of the metal include
aluminum, magnesium, titanium, nickel, chromium, iron, copper,
gold, silver, tungsten, zirconium, yttrium, indium, iridium, and
the like, and examples of the metalloid include silicon, germanium,
GaAs, InGaAs, InAlAs, LiTaOx, NbTaOx, ZnTe, GaSe, GaP, CdTe,
diamond, diamond-like carbon, and the like. Therefore, examples of
the metal oxide include oxides of these metals, and examples of the
metalloid oxide include oxides of these metalloids and the like.
Examples of an oxide of silicon includes glass such as quartz glass
and soda glass, and examples of an oxide of aluminum include
sapphire and the like. The nitride may include aluminum nitride,
silicon nitride, and the like. The carbide include silicon carbide.
Further, the carbon material includes diamond and the like.
[0050] The surface of the inorganic substrate, in particular the
metal or the metalloid, may be subjected to a treatment such as
ozonation, ultraviolet treatment, or the like, in order to increase
a functional group, e.g., a hydroxyl group, which can be utilized
for the bonding with the first thermally modified polymer
layer.
[0051] From the viewpoint of stably forming the thermally modified
olefin polymer layer on the inorganic substrate, an inorganic
material having a melting point higher than the thermal
modification temperature (thermal denaturation temperature) of the
thermally modified polymer layer can be preferably used.
[0052] The inorganic substrate may be in any form, and may be, for
example, in the form of a film, a sheet, a plate, a tube, a rod, a
disk, or the like. In addition, the inorganic substrate may be of
any size.
<Thermally Modified Polymer Layer>
[0053] A first polymer layer may be formed on an inorganic
substrate, and then the first polymer layer may be heated to form a
first thermally modified polymer layer, in order to adhere the
first thermally modified polymer layer onto the inorganic
substrate.
[0054] After the formation of the first thermally modified polymer
layer, a second polymer layer may be formed on the first thermally
modified polymer layer, and then the second polymer layer may be
heated to form a second thermally modified polymer layer, in order
to adhere the second thermally modified polymer layer onto the
first thermally modified polymer layer.
[0055] When the second thermally modified polymer layer is used,
the degree of thermal modification of the second thermally modified
polymer layer may be less than the degree of thermal modification
of the first thermally modified polymer layer, so that the first
thermally modified polymer layer provides good bonding to the
inorganic substrate and the second thermally modified polymer layer
provides good bonding to the first thermally modified polymer layer
and the polymer member.
[0056] Further, in the method of the present invention, after
forming the second thermally modified polymer layer, a third
polymer layer may be formed on the second thermally modified
polymer layer, and then the third polymer layer may be heated to
form a third thermally modified polymer layer, in order to adhere
the third thermally modified polymer layer onto the second
thermally modified polymer layer.
[0057] When the third thermally modified polymer layer is used, the
degree of thermal modification of the third thermally modified
polymer layer may be less than the degree of thermal modification
of the second thermally modified polymer layer, so that the second
thermally modified polymer layer provides good bonding to the first
thermally modified polymer layer and the third thermally modified
polymer layer provides good bonding to the second thermally
modified polymer layer and the polymer member.
[0058] Further, additional thermally modified polymer layers such
as a fourth thermally modified polymer layer, a fifth thermally
modified polymer layer, or the like, can be used in the same
manner.
[0059] The degree of thermal modification of these thermally
modified polymer layers can be adjusted by the temperature, time,
ambient atmosphere, and the like of the heating for thermal
modification.
[0060] Specifically, for example, the degree of thermal
modification of the first thermally modified polymer layer may be
such that the first thermally modified polymer layer adheres onto
the inorganic substrate, i.e., such that the adhesion of the first
thermally modified polymer layer to the inorganic substrate is
greater than the adhesion of the thermally unmodified first polymer
layer to the inorganic substrate.
[0061] Similarly, the degree of thermal modification of the second
thermally modified polymer layer may be such that the second
thermally modified polymer layer adheres onto the first thermally
modified polymer layer, i.e., such that the adhesion of the second
thermally modified polymer layer to the first thermally modified
polymer layer is greater than the adhesion of the thermally
unmodified second polymer layer to the first thermally modified
polymer layer.
[0062] Similarly, the degree of thermal modification of the third
thermally modified polymer layer may be such that the third
thermally modified polymer layer adheres to the second thermally
modified polymer layer, i.e., such that the adhesion of the third
thermally modified polymer layer to the second thermally modified
polymer layer is greater than the adhesion of the thermally
unmodified third polymer layer to the second thermally modified
polymer layer.
[0063] The degree of thermal modification of these thermally
modified polymer layers can be adjusted, for example, by the
heating temperature, the oxygen concentration in an atmosphere for
heating, and the like, for the thermal modification of the
thermally modified polymer layer. In other words, in order to
increase the degree of thermal modification, the heating
temperature can be increased and/or the oxygen concentration in the
atmosphere for heating can be increased. On the contrary, in order
to decrease the degree of thermal modification, the heating
temperature can be decreased, and/or the oxygen concentration in
the atmosphere for heating can be decreased.
[0064] The heating temperature for thermal modification of the
thermally modified polymer layer may be 50.degree. C. or more,
100.degree. C. or more, 140.degree. C. or more, 160.degree. C. or
more, 180.degree. C. or more, or 200.degree. C. or more, and may be
500.degree. C. or less, 400.degree. C. or less, 360.degree. C. or
less, 320.degree. C. or less, or 280.degree. C. or less. Further,
this heating can be performed in an oxygen-containing atmosphere,
in particular in air.
[0065] The degree of thermal modification of these thermally
modified polymer layers can be evaluated, for example, using the
oxygen content of the thermally modified polymer constituting the
thermally modified polymer layer, specifically, the ratio of the
number of oxygen atoms contained in the thermally modified polymer
layer to the total number of oxygen atoms and carbon atoms
contained in the thermally modified polymer layer (number of oxygen
atoms/(number of oxygen atoms+number of carbon
atoms).times.100(%)). In this case, it is considered that the
larger the ratio, the larger the degree of thermal modification. A
method for evaluating the content of oxygen atoms and carbon atoms
of the thermally modified polymer layer includes, for example,
X-ray photoelectron spectroscopy (XPS). An XPS device for this
purpose includes a K-Alpha (Thermo Fisher Scientific).
[0066] When such a ratio (number of oxygen atoms/(number of oxygen
atoms+number of carbon atoms).times.100(%)) is 0.3% or more, 0.5%
or more, 1.0% or more, 2.0% or more, or 5.0% or more, and 50% or
less, 30% or less, 20% or less, 10% or less, or 8% or less, it is
particularly appropriate to use this ratio as an index indicating
the degree of thermal modification of the thermally modified
polymer layer.
[0067] When evaluating the degree of thermal modification using the
above ratio (number of oxygen atoms/(number of oxygen atoms+number
of carbon atoms).times.100(%)), the difference in this ratio
between neighboring thermally modified polymer layers, such as the
difference between the ratio of the first thermally modified
polymer layer and the ratio of the second thermally modified
polymer layer, may be 0.1% or more, 0.2% or more, 0.3% or more,
0.4% or more, 0.5% or more, 0.8% or more, 1.0% or more, 2.0% or
more, or 3.0% or more, and may be 10.0% or less, 7.0% or less, 5.0%
or less, 3.0% or less, 2.0% or less, 1.0% or less, 0.5% or less,
0.3% or less or 0.1% or less.
[0068] In other words, for example, the ratio of the number of
oxygen atoms contained in the second thermally modified polymer
layer to the total number of oxygen atoms and carbon atoms
contained in the second thermally modified polymer layer (i.e., the
ratio of the number of oxygen atoms/(the number of oxygen atoms+the
number of carbon atoms).times.100(%) for the second thermally
modified polymer layer) may be 0.1% or more and 10.0% or less
smaller than the ratio of the number of oxygen atoms contained in
the first thermally modified polymer layer to the total number of
oxygen atoms and carbon atoms contained in the first thermally
modified polymer layer (i.e., the ratio of the number of oxygen
atoms/(the number of oxygen atoms+the number of carbon
atoms).times.100(%) for the first thermally modified polymer
layer)
[0069] Further, the degree of thermal modification of these
thermally modified polymer layers can be evaluated, for example, by
IR absorption spectrum of the thermally modified polymer
constituting the thermally modified polymer layer. An IR absorption
analyzer for this purpose includes Nicolet 6700 (Thermo Fisher
SCIENTIFIC). Specifically, the degree of thermal modification of
the thermally modified polymer layer can be evaluated by the ratio
of the intensity of the absorption peak of the C.dbd.O stretching
vibration to the intensity of the absorption peak of the C--H
stretching vibration (a ratio of the intensity of the absorption
peak of C.dbd.O stretching vibration/intensity of the absorption
peak of C--H stretching vibration (-)). In this case, it is
considered that the larger the ratio, the larger the degree of
thermal modification. The intensity of the absorption peak can be
determined by reading the maximum value of the absorbance value of
the absorption peak.
[0070] When such a ratio (a ratio of intensity of absorption peak
of C.dbd.O stretching vibration/intensity of absorption peak of
C--H stretching vibration (-)) is 0.01 or more, 0.02 or more, 0.05
or more, 0.1 or more, 0.15 or more, or 0.20 or more, and 20 or
less, 10 or less, or 5 or less, it is particularly appropriate to
use the ratio as an index indicating the degree of thermal
modification of the thermally modified polymer layer.
[0071] When the degree of thermal modification is evaluated using
the above-described ratio (a ratio of intensity of absorption peak
of C.dbd.O stretching vibration/intensity of absorption peak of
C--H stretching vibration (-)), the difference in this ratio
between neighboring thermally modified polymer layers, such as the
difference between the ratio of the first thermally modified
polymer layer and the ratio of the second thermally modified
polymer layer, may be 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or
more, 0.5 or more, 0.8 or more, 1.0 or more, 2.0 or more, or 3.0 or
more, and may be 10.0 or less, 7.0 or less, 5.0 or less, 3.0 or
less, 2.0 or less, 1.0 or less, 0.5 or less, 0.3 or less, or 0.1 or
less.
