U.S. patent application number 15/013193 was filed with the patent office on 2016-06-02 for flourine-containing compound, substrate for patterning, photodegradable coupling agent, patterning method, and compound.
This patent application is currently assigned to Kanagawa University. The applicant listed for this patent is Kanagawa University, NIKON CORPORATION. Invention is credited to Yusuke KAWAKAMI, Kazuo YAMAGUCHI.
Application Number | 20160152642 15/013193 |
Document ID | / |
Family ID | 52586538 |
Filed Date | 2016-06-02 |
United States Patent
Application |
20160152642 |
Kind Code |
A1 |
YAMAGUCHI; Kazuo ; et
al. |
June 2, 2016 |
FLOURINE-CONTAINING COMPOUND, SUBSTRATE FOR PATTERNING,
PHOTODEGRADABLE COUPLING AGENT, PATTERNING METHOD, AND COMPOUND
Abstract
A fluorine-containing compound represented by General formula
(1), wherein X represents a halogen atom or an alkoxy group,
R.sup.1 represents a hydrogen atom or a linear, branched, or cyclic
alkyl group having 1 to 10 carbon atoms, R.sup.f1 and R.sup.f2 are
each independently a fluorinated alkoxy group, and n represents an
integer of 0 or more. ##STR00001##
Inventors: |
YAMAGUCHI; Kazuo; (Yokohama,
JP) ; KAWAKAMI; Yusuke; (Yokohama, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Kanagawa University
NIKON CORPORATION |
Yokohama-shi
Tokyo |
|
JP
JP |
|
|
Assignee: |
Kanagawa University
Yokohama-shi
JP
NIKON CORPORATION
Tokyo
JP
|
Family ID: |
52586538 |
Appl. No.: |
15/013193 |
Filed: |
February 2, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2014/072257 |
Aug 26, 2014 |
|
|
|
15013193 |
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Current U.S.
Class: |
430/319 ;
430/322; 548/542; 556/423 |
Current CPC
Class: |
G03F 7/0755 20130101;
G03F 7/16 20130101; C07F 7/1804 20130101; G03F 7/20 20130101; C07D
207/46 20130101 |
International
Class: |
C07F 7/18 20060101
C07F007/18; G03F 7/20 20060101 G03F007/20; C07D 207/46 20060101
C07D207/46 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 27, 2013 |
JP |
2013-176023 |
Claims
1. A fluorine-containing compound represented by the following
General formula (1): ##STR00031## wherein X represents a halogen
atom or an alkoxy group, R.sup.1 represents a hydrogen atom or a
linear, branched, or cyclic alkyl group having 1 to 10 carbon
atoms, R.sup.f1 and R.sup.f2 are each independently a fluorinated
alkoxy group, and n represents an integer of 0 or more.
2. A substrate for patterning, having a surface chemically modified
with the fluorine-containing compound according to claim 1.
3. A photodegradable coupling agent consisted of the
fluorine-containing compound according to claim 1.
4. A patterning method for forming a pattern on a surface to be
treated of an object, comprising: a first step of chemically
modifying the surface to be treated using the fluorine-containing
compound according to claim 1; a second step of producing a latent
image formed of a hydrophilic region and a water-repellent region
by irradiating the chemically modified surface to be treated with
light having a predetermined pattern; and a third step of disposing
a patterning material on the hydrophilic region or the
water-repellent region.
5. A patterning method for forming a circuit pattern for an
electronic device on a flexible substrate, comprising: a first step
of chemically modifying the entire surface or a specific region of
the substrate using the fluorine-containing compound according to
claim 1; a second step of producing a latent image of the circuit
pattern on the surface of the substrate by using the difference in
the hydrophilicity and the water repellency by irradiating the
surface of the chemically modified substrate with light energy
having a distribution corresponding to the circuit pattern; and a
third step of bringing the flexible patterning material into
contact with the latent image portion on the surface of the
substrate, and thereby capturing the patterning material in the
shape of the circuit pattern by using the difference in the
hydrophilicity and the water repellency.
6. The patterning method according to claim 4, wherein the
patterning material includes a liquid conductive material, a liquid
semiconductor material, or a liquid insulating material.
7. The patterning method according to claim 4, wherein the light
includes light at a wavelength in the range of 200 nm to 450
nm.