[0072] In other words, for example, the ratio of the intensity of
the absorption peak of the C.dbd.O stretching vibration of the
second thermally modified polymer layer to the intensity of the
absorption peak of the C--H stretching vibration of the second
thermally modified polymer layer (i.e., the ratio of the intensity
of the absorption peak of the C.dbd.O stretching vibration/the
intensity of the absorption peak of the C--H stretching vibration
(-) for the second thermally modified polymer layer) may be 0.1 or
more and 20.0 or less smaller than the ratio of the intensity of
the absorption peak of the C.dbd.O stretching vibration of the
first thermally modified polymer layer to the intensity of the
absorption peak of the C--H stretching vibration of the first
thermally modified polymer layer (i.e., the ratio of the intensity
of the absorption peak of the C.dbd.O stretching vibration/the
intensity of the absorption peak of the C--H stretching vibration
(-) for the first thermally modified polymer layer).
[0073] A method for the heating is not particularly limited. The
method for the heating may include a method using a heating source
such as an oven, a hot plate, infrared rays, a flame, a laser, or a
flash lamp.
[0074] Note that the formation of the polymer layer such as the
first polymer layer can be performed by coating and/or
thermocompression bonding.
[0075] When the formation of the polymer layer is carried out by
coating, a polymer constituting the polymer layer may be dissolved
in a solvent to form a solution, a coating may be carried out with
this solution, and then the coated solution may be dried to form a
polymer layer. A coating method in this case may include methods
using a solution, such as a spin coating method, a roll coater
method, a spray coating method, a die coater method, an applicator
method, an immersion coating method, a brush coating, a spatula
coating, a roller coating, a curtain flow coater method and the
like.
[0076] When the polymer layer such as the first polymer layer is
formed by a method using a solution, the method may include a step
of removing the solvent by heating after the coating of the
solution. In this case, as the heating condition, it is possible to
select temperature, heating time and atmospheric pressure condition
which are sufficient to remove the solvent from the coating
film.
[0077] Further, when the coating layer is formed by
thermocompression bonding, it is possible to use a method of
melting or welding a bulk solid, a powder, a film or the like while
optionally applying pressure, such as a hot press method, a welding
method, a powder coating method, or the like.
[0078] Note that the thickness of the polymer layer such as the
first polymer layer may have any thickness, and may have a
thickness which ensures that a thermally modified polymer layer to
be obtained provides good bonding between the inorganic substrate
and the polymer member. The thickness may be, for example, 1 nm or
more, 5 nm or more, or 10 nm or more, and may be 100 .mu.m or less,
30 .mu.m or less, or 10 .mu.m or less, or even 1000 nm or less, 500
nm or less, or 100 nm or less.
[0079] As described above, the thermally modified polymer layer is
a layer via which the polymer member is bonded to the inorganic
substrate. Therefore, this thermally modified polymer layer is
preferably composed of the same type of polymer as the polymer
constituting the polymer member, in order to promote the bonding
between the thermally modified polymer layer and the polymer
member.
[0080] Thus, the polymer layer such as the first polymer layer may
be formed of an olefin polymer, for example, a cyclic olefin
polymer.
[0081] Note that the olefin polymer means a polymer obtained by
polymerizing monomers containing an olefin as the main component;
in other words, the olefin polymer means a polymer obtained by
polymerizing monomers containing 50% by mass or more, 60% by mass
or more, 70% by mass or more, 80% by mass or more, 90% by mass or
more, or 95% by mass or more of a monomer portion derived from an
olefin. Examples of the olefin polymer include polyethylene,
polypropylene, polybutene, polymethylpentene, copolymers of
.alpha.-olefin and ethylene or propylene such as propylene-ethylene
copolymer and propylene-butene copolymer, styrene-butadiene-styrene
block copolymer, styrene-hexadiene-styrene copolymer,
styrene-pentadiene-styrene copolymer, ethylene-propylene-diene
copolymer (RPDM), cyclic olefin polymer, and the like. However, the
present invention is not limited to these examples. These olefin
polymers may be used alone, or two or more thereof may be used in
combination.
[0082] Among these olefin polymers, mention may be made, in
particular, of cyclic olefin polymers.
[0083] The cyclic olefin polymer is a polymer having a cyclic
olefin portion in the polymer main chain. Examples of such a cyclic
olefin polymer include a ring-opening polymer of a cyclic olefin
monomer, an addition polymer of a cyclic olefin monomer, a
copolymer of a cyclic olefin monomer and a linear olefin, and the
like. However, the present invention is not limited to these
examples.
[0084] The cyclic olefin monomer is a compound having a ring
structure formed of carbon atoms and having a carbon-carbon double
bond in the ring structure. Examples of the cyclic olefin monomer
include a norbornene-based monomer containing a norbornene ring,
such as 2-norbornene, norbornadiene and other bicyclic compounds,
dicyclopentadiene, dihydrodicyclopentadiene and other tricyclic
compounds, a tetracyclododecene, ethylidene-tetracyclododecene,
phenyl-tetracyclododecene and other tetracyclic compounds,
tricyclopentadiene and other five-membered ring compounds,
tetracyclopentadiene and other seven-membered ring compounds; and a
monocyclic cyclic olefin such as cyclobutene, cyclopentene,
cyclooctene, cyclododecene, and 1,5-cyclooctadiene. However, the
present invention is not limited to these examples. The cyclic
olefin monomer may have substituent(s) within a range in which the
object of the present invention is not inhibited.
[0085] Cyclic olefin polymers are readily available commercially,
for example, ZEONEX (trade name) Series and ZEONOR (trade name)
Series, etc., from Zeon Corporation; SUMILITE (trade name) Series
from Sumitomo Bakelite Co., LTD.; ARTON (trade name) Series from
JSR Corporation; APEL Series, Mitsui Chemicals Inc.; TOPAS (trade
name) from Ticona; Optolets Series, etc., from Hitachi Chemical
Co., LTD.
[0086] When the polymer member is bonded to a thermally unmodified
polymer layer situated on one or more thermally modified polymer
layers, the thermally unmodified polymer layer is preferably the
same type of polymer as the thermally modified polymer layer such
as the first thermally modified polymer layer and the polymer
member. For example, the thermally modified polymer layer such as
the first thermally modified polymer layer, the thermally
unmodified polymer layer and the polymer member may all be formed
of an olefin polymer such as a cyclic olefin polymer. As for the
specific materials and methods for the formation of the polymer
member, reference may be made to the above description regarding
the thermally modified polymer layers such as the first thermally
modified polymer layer.
<Polymer Member>
[0087] In the method of the present invention, the polymer member
may be a member of any shape, and may be, for example, in the form
of a membrane or film. In this case, the bonding of the polymer
member may be carried out by coating or thermocompression bonding,
in particular by thermocompression bonding. The polymer member at
least comprises inorganic particles and a polymer, and particularly
preferably at least comprises inorganic particles and a cyclic
olefin polymer.
[0088] When the polymer member is in the form of a membrane or a
film, the thickness thereof is preferably 1 cm or less, 5 mm or
less, 2 mm or less, 1 mm or less, 500 .mu.m or less, 200 .mu.m or
less, 100 .mu.m or less, or 50 .mu.m or less, and 1 .mu.m or more,
2 .mu.m or more, 5 .mu.m or more, 10 .mu.m or more, or 15 .mu.m or
more.
[0089] The polymer member preferably further comprises a coupling
agent, in particular a silane coupling agent.
[0090] Such a polymer member may be an optical member, in
particular an anti-reflection film. The polymer member may consist
of a plurality of portions, and in particular, the polymer member
may be a composite film which is a laminate of a plurality of
layers.
[0091] When the polymer member is a composite film which is a
laminate of a plurality of layers, the number of layers of the
laminate is preferably 2 or more, and preferably 500 or less, 100
or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or
less, 10 or less, or 5 or less.
[0092] The thermally modified polymer layer such as the first
thermally modified polymer layer and the polymer member are
preferably the same type of polymer. For example, the thermally
modified polymer layer such as the first thermally modified polymer
layer and the polymer member may be formed of an olefin polymer
such as a cyclic olefin polymer. As for the specific polymers and
methods for the formation of the polymer member, reference may be
made to the above description regarding the thermally modified
polymer layers such as the first thermally modified polymer
layers.
(Inorganic Particle)
[0093] The inorganic particles in the present invention may include
any inorganic particles which can be dispersed in the polymer
member, and examples of such inorganic particles include particles
of metal or metalloid, particles of an oxide or fluoride of metal
or metalloid, and particles of compounds containing metal or
metalloid.
[0094] As the metal or the metalloid, at least one selected from
the group consisting of Si, Ge, Al, Mg, Ti, Ni, Cr, Fe, Cu, Au, Ag,
W, Zr, Y, In, and Ir may be preferably used, and Si and Ge may be
particularly preferably used. Further, as the oxide and the
fluoride of the metal or the metalloid, at least one selected from
the group consisting of MgO, Al.sub.2O.sub.3, Bi.sub.2O.sub.3,
CaF.sub.2, In.sub.2O.sub.3, In.sub.2O.sub.3.SnO.sub.2, HfO.sub.2,
La.sub.2O.sub.3, MgF.sub.2, Sb.sub.2O.sub.5,
Sb.sub.2O.sub.5.SnO.sub.2, SiO.sub.2, SnO.sub.2, TiO.sub.2,
Y.sub.2O.sub.3, ZnO and ZrO.sub.2 may be preferably used, and MgO,
Al.sub.2O.sub.3, SiO.sub.2, TiO.sub.2 may be particularly
preferably used. Further, the compound containing the metal or the
metalloid includes GaAs, InGaAs, InAlAs, LiTaOx, NbTaOx, ZnTe,
GaSe, GaP, CdTe, diamond, diamond-like carbon, SiC, and the
like.
[0095] When the inorganic particles are silicon particles, the
inorganic particles may be silicon particles obtained by a laser
pyrolysis method, in particular, a laser pyrolysis method using a
CO.sub.2 laser.
[0096] The above inorganic particles, particularly the silicon
particles, may contain impurity elements such that the
concentration of each impurity element is 1000 ppm or less, 500 ppm
or less, 300 ppm or less, 100 ppm or less, 50 ppm or less, 10 ppm
or less, or 1 ppm or less, in order to obtain good optical
properties. When the inorganic particles described above are
silicon particles, examples of such impurities include elements in
Group 13 and Group 15.
[0097] Preferably, the average primary particle diameter of the
inorganic particles is 1 nm or more, or 3 nm or more, and 10000 nm
or less, 5000 nm or less, 2000 nm or less, 1000 nm or less, 500 nm
or less, 200 nm or less, 100 nm or less, 50 nm or less, 30 nm or
less, 20 nm or less, or 10 nm or less.
[0098] In the present invention, the average primary particle
diameter of the particles may be obtained as the number average
primary particle diameter, by taking images of the particles with a
scanning electron microscope (SEM), a transmission electron
microscope (TEM) or the like, by measuring the particle diameter
directly based on the images, and by analyzing a group of particles
of 100 or more.
[0099] When the particle diameter is too large, scattering tends to
occur, which may not be preferable. When the particle diameter of
the particles is too small, activation of the particle surface is
facilitated due to an increase in the specific surface area of the
particles, causing a remarkably high cohesiveness between the
particles, and resulting in poor handleability, which may not be
preferable.
[0100] The content ratio of the inorganic particles may be, for
example, such that the volume ratio of the polymer to the inorganic
particles is 1:99 to 99:1, 5:95 to 95:5, 10:90 to 85:15, 20:80 to
80:20, 30:70 to 75:25, or 40:60 to 70:30. When the content of the
inorganic particle is too low, the degree of adjustment of the
refractive index and the like of the polymer member may be reduced,
and when the content of the inorganic particles is too high, the
strength and the like as the polymer member may not be maintained.
When the polymer member is composed of a plurality of portions as
described above, it is preferable that a portion of the polymer
member to be bonded to a composite of thermally modified polymer
layer and inorganic substrate satisfies the above-described volume
ratio of the polymer and the inorganic particles. Thus, for
example, when the polymer member is a composite film which is a
laminate of a plurality of layers, it is preferable that a layer of
the composite film to be bonded to a composite of thermally
modified polymer layer and inorganic substrate satisfies the
above-described volume ratio of the polymer and the inorganic
particles.
[0101] As the coupling agent in the present invention, any coupling
agent which can be combined with the inorganic particles may be
used. Specifically, as the coupling agent, a silane coupling agent,
a titanate coupling agent, or an aluminate coupling agent may be
used, and in particular, a silane coupling agent may be used. When
an olefin polymer such as a cyclic olefin polymer is used as a
polymer of the polymer member, it is possible to use a coupling
agent with a functional group exhibiting good miscibility to these
polymers, for example, a coupling agent with an alkyl chain, a
cyclohexyl group, or a benzene ring, and more specifically, a
coupling agent with an alkyl chain having 1 to 30, 1 to 25, or 1 to
20 carbon atoms, a cyclohexyl group, or a benzene ring. The
coupling agent and/or a hydrolytic condensate of the coupling agent
may be used alone or in combination of two or more.
[0102] Specifically, the coupling agent includes
octadecyltriethoxysilane (OTS), octyltriethoxysilane,
triethoxyphenylsilane, 3-phenylpropyltriethoxysilane,
cyclohexyltrimethoxysilane, octadecyltrimethoxysilane,
octadecyltrichlorosilane, 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltrimethoxysilane,
.gamma.-(2-aminoethyl)aminopropyltriethoxysilane,
.gamma.-(2-aminoethyl)aminopropylmethyldimethoxysilane,
.gamma.-(2-aminoethyl)aminopropylmethyldiethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-methacryloxypropyltriethoxysilane,
N-.beta.-(N-vinylbenzylaminoethyl)-.gamma.-aminopropyltrimethoxysilane
hydrochloride,
N-.beta.-(N-vinylbenzylaminoethyl)-.gamma.-aminopropyltriethoxysilane
hydrochloride, .gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltriethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropyltriethoxysilane, vinyltriacetoxysilane,
.gamma.-anilinopropyltrimethoxysilane,
.gamma.-anilinopropyltriethoxysilane, vinyltrimethoxysilane,
vinyltriethoxysilane,
octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride,
octadecyldimethyl[3-(triethoxysilyl)propyl]ammonium chloride,
.gamma.-ureidopropyltrimethoxysilane,
.gamma.-ureidopropyltriethoxysilane,
3-isocyanatopropyltrimethoxysilane, and
3-isocyanatopropyltriethoxysilane.
[0103] The content ratio of the coupling agent may be, for example,
such that the mass ratio of the inorganic particles to the coupling
agent is 1:99 to 99:1, 5:95 to 95:5, 10:90 to 90:10, 20:80 to
80:20, 30:70 to 70:30, or 40:60 to 60:40. When the content of the
coupling agent is too low, the adhesion between the polymer member
and the thermally modified polymer layer may be insufficient, and
when the content of the coupling agent is too high, strength and
the like as the polymer member may not be maintained.
<<Composite of Polymer Member and Inorganic
Substrate>>
[0104] In the composite of thermally modified polymer layer and
inorganic substrate which can be used for the manufacturing of the
composite of polymer member and inorganic substrate of the present
invention, the one or more thermally modified polymer layers are
adhered to the inorganic substrate. In addition, in the composite
of polymer member and inorganic substrate of the present invention,
the polymer member is adhered to the inorganic substrate via the
one or more thermally modified polymer layers of the composite of
thermally modified polymer layer and inorganic substrate of the
present invention.
[0105] Specifically, as shown in FIG. 1A and FIG. 1B, in the
composites of polymer member and inorganic substrate 210, 220 of
the present invention, the polymer members 30, 31, 32 are bonded to
the inorganic substrate 10 via the one or more thermally modified
polymer layers 20, 21, 22 of the composites of thermally modified
polymer layer and inorganic substrate 110, 120.
[0106] According to the composite of polymer member and inorganic
substrate of the present invention described above, it is possible
to improve the adhesion of the polymer member to the inorganic
substrate.
[0107] For details of each component of the composite of thermally
modified polymer layer and inorganic substrate of the present
invention and the composite of polymer member and inorganic
substrate of the present invention, reference may be made to the
description relating to the method of the present invention.
<<Composite Polymer Member>>
[0108] The polymer member according to the present disclosure may
form a composite polymer member together with an additional polymer
member at least comprising a polymer.
[0109] With respect to the additional polymer member, reference may
be made to the description relating to the polymer member, except
that the additional polymer member may not contain inorganic
particles.
EXAMPLES
Examples 1 to 9 and Comparative Example 1
[0110] In Examples 1 to 9, a laminate was formed which has, on a
silicon substrate 10, first and second thermally modified polymer
layers 21, 22 and first and second anti-reflection layers 31, 32 as
polymer members in this order, as shown in FIG. 1B. For this
laminate, the adhesion of the anti-reflection composite film
composed of the first and second anti-reflection layers to the
silicon substrate was evaluated.
[0111] In Comparative Example 1, a laminate was formed which has,
on a silicon substrate, first and second anti-reflection layers as
polymer members in this order. For this laminate, the adhesion of
the anti-reflection composite film composed of the first and second
anti-reflection layers to the silicon substrate was evaluated.
[0112] Incidentally, in Examples 1 to 9 and Comparative Example 1,
a cyclic olefin polymer (COP) (ZEONEX.TM. 480R; from Zeon
Corporation; glass transition temperature of 138.degree. C.) was
used as a material for both the thermally modified polymer layer
and the polymer member.
Example 1
(1) Preparation of COP Solution A
[0113] A COP solution A was obtained by mixing and stirring 7% by
mass of COP and 93% by mass of toluene at room temperature.
(2) Preparation of the Anti-Reflection Composite Film with the
First and Second Anti-Reflection Films
(a) Preparation of COP Solution B1 (Containing No Silicon
Particles)
[0114] A COP solution B1 was obtained by mixing and stirring 35% by
mass of COP and 65% by mass of toluene at room temperature
(b) Preparation of COP Solution B2 (Containing OTS-Treated Silicon
Particles)
[0115] (b-1) Fabrication of Silicon Particles
[0116] Silicon particles were prepared by laser pyrolysis (LP)
method using carbon dioxide laser, using monosilane gas as a raw
material. Further, the metal impurity content of the obtained
silicon particles was measured using an inductively coupled plasma
mass spectrometer (ICP-MS). As a result, the content of Fe was 15
ppb, the content of Cu was 18 ppb, the content of Ni was 10 ppb,
the content of Cr was 21 ppb, the content of Co was 13 ppb, the
content of Na was 20 ppb, and the content of Ca was 10 ppb. The
average primary particle diameter of the inorganic particles was
100 nm.
(b-2) Surface Treatment of Silicon Particles
[0117] Silicon particles and octadecyltriethoxysilane (OTS) were
placed in a sealed container in an amount such that a ratio of
silicon particles and OTS was 1:1 (mass ratio), and then, after
mixing, heated to 120.degree. C. and held for 3 hours, to obtain
OTS-treated silicon particles.
(b-3) Preparation of COP Solution B2
[0118] A COP solution was obtained by mixing and stirring 10% by
mass of COP and 90% by mass of toluene at room temperature. To this
COP solution, the OTS-treated silicon particles were added and
mixed such that the volume ratio of the COP and the silicon
particles was 65:35. Further, by homogenizing this mixture in a
homogenizer for 15 minutes, a COP solution B2 containing the
OTS-treated silicon particles was prepared.
(c) Preparation of Anti-Reflection Composite Films
[0119] (c-1) Formation of Second Anti-Reflection Layer
[0120] The COP solution B1 obtained as described above was coated
on a glass substrate using a doctor blade to obtain a coating film,
and the solvent in the coating film was removed by heating at
110.degree. C., in order to obtain a second anti-reflection layer
having a thickness of 25 .mu.m on the glass plate.
(c-2) Formation of First Anti-Reflection Layer
[0121] The COP solution B2 obtained as described above was coated
on the second anti-reflection layer using a doctor blade to obtain
a coating film, and the solvent in the coating film was removed by
heating at 110.degree. C., in order to form a first anti-reflection
layer having a thickness of 20 .mu.m on the second anti-reflection
layer having a thickness of 25 .mu.m.
(c-3) Peeling of Anti-Reflection Composite Film
[0122] The first and second anti-reflection layers obtained as
described above were peeled off from the glass plate to obtain an
anti-reflection composite film (a composite polymer member) having
the first and second anti-reflection layers.
(3) Formation of First Thermally Modified Polymer Layer
[0123] A silicon substrate was used as an inorganic substrate, and
a COP solution A was spin-coated on the silicon substrate. The spin
coating was performed by maintaining the rotation speed at 2000 rpm
for 20 seconds.
[0124] Thereafter, the silicon substrate coated with the COP
solution A in this manner was held on a hot plate heated to
120.degree. C. and dried to obtain a silicon substrate having a
first polymer layer. Thereafter, the first polymer layer was
thermally modified (thermally denatured) by holding the substrate
on a hot plate heated to 280.degree. C. over a period of 1 minutes,
in order to form a first thermally modified polymer layer having a
film thickness of 23 nm, which was adhered to the silicon
substrate.
(4) Formation of Second Thermally Modified Polymer Layer
[0125] A COP solution A was spin-coated on the first thermally
modified polymer layer of the silicon substrate obtained as
described above. The spin coating was performed by maintaining the
rotation speed at 2000 rpm for 20 seconds.
[0126] Thereafter, the silicon substrate coated with COP solution A
in this manner was held on a hot plate heated to 120.degree. C. and
dried to form a second polymer layer on the first thermally
modified polymer layer. Thereafter, the second polymer layer was
thermally modified by holding the substrate on a hot plate heated
to 200.degree. C. for 2 minutes, in order to form a second
thermally modified polymer layer having a film thickness of 23 nm,
which was adhered onto the first thermally modified polymer
layer.
(5) Bonding of the Anti-Reflection Composite Film
[0127] The anti-reflection composite film obtained as described
above was adhered onto the second thermally modified polymer layer
of the silicon substrate obtained as described above such that the
first anti-reflection layer was in contact with the second
thermally modified polymer layer, and thermocompression bonding was
performed at 115.degree. C. and 0.2 MPa pressure for 60 minutes to
adhere the anti-reflection composite film onto the second thermally
modified polymer layer. The obtained evaluation laminate had, on
the silicon substrate, the first thermally modified polymer layer,
the second thermally modified polymer layer, the first
anti-reflection layer, and the second anti-reflection layer in this
order.
(Cross-Cut Test)
[0128] The evaluation laminate obtained as described above was
subjected to a cross-cut test.
[0129] Specifically, on the anti-reflection composite film formed
on the silicon substrate, cuts were made at 1 mm intervals to reach
the silicon substrate using a utility knife. After six cuts were
made, six more cuts were made orthogonal to these cuts, in order to
form grid-like cuts.
[0130] Thereafter, Scotch-Mending Tape (manufactured by 3M Company;
810, 24-mm wide) was applied to the surfaces of the polymer member,
and after finger-rubbing the tape from above to adhere it, the tape
was peeled off. The area where the tape was stuck and peeled off in
this way was observed by a stereomicroscope.
[0131] The evaluation results were classified as follows.
[0132] A: The edges of the cuts were perfectly smooth and no
peeling was observed in any cells of the grid.
[0133] B: Although the polymer member was partially peeled off,
less than 35% of the cross-cut section was affected.
[0134] C: Large part of the polymer member was peeled off; 35% or
more of the cross-cut section was affected.
[0135] D: A cross-cut test was not performed because of poor
adhesion of the polymer member to the substrate.
[0136] In the anti-reflection composite film of Example 1, the
edges of the cut were completely smooth, and no peeling was
observed in any cells of the grid (Rating A). The preparation
conditions and evaluation results of the evaluation laminate
according to Example 1 having the first and second thermally
modified polymer layers and the first and second anti-reflection
layers on the silicon substrate are shown in Table 1 below.
Examples 2 to 8
[0137] Evaluation laminates of Examples 2 to 8 having first and
second thermally modified polymer layers and first and second
anti-reflection layers on a silicon substrate were obtained in the
same manner as in Example 1 except that a spray method was used as
the method of forming the second anti-reflection layer (Example 2)
and the volume ratio of the COP and the silicon particles was
changed in the COP solution for preparing COP solution B2 (Examples
3 to 8). The evaluation laminates of Examples 2 to 8 were evaluated
in the same manner as in Example 1. The preparation conditions and
evaluation results of the evaluation laminates according to
Examples 2 to 8 are shown in Table 1 below.
Example 9
[0138] An evaluation laminate having first and second thermally
modified polymer layers and first and second anti-reflection layers
on a silicon substrate was obtained in the same manner as in
Example 1, except that the COP solution B2' (containing
non-OTS-treated silicon particles) was obtained without performing
surface treatment of the silicon particles using OTS in the
manufacturing process of the COP solution B2, and that this COP
solution B2' was used instead of the COP solution B2. The
evaluation laminate according to Example 9 was evaluated in the
same manner as in Example 1. The preparation conditions and
evaluation results of the evaluation laminate according to Example
9 are shown in Table 1 below.
Comparative Example 1
[0139] An evaluation laminate having first and second
anti-reflection layers on a silicon substrate was obtained in the
same manner as in Example 9 except that the first and second
thermally modified polymer layers were not formed. This evaluation
laminate according to Comparative Example 1 was evaluated in the
same manner as in Example 1. The preparation conditions and
evaluation results of the evaluation laminate according to
Comparative Example 1 are shown in Table 1 below.
Example 10
[0140] An evaluation laminate having first and second thermally
modified polymer layers and first to fourth anti-reflection layers
on a silicon substrate was obtained in the same manner as in
Example 1, except as follows:
[0141] (i) A coating film was obtained by applying a COP solution
B1 on a glass plate using a doctor blade, and a solvent in the
coating film was removed by heating at 110.degree. C. to obtain a
fourth anti-reflection layer having a thickness of 25 .mu.m on the
glass plate;
[0142] (ii) After (i) above, a coating film was obtained by
applying the COP solution B2 on the fourth anti-reflection layer
using a doctor blade, and a solvent in the coating film was removed
by heating at 110.degree. C. to obtain a third anti-reflection
layer having a thickness of 20 .mu.m on the fourth anti-reflection
layer;
[0143] (iii) Further, after (ii) above, a coating film was obtained
by applying the COP solution B1 on the third anti-reflection layer
using a doctor blade, and a solvent in the coating film was removed
by heating at 110.degree. C. to obtain a second anti-reflection
layer having a thickness of 25 .mu.m on the third anti-reflection
layer;
[0144] (iv) Further, after (iii) above, a coating film was obtained
by applying COP solution B2 on the second anti-reflection layer
using a doctor blade, and a solvent in the coating film was removed
by heating at 110.degree. C. to obtain a first anti-reflection
layer having a thickness of 20 .mu.m on the second anti-reflection
layer.
[0145] This evaluation laminate according to Example 10 was
evaluated in the same manner as in Example 1. The preparation
conditions and evaluation results of the evaluation laminate
according to Example 10 are shown in Table 2 below.
Example 11
[0146] An evaluation laminate having first and second thermally
modified polymer layers and first to third anti-reflection layers
on a silicon substrate was obtained in the same manner as in
Example 1, except as follows:
[0147] (i) A coating film was obtained by coating a COP solution B1
on a glass plate using a doctor blade, and a solvent in the coating
film was removed by heating at 110.degree. C. to obtain a third
anti-reflection layer having a thickness of 25 .mu.m on the glass
plate;
[0148] (ii) After (i) above, a coating film was obtained by
applying the COP solution B2' used in Example 9, i.e., the COP
solution containing silicon particles not subjected to a surface
treatment with OTS, on the third anti-reflection layer using a
doctor blade, and a solvent in the coating film was removed by
heating at 110.degree. C. to obtain a second anti-reflection layer
having a thickness of 15 .mu.m on the third anti-reflection
layer;
[0149] (iii) Further, after (ii) above, a coating film was obtained
by applying COP solution B2 on the second anti-reflection layer
using a doctor blade, and a solvent in the coating film was removed
by heating at 110.degree. C. to obtain a first anti-reflection
layer having a thickness of 5 .mu.m on the second anti-reflection
layer.
[0150] This evaluation laminate according to Example 11 was
evaluated in the same manner as in Example 1. The preparation
conditions and evaluation results of the evaluation laminate
according to Example 11 are shown in Table 2 below.
TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4
Example 5 Inorganic substrate Si Si Si Si Si First thermally
Polymer C0P C0P C0P C0P C0P modified Thermal 280.degree. C.
280.degree. C. 280.degree. C. 280.degree. C. 280.degree. C. polymer
layer modification temp. Second thermally Polymer C0P C0P C0P C0P
C0P modified Thermal 200.degree. C. 200.degree. C. 200.degree. C.
200.degree. C. 200.degree. C. polymer layer modification temp.
First Polymer C0P C0P C0P C0P C0P anti-reflection Filler Si
particles Si particles Si particles Si particles Si particles layer
Filler content 35 vol % 35 vol % 30 vol % 25 vol % 20 vol %
Coupling agent 0TS 0TS 0TS 0TS 0TS Preparation Blade Blade Blade
Blade Blade method coating coating coating coating coating
Thickness 20 .mu.m 20 .mu.m 20 .mu.m 20 .mu.m 20 .mu.m Second
Polymer C0P C0P C0P C0P C0P anti-reflection Filler -- -- -- -- --
layer Filler content -- -- -- -- -- Coupling agent -- -- -- -- --
Preparation Blade Spraying Blade Blade Blade method coating coating
coating coating Thickness 25 .mu.m 25 .mu.m 25 .mu.m 25 .mu.m 25
.mu.m Bonding method for Thermo- Thermo- Thermo- Thermo- Thermo-
anti-reflection composite film compression compression compression
compression compression bonding bonding bonding bonding bonding
Evaluation result A A A A A Comp. Example 6 Example 7 Example 8
Example 9 Example 1 Inorganic substrate Si Si Si Si Si First
thermally Polymer C0P C0P C0P C0P -- modified Thermal 280.degree.
C. 280.degree. C. 280.degree. C. 280.degree. C. -- polymer layer
modification temp. Second thermally Polymer C0P C0P C0P C0P --
modified Thermal 200.degree. C. 200.degree. C. 200.degree. C.
200.degree. C. -- polymer layer modification temp. First Polymer
C0P C0P C0P C0P C0P anti-reflection Filler Si particles Si
particles Si particles Si particles Si particles layer Filler
content 15 vol % 10 vol % 5 vol % 35 vol % 35 vol % Coupling agent
0TS 0TS 0TS -- -- Preparation Blade Blade Blade Blade Blade method
coating coating coating coating coating Thickness 20 .mu.m 20 .mu.m
20 .mu.m 20 .mu.m 20 .mu.m Second Polymer C0P C0P C0P C0P C0P
anti-reflection Filler -- -- -- -- -- layer Filler content -- -- --
-- -- Coupling agent -- -- -- -- -- Preparation Blade Blade Blade
Blade Blade method coating coating coating coating coating
Thickness 25 .mu.m 25 .mu.m 25 .mu.m 25 .mu.m 25 .mu.m Bonding
method for Thermo- Thermo- Thermo- Thermo Thermo- anti-reflection
composite film compression compression compression compression
compression bonding bonding bonding bonding bonding Evaluation
result A A A C D
TABLE-US-00002 TABLE 2 Example 10 Example 11 Inorganic substrate Si
Si First thermally Polymer COP COP modified polymer Thermal
280.degree. C. 280.degree. C. layer modification temp. Second
thermally Polymer COP COP modified polymer Thermal 200.degree. C.
200.degree. C. layer modification temp. First anti- Polymer COP COP
reflection layer Filler Si particles Si particles Filler content 35
vol % 35 vol % Coupling agent OTS OTS Preparation method Blade
coating Blade coating Thickness 20 .mu.m 5 .mu.m Second anti-
Polymer COP COP reflection layer Filler -- Si particles Filler
content -- 35 vol % Coupling agent -- -- Preparation method Blade
coating Blade coating Thickness 25 .mu.m 15 .mu.m Third anti-
Polymer COP COP reflection layer Filler Si particles -- Filler
content 5 vol % -- Coupling agent OTS -- Preparation method Blade
coating Blade coating Thickness 20 .mu.m 25 .mu.m Fourth anti-
Polymer COP -- reflection layer Filler -- -- Filler content -- --
Coupling agent -- -- Preparation method Blade coating -- Thickness
25 .mu.m -- Bonding method for anti-reflection (.asterisk-pseud.)
(.asterisk-pseud.) composite film Evaluation result A A
(.asterisk-pseud.) Thermocompression bonding
[0151] From the comparison between Examples 1 to 11 and Comparative
Example 1, it is understood that by bonding an anti-reflection film
(polymer member) to an inorganic substrate via a thermally modified
polymer layer, adhesion of the anti-reflection film to the
inorganic substrate is improved.
[0152] Further, as can be seen in Table 1 and Table 2, it is
understood that when an anti-reflection film (polymer member)
contains a coupling agent, adhesion between the thermally modified
polymer layer and the anti-reflection film is further improved even
when the anti-reflection layer contains inorganic particles.
Reference Examples 1 to 14 and Reference Comparative Examples 1 and
2
[0153] In the following Reference Examples and Reference
Comparative Examples, the formation of thermally modified polymer
layers and the adhesion of a polymer member to a thermally modified
polymer layer are evaluated.
[0154] Polymers used for the formation of thermally modified
polymer layers and polymer members in the following reference
examples are as follows:
[0155] COP1: Cyclic olefin polymer (ARTON.TM. (JSR
Corporation))
[0156] COP2: Cyclic olefin polymer (Zeon Corporation, ZEONEX.TM.
480R, glass transition temperature 138.degree. C.)
Reference Examples 1 to 14 and Reference Comparative Examples 1 and
2
[0157] As described below, in Reference Examples 1 to 14, COP1 was
used as a material for both thermally modified polymer layers and
polymer members. In addition, in Reference Comparative Examples 1
and 2, thermally modified polymer layers were not used, and COP1
was used as a material of a polymer member.
Reference Example 1
(Preparation of Solution for Thermally Modified Polymer Layer)
[0158] A solution for thermally modified polymer layer was obtained
by mixing and stirring 7% by mass of COP1 and 93% by mass of
chloroform at room temperature.
(Formation of First Thermally Modified Polymer Layer)
[0159] A silicon substrate was used as inorganic substrate, and the
solution for thermally modified polymer layer was spin-coated on
the silicon substrate. The spin coating was performed by
maintaining the rotation speed at 2000 rpm for 20 seconds.
[0160] Thereafter, the silicon substrate coated with the solution
for thermally modified polymer layer in this manner was held on a
hot plate heated to 120.degree. C. to dry the solution for
thermally modified polymer layer, in order to obtain a silicon
substrate with a first polymer layer, and then the first polymer
layer was thermally modified (thermally denatured) by holding the
substrate on a hot plate heated to 280.degree. C. for 1 minutes to
obtain a silicon substrate with a first thermally modified polymer
layer having a film thickness of 23 nm.
(Formation of Second Thermally Modified Polymer Layer)
[0161] The solution for thermally modified polymer layer was
spin-coated on the first thermally modified polymer layer of the
silicon substrate obtained as described above. The spin coating was
performed by maintaining the rotation speed at 2000 rpm for 20
seconds.
[0162] Thereafter, the silicon substrate coated with the solution
for thermally modified polymer layer in this manner was held on a
hot plate heated to 120.degree. C. to dry the solution for
thermally modified polymer layer, in order to form a second polymer
layer on the first thermally modified polymer layer. Then, the
second polymer layer was thermally modified by holding the
substrate on a hot plate heated to 200.degree. C. for 2 minutes to
obtain a second thermally modified polymer layer having a film
thickness of 23 nm, which was adhered onto the first thermally
modified polymer layer. A composite of thermally modified polymer
layer and inorganic substrate thus obtained was used as the
composite of thermally modified polymer layer and inorganic
substrate according to Reference Example 1.
(Preparation of Solution for Polymer Member)
[0163] A solution for polymer member was obtained by mixing and
stirring 7% by mass of COP1 and 93% by mass of chloroform at room
temperature.
(Bonding of Polymer Member)
[0164] The solution for polymer member was spin-coated on the
second thermally modified polymer layer obtained as described
above. The spin coating was performed by maintaining the rotation
speed at 2000 rpm for 20 seconds.
[0165] Thereafter, the silicon substrate coated with the solution
for polymer member in this manner was held on a hot plate heated to
140.degree. C. for 10 minutes to dry the solution for polymer
member, in order to bond a polymer member having a film thickness
of 23 nm onto the second thermally modified polymer layer. A
composite of polymer member and inorganic substrate thus obtained
was used as the composite of polymer member and inorganic substrate
according to Reference Example 1.
(Cross-Cut Test)
[0166] On the laminate of the first and second thermally modified
polymer layers and the polymer member formed on the silicon
substrate, cuts reaching the silicon substrate were made at 1 mm
intervals by using a utility knife. After six cuts were made, six
more cuts were made orthogonal to these cuts to form grid-like
cuts.
[0167] Thereafter, Scotch-Mending Tape (3M Company; 810, 24-mm
wide) was applied to the surfaces of the polymer member, and after
finger-rubbing the tape from above to adhere it, the tape was
peeled off. The area where the tape was stuck and peeled off in
this way was observed by a stereomicroscope.
[0168] The evaluation results were classified as follows.
[0169] A: The edges of the cuts were perfectly smooth and no
peeling was observed in any cells of the grids.
[0170] B: Although the polymer member was partially peeled off,
less than 35% of the cross-cut section was affected.
[0171] C: Large part of the polymer member was peeled off, and 35%
or more of the cross-cut section was affected.
[0172] In the composite of polymer member and inorganic substrate
of Reference Example 1, the edges of the cuts were completely
smooth, and no peeling was observed in any cells of the grids
(Rating A). The preparation conditions and evaluation results for
this composite material are shown in Table R1 below.
Reference Examples 2 to 8
[0173] Composites of polymer member and inorganic substrate
according to Reference Examples 2 to 8 was prepared in the same
manner as in Reference Example 1, except that the concentration of
the polymer in the solution for thermally modified polymer layer
was changed (Reference Examples 2 and 3), the spin coating
condition of the solution for thermally modified polymer layer was
changed (Reference Example 4), or the temperature of thermal
modification of the first thermally modified polymer was changed
(Reference Examples 5 to 8), as in Tables R1 and R2. The composites
thus prepared were evaluated in the same manner as in Reference
Example 1. The preparation conditions and evaluation results of
these composite materials are shown in Tables R1 and R2 below.
Reference Example 3A
(Formation of First and Second Thermally Modified Polymer
Layers)
[0174] A first thermally modified polymer layer and a second
thermally modified polymer were formed on a silicon substrate in
the same manner as in Reference Example 1, except that the
temperature of thermal modification for the first thermally
modified polymer was 300.degree. C., and the temperature of thermal
modification for the second thermally modified polymer was
280.degree. C. and the treatment was performed for 1 minute.
(Formation of Third Thermally Modified Polymer Layer)
[0175] The solution for thermally modified polymer layer was
spin-coated on the second thermally modified polymer layer obtained
as described above. The spin coating was performed by maintaining
the rotation speed at 2000 rpm for 20 seconds.
[0176] Thereafter, the silicon substrate coated with the solution
for thermally modified polymer layer in this manner was held on a
hot plate heated to 120.degree. C. to dry the solution for
thermally modified polymer layer, in order to form a third polymer
layer on the second thermally modified polymer layer. Then, the
third polymer layer was thermally modified by holding the substrate
on a hot plate heated to 200.degree. C. for 2 minutes to obtain a
third thermally modified polymer layer having a film thickness of
23 nm, which was adhered onto the second thermally modified polymer
layer. A composite of thermally modified polymer layer and
inorganic substrate thus obtained was used as the composite of
thermally modified polymer layer and inorganic substrate of
Reference Example 3A
(Bonding of Polymer Member)
[0177] Thereafter, the composite of polymer member and inorganic
substrate according to Reference Example 3A was prepared by
performing bonding of the polymer member in the same manner as in
Reference Example 1.
(Cross-Cut Test)
[0178] The composite of polymer member and inorganic substrate
according to Reference Example 3A was evaluated in the same manner
as in Reference Example 1.
[0179] The preparation conditions and evaluation results of this
composite material are shown in Table R1 below.
Reference Comparative Example 1
[0180] The composite of polymer member and inorganic substrate
according to Reference Comparative Example 1 was prepared in the
same manner as in Reference Example 1, except that first and second
thermally modified polymer layers were not formed on a silicon
substrate which was used as an inorganic substrate, and that COP1
was spin-coated directly on the silicon substrate. The obtained
composite was evaluated in the same manner as in Reference Example
1. The preparation conditions and evaluation results of this
composite material are shown in Tables R1 and R2 below.
Reference Example 9
[0181] The composite of polymer member and inorganic substrate
according to Reference Example 9 was prepared and evaluated in the
same manner as in Reference Example 1, except that instead of
spin-coating the cyclic olefin polymer during bonding of the
polymer member, a film of COP1 (with a thickness of 100 .mu.m) was
placed on the second thermally modified polymer layer and held at
50 MPa pressure and 140.degree. C. for 2 hours for the
thermocompression-bonding of the film and the second thermally
modified polymer layer. The preparation conditions and evaluation
results of this composite material are shown in Table R3 below.
Reference Comparative Example 2
[0182] The composite polymer member and inorganic substrate
according to Reference Comparative Example 2 was prepared in the
same manner as in Reference Example 9, except that first and second
thermally modified polymer layer were not formed on a silicon
substrate which was used as an inorganic substrate, and a film of
COP1 (thickness: 100 .mu.m) was bonded directly onto the silicon
substrate by thermocompression-bonding. The obtained composite was
evaluated in the same manner as in Reference Example 1. The
preparation conditions and evaluation results of this composite
material are shown in Table R3 below.
Reference Examples 10 to 14
[0183] Composites of polymer member and inorganic substrate
according to Reference Examples 10 to 14 were prepared in the same
manner as in Reference Examples 5, 6, 1, 7 and 8, respectively,
except that after the first thermally modified polymer layer was
formed on the silicon substrate which was used as an inorganic
substrate, a solution for polymer member was spin-coated directly
on the first thermally modified polymer layer without forming a
second thermally modified polymer layer. The obtained composites
were evaluated in the same manner as in Reference Example 1. The
preparation conditions and evaluation results for these composite
materials are shown in Table R4 below.
Reference Examples 15 to 20 and Reference Comparative Example 3
[0184] As described below, in Reference Examples 15 to 20, COP2 was
used as a material for both the thermally modified polymer layer
and the film of the polymer member. In addition, in Reference
Comparative Example 3, the thermally modified polymer layer was not
used, and COP2 was used as a material of the film of the polymer
member.
Reference Example 15
[0185] The composite of polymer member and inorganic substrate
according to Reference Example 15 was prepared in the same manner
as in Reference Example 1, except that in the preparation of both
the solution for thermally modified polymer layer and the solution
for polymer member, a solution for thermally modified polymer layer
was obtained by mixing and stirring 10% by mass of COP2 and 90% by
mass of toluene at room temperature. The obtained composite was
evaluated in the same manner as in Reference Example 1. The
conditions and evaluation results of this composite material are
shown in Table R5 below.
Reference Example 16
[0186] The composite of polymer member and inorganic substrate
according to Reference Example 16 was prepared in the same manner
as in Reference Example 15, except that the concentration of
polymer in the solution for forming thermally modified polymer
layer was changed from 10% by mass to 1% by mass. The obtained
composite was evaluated in the same manner as in Reference Example
1. The preparation conditions and evaluation results of this
composite are shown in Table R5 below.
Reference Comparative Example 3
[0187] The composite of polymer member and inorganic substrate
according to Reference Comparative Example 3 was prepared in the
same manner as in Reference Example 15, except that first and
second thermally modified polymer layers were not formed on the
silicon substrate which was used as an inorganic substrate, and
that COP2 was spin-coated directly on the silicon substrate. The
obtained composite was evaluated in the same manner as in Reference
Example 1. The preparation conditions and evaluation results for
this composite material are shown in Table R5 below.
Reference Examples 17 to 20
[0188] Composites of polymer member and inorganic substrate
according to Reference Examples 17 to 20 were prepared in the same
manner as in Reference Example 15, except that the temperature of
thermal modification for the first thermally modified polymer was
changed as in Table R6. The obtained composites were evaluated in
the same manner as in Reference Example 1. The preparation
conditions and evaluation results for these composite materials are
shown in Table R6 below.
Reference Example 21 and Reference Comparative Example 4
[0189] As described below, in Reference Example 21, a polyethylene
(PE) film (thickness: 30 .mu.m) was used as a material for both the
thermally modified polymer layer and the polymer member. In
addition, in Reference Comparative Example 4, the thermally
modified polymer layer was not used, and a polyethylene film
(thickness: 30 .mu.m) was used as a material of the polymer
member.
Reference Example 21
(Formation of First Thermally Modified Polymer Layer)
[0190] A silicone substrate as inorganic substrate having a
polyethylene film (30 .mu.m thickness) thereon was heated to
120.degree. C. and held for 1 minute to obtain a silicon substrate
with a polyethylene film, and then the polyethylene film was
thermally modified by holding the substrate on a hot plate heated
to 280.degree. C. for 1 minute, in order to obtain a silicon
substrate with a first thermally modified polymer layer.
(Formation of Second Thermally Modified Polymer Layer)
[0191] A polyethylene film (thickness: 30 .mu.m) was placed on the
first thermally modified polymer layer of the silicon substrate
obtained as described above, and the substrate was heated to
120.degree. C. and held for 1 minute to adhere the polyethylene
film onto the first thermally modified polymer layer. Then, the
polyethylene film was thermally modified by holding the substrate
on a hot plate heated to 200.degree. C. for 2 minutes, in order to
obtain a second thermally modified polymer layer, which was adhered
onto the first thermally modified polymer layer. A composite of
thermally modified polymer layer and inorganic substrate thus
obtained was used as the composite of thermally modified polymer
layer and inorganic substrate according to Reference Example
21.
(Bonding of Polymer Member)
[0192] A polyethylene film (thickness: 30 .mu.m) was placed on the
second thermally modified polymer layer obtained as described
above, and the substrate was heated to 120.degree. C. and held for
1 minute, and further heated to 140.degree. C. and held for 10
minutes, to bond the polyethylene film as polymer member onto the
first thermally modified polymer layer. A composite of polymer
member and inorganic substrate thus obtained was used as the
composite of polymer member and inorganic substrate according to
Reference Example 21, and evaluated in the same manner as in
Reference Example 1. The preparation conditions and evaluation
results for this composite material are shown in Table R7
below.
Reference Comparative Example 4
[0193] The composite of polymer member and inorganic substrate
according to Reference Comparative Example 4 was prepared in the
same manner as in Reference Example 21, except that first and
second thermally modified polymer layer were not formed on a
silicon substrate which was used as an inorganic substrate, and a
polyethylene film as polymer member was bonded directly onto the
silicon substrate. The obtained composite was evaluated in the same
manner as in Reference Example 1. The preparation conditions and
evaluation results for this composite material are shown in Table
R7 below.
Reference Examples 22 to 27
[0194] As described below, in Reference Examples 22 to 27,
different polymers were used for the material of thermally modified
polymer layer and for the material of polymer member.
Reference Examples 22 and 23
(Formation of First and Second Thermally Modified Polymer
Layer)
[0195] A silicon substrate was used as an inorganic substrate, and,
as in Reference Example 1, COP1 was used to form first and second
thermally modified polymer layers on the silicon substrate.
(Bonding of Polymer Member)
[0196] In Reference Example 22, the solution for polymer member of
COP2 obtained as described in Reference Example 15 was spin-coated
on the second thermally modified polymer layer obtained as
described above, and dried to form a composite of polymer member
and inorganic substrate according to Reference Example 22. The
obtained composite was evaluated in the same manner as in Reference
Example 1. The preparation conditions and evaluation results for
this composite material are shown in Table R8 below.
[0197] In Reference Example 23, a polyethylene film (thickness: 30
.mu.m) was bonded as in Reference Example 21 on the second
thermally modified polymer layer obtained as described above to
form a composite of polymer member and inorganic substrate
according to Reference Example 23. The obtained composite was
evaluated in the same manner as in Reference Example 1. The
preparation conditions and evaluation results of this composite
material are shown in Table R8 below.
Reference Examples 24 and 25
(Formation of First and Second Thermally Modified Polymer
Layer)
[0198] A silicon substrate was used as an inorganic substrate, and
as in Reference Example 15, COP2 was used to form first and second
thermally modified polymer layers on the silicon substrate.
(Bonding of Polymer Member)
[0199] In Reference Example 24, the solution for polymer member of
COP1 obtained as described in Reference Example 1 was spin-coated
on the second thermally modified polymer layer obtained as
described above, and dried to form a composite of polymer member
and inorganic substrate according to Reference Example 24. The
obtained composite was evaluated in the same manner as in Reference
Example 1. The preparation conditions and evaluation results of
this composite material are shown in Table R8 below.
[0200] In Reference Example 25, a polyethylene film (thickness: 30
.mu.m) was bonded as in Reference Example 21 on the second
thermally modified polymer layer obtained as described above to
form a composite of polymer member and inorganic substrate
according to Reference Example 25. The obtained composite was
evaluated in the same manner as in Reference Example 1. The
preparation conditions and evaluation results for this composite
material are shown in Table R8 below.
Reference Examples 26 and 27
(Formation of First and Second Thermally Modified Polymer
Layer)
[0201] A silicon substrate was used as an inorganic substrate, and
as in Reference Example 21, a polyethylene film (thickness: 30
.mu.m) was used to form first and second thermally modified polymer
layer on the silicon substrate.
(Bonding of Polymer Member)
[0202] In Reference Example 26, the solution for polymer member of
COP1 obtained as described in Reference Example 1 was spin-coated
on the second thermally modified polymer layer obtained as
described above, and dried to form a composite of polymer member
and inorganic substrate according to Reference Example 26. The
obtained composite was evaluated in the same manner as in Reference
Example 1. The preparation conditions and evaluation results of
this composite material are shown in Table R8 below.
[0203] In Reference Example 27, the solution for polymer member of
COP2 obtained as described in Reference Example 15 was spin-coated
on the second thermally modified polymer layer obtained as
described above, and dried to form a composite of polymer member
and inorganic substrate of Reference Example 26. The obtained
composite was evaluated in the same manner as in Reference Example
1. The preparation conditions and evaluation results of this
composite material are shown in Table R8 below.
Reference Examples 28 to 30 and Reference Comparative Examples 5 to
7
Reference Examples 28 to 30
[0204] Composites of polymer member and inorganic substrate
according to Reference Examples 28 to 30 were prepared in the same
manner as in Reference Example 15, except that a silicon substrate
with an SiN layer formed on the surface thereof (Reference Example
28), a copper plate (Reference Example 29), and an aluminum plate
(Reference Example 30) were used as an inorganic substrate,
respectively, instead of a silicon substrate. The obtained
composites were evaluated in the same manner as in Reference
Example 1. The preparation conditions and evaluation results of
these composite materials are shown in Table R9 below.
Reference Comparative Examples 5 to 7
[0205] Composites of polymer member and inorganic substrate
according to Reference Comparative Examples 5 to 7 were prepared in
the same manner as in Reference Examples 28 to 30, respectively,
except that the thermally modified polymer layer was not used. The
obtained composites were evaluated in the same manner as in
Reference Example 1. The preparation conditions and evaluation
results of these composite materials are shown in the following
table.
Reference Comparative Examples 8 to 13
[0206] As described below, in Reference Comparative Examples 8 to
13, a silicon substrate as inorganic substrate was treated with a
silane coupling agent, and a polymer member was bonded to this
treated surface.
Reference Comparative Examples 8 and 9
[0207] An OTS-treated silicon substrate was obtained by treating a
silicon substrate as an inorganic substrate with ultraviolet and
ozone (UV/O.sub.3 treatment), and then by holding the substrate for
3 hours in a saturated vapor pressure atmosphere at 150.degree. C.
of octadecyltriethoxysilane (OTS) as a silane coupling agent.
[0208] In Reference Comparative Example 8, without forming a
thermally modified polymer layer on the surface of the OTS-treated
silicon substrate thus obtained, a polymer member was bonded by
spin-coating in the same manner as in Reference Example 15 to form
a composite of polymer member and inorganic substrate according to
Reference Comparative Example 8. The obtained composite was
evaluated in the same manner as in Reference Example 1. The
preparation conditions and the evaluation results for this
composite material are shown in Table R10 below.
[0209] In Reference Comparative Example 9, without forming a
thermally modified polymer layer on the surface of the OTS-treated
silicon substrate thus obtained, a polymer member was bonded by
thermocompression-bonding in the same manner as in Reference
Example 21 to form a composite of polymer member and inorganic
substrate according to Reference Comparative Example 9. The
obtained composite was evaluated in the same manner as in Reference
Example 1. The preparation conditions and evaluation results of
this composite material are shown in Table R10 below.
Reference Comparative Examples 10 and 11
[0210] Composites of polymer member and inorganic substrate
according to Reference Comparative Examples 10 to 11 were prepared
in the same manner as in Reference Comparative Examples 8 and 9,
respectively, except that 3-phenylpropyltriethoxysilane (PTS) was
used as a silane coupling agent instead of octadecyltriethoxysilane
(OTS). The obtained composites were evaluated in the same manner as
in Reference Example 1. The preparation conditions and evaluation
results of these composite material are shown in Table R10
below.
Reference Comparative Examples 12 and 13
[0211] Composites of polymer member and inorganic substrate
according to Reference Comparative Examples 12 to 13 were prepared
in the same manner as in Reference Comparative Examples 8 and 9,
respectively, except that 3-aminopropyltriethoxysilane (ATS) was
used as a silane coupling agent instead of octadecyltriethoxysilane
(OTS). The obtained composites were evaluated in the same manner as
in Reference Example 1. The preparation conditions and evaluation
results of these composite material are shown in Table R10
below.
TABLE-US-00003 TABLE 3 Table R1 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Third thermally Result Polymer modified modified modified of
concen- polymer layer polymer layer polymer layer Polymer member
cross Inorganic tration Temp. Time Temp. Time Temp. Time Bonding
cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) (.degree. C.) (min) Material method test Ref.
Ex. 1 Si Chloroform COP1*.sup.1 7 280 1 200 2 COP1 Spin A coating
Ref. Ex. 2 Si Chloroform COP1 3 280 1 200 2 COP1 Spin A coating
Ref. Ex. 3 Si Chloroform COP1 1 280 1 200 2 COP1 Spin A coating
Ref. Ex. 3A Si Chloroform COP1 1 300 1 280 1 200 2 COP1 Spin A
coating Ref. Ex. 4*.sup.2 Si Chloroform COP1 1 280 1 200 2 COP1
Spin A coating Ref. Comp. Si COP1 Spin C Ex. 1 coating *.sup.1COP1
is a cyclic olefin polymer(JSR Corporation, ARTON .TM.)
*.sup.2Reference Ex. 4 iSidentical to Reference Ex. 3 except that
the rotation speed of the spin coating in preparation of thermally
modified polymer layer was changed from 2000 rpm to 6000 rpm
TABLE-US-00004 TABLE 4 Table R2 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Result Polymer modified modified of concen- polymer layer polymer
layer Polymer member cross Inorganic tration Temp. Time Temp. Time
Bonding cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) Material method test Ref. Ex. 5 Si Chloroform
COP1*.sup.1 7 360 1 200 2 COP1 Spin B coating Ref. Ex. 6 Si
Chloroform COP1 7 320 1 200 2 COP1 Spin B coating Ref. Ex. 1 Si
Chloroform COP1 7 280 1 200 2 COP1 Spin A coating Ref. Ex. 7 Si
Chloroform COP1 7 240 1 200 2 COP1 Spin B coating Ref. Ex. 8 Si
Chloroform COP1 7 200 1 200 2 COP1 Spin B coating Ref. Comp. Si
COP1 Spin C Ex. 1 coating *.sup.1COP1 is a cyclic olefin
polymer(JSR Corporation, AHTON .TM.)
TABLE-US-00005 TABLE 5 Table R3 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Result Polymer modified modified of concen- polymer layer polymer
layer Polymer member cross Inorganic tration Temp. Time Temp. Time
Bonding cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) Material method test Ref. Ex. 9 Si Chloroform
COP1*.sup.1 7 280 1 200 2 COP1 (.asterisk-pseud.) A film Ref. Comp.
Si COP1 (.asterisk-pseud.) C Ex. 2 film *.sup.1COP1 is a cyclic
olefin polymer (JSR Corporation, ARTON .TM.) (.asterisk-pseud.)
Thermocompression bonding
TABLE-US-00006 TABLE 6 Table R4 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Result Polymer modified modified of concen- polymer layer polymer
layer Polymer member cross Inorganic tration Temp. Time Temp. Time
Bonding cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) Material method test Ref. Ex. 10 Si Chloroform
COP1*.sup.1 7 360 1 COP1 Spin B coating Ref. Ex. 11 Si Chloroform
COP1 7 320 1 COP1 Spin B coating Ref. Ex. 12 Si Chloroform COP1 7
280 1 COP1 Spin B coating Ref. Ex. 13 Si Chloroform COP1 7 240 1
COP1 Spin B coating Ref. Ex. 14 Si Chloroform COP1 7 200 1 COP1
Spin B coating Ref. Comp. Si COP1 Spin C Ex. 1 coating *.sup.1COP1
is a cyclic olefin polymer (JSR Corporation, ARTON .TM.)
TABLE-US-00007 TABLE 7 Table R5 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Result Polymer modified modified of concen- polymer layer polymer
layer Polymer member cross Inorganic tration Temp. Time Temp. Time
Bonding cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) Material method test Ref. Ex. 15 Si Toluene
COP2*.sup.3 10 280 1 200 2 COP2 Spin A coating Ref. Ex. 16 Si
Toluene COP2 1 280 1 200 2 COP2 Spin A coating Ref. Comp. Si COP2
Spin C Ex. 3 coating *.sup.3COP2 is a cyclic olefin polymer (Zeon
Corporation, Zeonex .TM. 480R)
TABLE-US-00008 TABLE 8 Table R6 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Result Polymer modified modified of concen- polymer layer polymer
layer Polymer member cross Inorganic tration Temp. Time Temp. Time
Bonding cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) Material method test Ref. Ex. 17 Si Toluene
COP2*.sup.3 10 360 1 200 2 COP2 Spin B coating Ref. Ex. 18 Si
Toluene COP2 10 320 1 200 2 COP2 Spin B coating Ref. Ex. 10 Si
Toluene COP2 10 280 1 200 2 COP2 Spin A coating Ref. Ex. 19 Si
Toluene COP2 10 240 1 200 2 COP2 Spin B coating Ref. Ex. 20 Si
Toluene COP2 10 200 1 200 2 COP2 Spin B coating Ref. Comp. Si COP2
Spin C Ex. 3 coating *.sup.3COP2 is a cyclic olefin polymer (Zeon
Corporation, Zeonex .TM. 480R)
TABLE-US-00009 TABLE 9 Table R7 Thermally modified polymer layer
Preparation condition First thermally Second thermally Result
modified modified of polymer layer polymer layer Polymer member
cross Inorganic Temp. Time Temp. Time Bonding cut substrate
Material (.degree. C.) (min) (.degree. C.) (min) Material method
test Ref. Ex. 21 Si PE film*.sup.4 280 1 200 2 PE film
(.asterisk-pseud.) A Ref. Comp. Si PE film (.asterisk-pseud.) C Ex.
4 *.sup.4PE film is a polyethylene film (thickness of 30 .mu.m)
(.asterisk-pseud.) Thermocompression bonding
TABLE-US-00010 TABLE 10 Table R8 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Result Polymer modified modified of concen- polymer layer polymer
layer Polymer member cross Inorganic tration Temp. Time Temp. Time
Bonding cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) Material method test Ref. Ex. 22 Si Chloroform
COP1*.sup.1 7 280 1 200 2 COP2 Spin B coating Ref. Ex. 23 Si
Chloroform COP1 7 280 1 200 2 PE film (.asterisk-pseud.) B Ref. Ex.
24 Si Toluene COP2*.sup.3 10 280 1 200 2 COP1 Spin A coating Ref.
Ex. 25 Si Toluene COP2 10 280 1 200 2 PE film (.asterisk-pseud.) B
Ref. Ex. 26 Si PE film*.sup.4 280 1 200 2 COP1 Spin B coating Ref.
Ex. 27 Si PE film 280 1 200 2 COP2 Spin B coating Ref. Comp. Si
COP1 Spin C Ex. 1 coating Ref. Comp. Si COP2 Spin C Ex. 3 coating
Ref. Comp. Si PE film (.asterisk-pseud.) C Ex. 4 *.sup.1COP1 is a
cyclic olefin polymer (JSR Corporation, ARTON .TM.) *.sup.3COP2 is
a cyclic olefin polymer (Zeon Corporation, Zeonex .TM. 480R)
*.sup.4PE film is a polyethylene film (thickness of 30 .mu.m)
(.asterisk-pseud.) Thermocompression bonding
TABLE-US-00011 TABLE 11 Table R9 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Result Polymer modified modified of concen- polymer layer polymer
layer Polymer member cross Inorganic tration Temp. Time Temp. Time
Bonding cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) Material method test Ref. Ex. 28 SiN Toluene
COP2*.sup.3 10 280 1 200 2 COP2 Spin A coating Ref. Comp. SiN COP2
Spin C Ex. 5 coating Ref. Ex. 29 Cu Toluene COP2 10 280 1 200 2
COP2 Spin A coating Ref. Comp. Cu COP2 Spin C Ex. 6 coating Ref.
Ex. 30 Al Toluene COP2 10 280 1 200 2 COP2 Spin A coating Ref.
Comp. Al COP2 Spin C Ex. 7 coating *.sup.3COP2 is a cyclic olefin
polymer (Zeon Corporation, Zeonex .TM. 480R )
TABLE-US-00012 TABLE 12 Table R10 Thermally modified polymer layer
Preparation condition Material First thermally Second thermally
Result Polymer modified modified of concen- polymer layer polymer
layer Polymer member cross Inorganic tration Temp. Time Temp. Time
Bonding cut substrate Solvent Polymer (mass %) (.degree. C.) (min)
(.degree. C.) (min) Material method test Ref. Comp. OTS treated
COP2*.sup.3 Spin C Ex. 8 Si coating Ref. Comp. OTS treated PE
film*.sup.4 (.asterisk-pseud.) C Ex. 9 Si Ref. Comp. PTS treated
COP2 Spin C Ex. 10 Si coating Ref. Comp. PTS treated PE film
(.asterisk-pseud.) C Ex. 11 Si Ref. Comp. ATS treated COP2 Spin C
Ex. 12 Si coating Ref. Comp. ATS treated PE film (.asterisk-pseud.)
C Ex. 13 Si *.sup.3COP2 is a cyclic olefin polymer (Zeon
Corporation, Zeonex .TM. 480R) *.sup.4PE film is a polyethylene
film (thickness of 30 .mu.m) (.asterisk-pseud.) Thermocompression
bonding
<Evaluation Result>
[0212] From Table R1 above, it is understood that, when the polymer
concentration in the polymer solution for forming thermally
modified polymer layer was 1 to 7% by mass and the rotation speed
of the spin-coating at the time of forming thermally modified
polymer layer was 2000 to 4000 rpm (Reference Examples 1 to 4),
peeling of the polymer member was suppressed as compared with the
case where the thermally modified polymer layer was not used
(Reference Comparative Example 1).
[0213] In addition, from Table R1 above, it is understood that, not
only when two thermally modified polymer layers were used
(Reference Examples 1 to 4) but also when three thermally modified
polymer layers were used (Reference Example 3A), peeling of the
polymer member was suppressed as compared with the case where the
thermally modified polymer layer was not used (Reference
Comparative Example 1).
[0214] From Table R2 above, it is understood that, when the thermal
modification temperature for forming thermally modified polymer
layer was 200.degree. C. to 360.degree. C. (Reference Examples 1
and 5 to 8), peeling of the polymer member was suppressed as
compared with a case where the thermally modified polymer layer was
not used (Reference Comparative Example 1).
[0215] From Table R3 above, it is understood that, when the polymer
member film was bonded to the thermally modified polymer layer by
thermocompression-bonding (Reference Example 9), peeling of the
polymer member was suppressed as compared with the case where the
polymer member was directly bonded to the silicon substrate by
thermocompression-bonding without using the thermally modified
polymer layer (Reference Comparative Example 2).
[0216] From Table R4 above, it is understood that, even when only
one thermally modified polymer layer was used instead of two
thermally modified polymer layers (Reference Examples 10 to 14),
peeling of the polymer member was suppressed as compared with the
case where the thermally modified polymer layer was not used
(Reference Comparative Example 1)
[0217] From Table R5 above, it is understood that, when the polymer
concentration in the polymer solution for forming thermally
modified polymer layer was 1 to 10% by mass (Reference Examples 15
to 16), peeling of the polymer member was suppressed as compared
with the case where the thermally modified polymer layer was not
used (Reference Comparative Example 3)
[0218] From Table R6 above, it is understood that, when the thermal
modification temperature for forming thermally modified polymer
layer was 200.degree. C. to 360.degree. C. (Reference Examples 10
and 17 to 20), peeling of the polymer member was suppressed as
compared with the case where the thermally modified polymer layer
was not used (Reference Comparative Example 3).
[0219] From Table R7 above, it is understood that, when the polymer
member film was bonded to the thermally modified polymer layer by
thermocompression-bonding (Reference Example 21), peeling of the
polymer member was suppressed as compared with the case where the
polymer member film was directly bonded to the silicon substrate by
thermocompression-bonding without using the thermally modified
polymer layer (Reference Comparative Example 4).
[0220] From Table R8 above, it is understood that, even under the
condition where the polymer for forming thermally modified polymer
layer and the polymer for forming polymer member are different from
each other, when the thermally modified polymer layer was used
(Reference Examples 22 to 27), peeling of the polymer member was
suppressed, as compared with the case where the thermally modified
polymer layer was not used (Reference Comparative Examples 1, 3 and
4).
[0221] From Table R9 above, it is understood that, even under the
condition where a silicon substrate with SiN formed on the surface
thereof, a copper plate, and an aluminum plate were used as a
substrate instead of a silicon substrate, when the thermally
modified polymer layer was used (Reference Examples 28 to 30),
peeling of the polymer member was suppressed, as compared with the
case where the thermally modified polymer layer was not used
(Reference Comparative Examples 5 to 7).
[0222] From Table R10 above, it is understood that, even under the
condition where the substrate was a silicon substrate treated with
a silane coupling agent, peeling of the polymer member was not
suppressed as compared with the case where the thermally modified
polymer layers were used (Reference Examples).
Reference Examples 31 to 36
[0223] A silicon substrate was used as an inorganic substrate, and
a silicon substrate with thermally modified polymer layer was
obtained on the silicon substrate in the same manner as in
Reference Example 1, except that a solution for thermally modified
polymer layer was obtained by mixing and stirring 20% by mass of
COP1 and 80% by mass of chloroform at room temperature, and the
temperature of the hot plate for thermal modification was changed
to 400.degree. C. (Reference Example 31), 320.degree. C. (Reference
Example 32), 280.degree. C. (Reference Example 33), 240.degree. C.
(Reference Example 34), 200.degree. C. (Reference Example 35), and
160.degree. C. (Reference Example 36).
(Elemental Analysis by XPS)
[0224] For the thermally modified polymer layers of Reference
Examples 31 to 36, a ratio of the number of oxygen atoms contained
in the thermally modified polymer layer to the total number of
oxygen atoms and carbon atoms contained in the thermally modified
polymer layer (number of O atoms/(number of O atoms+number of C
atoms) (%)) was determined using an XPS device (K-Alpha (from
Thermo Fisher Scientific)).
[0225] Measurement was performed using monochromatized AlK.alpha.
rays as an X-ray source and with a photoelectron extraction angle
of 0 degree. The O1s peak area was determined by drawing a baseline
according to Shirley method in the range of 527 to 537 eV, and the
C1s peak area was determined by drawing a baseline according to
Shirley method in the range of 280 to 290 eV. The oxygen
concentration and carbon concentration on the surface of the film
were obtained by correcting the above-mentioned O1s peak area and
C1s peak area with a sensitivity coefficient inherent to respective
devices.
[0226] Preparation conditions and evaluation results of the
thermally modified polymer layer are shown in Table R11 below. It
is understood from this Table R11 that as the temperature for the
thermal modification decreases, i.e. as the degree of thermal
modification decreases, this ratio (number of O atoms/(number of O
atoms+number of C atoms) (%)) decreases. Therefore, it is
understood that this ratio can be used as an index of the degree of
thermal modification of a thermally modified polymer layer.
(Measurement of Infrared Absorption Spectrum)
[0227] For the thermally modified polymer layers of Reference
Examples 31 to 36, infrared transmission absorption spectrum
ranging from 4000 to 500 cm.sup.-1 was measured using an IR
absorption spectrometer (Nicolet 6700 (from Thermo Fisher
Scientific)) to determine the ratio of the absorption peak
intensity of C.dbd.O stretching vibration peaking at 1732 cm.sup.-1
to the absorption peak intensity of C--H stretching vibration
peaking at 2947 cm.sup.-1 (ratio of the absorption peak intensity
of C.dbd.O stretching vibration/the absorption peak intensity of
C--H stretching vibration (-)). The absorption peak intensity was
determined by reading the maximum value of the absorbance value of
the absorption peak.
[0228] Preparation conditions and evaluation results of the
thermally modified polymer layer are shown in Table R11 below. It
is understood from the Table R11 that as the temperature for
thermal modification decreases, i.e. as the degree of thermal
modification decreases, this ratio (a ratio of absorption peak
intensity of C.dbd.O stretching vibration/absorption peak intensity
of C--H stretching vibration (-)) decreases. Therefore, it is
understood that this ratio can be used as an index of the degree of
thermal modification of a thermally modified polymer layer.
TABLE-US-00013 TABLE 13 Table R11 Thermally modified polymer layer
Material Number of O atoms/ Ratio of Polymer Preparation condition
(Number of O atoms + absorption Inorganic concentration Temp. Time
Number of C atoms) intensity substrate Solvent Polymer (mass %)
(.degree. C.) (min) (%) (--) Ref. Ex. 31 Si Chloroform COP1 20 400
1 (not measured) 3.10 Ref. Ex. 32 Si Chloroform COP1 20 320 1 7.1
0.25 Ref. Ex. 33 Si Chloroform COP1 20 280 1 6.3 0.22 Ref. Ex. 34
Si Chloroform COP1 20 240 1 0.1 0 Ref. Ex. 35 Si Chloroform COP1 20
200 1 0.1 0 Ref. Ex. 36 Si Chloroform COP1 20 160 1 (not measured)
0
REFERENCE SIGNS
[0229] 10 inorganic substrate [0230] 20, 21, 22 thermally modified
polymer layer [0231] 30, 31, 32 polymer member [0232] 110, 120
composite of thermally modified polymer layer and inorganic
substrate [0233] 210, 220 composite of polymer member and inorganic
substrate according to the present invention
* * * * *