8. A compound represented by the following General formula (f):
##STR00032## wherein R.sup.1 represents a hydrogen atom or a
linear, branched, or cyclic alkyl group having 1 to 10 carbon
atoms, and R.sup.f1 and R.sup.f2 are each independently a
fluorinated alkoxy group.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] Priority is claimed on Japanese Patent Application No.
2013-176023, filed on Aug. 27, 2013, the content of which is
incorporated herein by reference. The present application is a
continuation application of International Application
PCT/JP2014/072257, filed on Aug. 26, 2014. The contents of the
above applications are incorporated herein.
BACKGROUND
Technical Field
[0002] The present invention relates to a fluorine-containing
compound, a substrate for patterning, a photodegradable coupling
agent, a patterning method, and a compound.
[0003] In recent years, in the production of micro-devices such as
a semiconductor element, an integrated circuit, and a device for an
organic EL display, a method in which patterns having different
surface characteristics are formed on a substrate and a
micro-device is manufactured by using the difference in the surface
characteristics has been proposed.
[0004] As a patterning method using the difference in the surface
characteristics on a substrate, there is a method in which a
hydrophilic region and a water-repellent region are formed on a
substrate, and an aqueous solution of a functional material is
applied to the hydrophilic region. In this method, since the
aqueous solution of the functional material is wet and spread only
in the hydrophilic region, a thin film pattern of the functional
material can be formed.
[0005] Recently, as the material capable of forming a hydrophilic
region and a water-repellent region on a substrate, a coupling
agent has been used in recent years. In Japanese Unexamined Patent
Application, First Publication No. 2008-50321, a photodegradable
coupling agent is described, wherein the photodegradable coupling
agent can change the contact angle significantly before and after
light irradiation, that is, which can change the hydrophilic
characteristics and the water-repellent characteristics
significantly before and after light irradiation.
SUMMARY
[0006] However, in the photodegradable coupling agent as described
in Japanese Unexamined Patent Application, First Publication No
2008-50321, there is still room for improvement in a difference in
the contact angles before and after light irradiation and in
sensitivity to the irradiated light.
[0007] The present invention has been made by taking into
consideration the above situations and has an object to provide a
fluorine-containing compound useful as a coupling agent, which has
a large difference in contact angles between before and after light
irradiation and has superior sensitivity; a substrate for
patterning using the fluorine-containing compound; a
photodegradable coupling agent using the fluorine-containing
compound; a patterning method; and a compound useful as an
intermediate in the production of the fluorine-containing
compound.
[0008] A first aspect of the present invention is a
fluorine-containing compound represented by the following General
formula (1).
##STR00002##
[0009] In General formula (1), X represents a halogen atom or an
alkoxy group,
[0010] R.sup.1 represents a hydrogen atom or a linear, branched, or
cyclic alkyl group having 1 to 10 carbon atoms,
[0011] R.sup.f1 and R.sup.f2 are each independently a fluorinated
alkoxy group, and
[0012] n represents an integer of 0 or more.
[0013] A second aspect of the present invention is a substrate for
patterning, which has a surface chemically modified with the
fluorine-containing compound according to the first aspect.
[0014] A third aspect of the present invention is a photodegradable
coupling agent consisted of the fluorine-containing compound
according to the first aspect.
[0015] A fourth aspect of the present invention is a patterning
method for forming a pattern on a surface to be treated of an
object, which comprises a first step of chemically modifying the
surface to be treated using the fluorine-containing compound
according to the first aspect, a second step of producing a latent
image formed of a hydrophilic region and a water-repellent region
by irradiating the chemically modified surface to be treated with
light having a predetermined pattern, and a third step of disposing
a patterning material on the hydrophilic region or the
water-repellent region.
[0016] A fifth aspect of the present invention is a patterning
method for forming a circuit pattern for an electronic device on a
flexible substrate, which comprises a first step of chemically
modifying the entire surface or a specific region of the substrate
using the fluorine-containing compound according to the first
aspect, a second step of producing a latent image of the circuit
pattern on the surface of the substrate by using the difference in
the hydrophilicity and the water repellency by irradiating the
surface of the chemically modified substrate with light energy
having a distribution corresponding to the circuit pattern, and a
third step of bringing the flexible patterning material into
contact with the latent image portion on the surface of the
substrate, and thereby capturing the patterning material in the
shape of the circuit pattern by using the difference in the
hydrophilicity and the water repellency.
[0017] In the patterning method of the fourth or fifth aspect of
the present invention, the patterning material preferably includes
a liquid conductive material, a liquid semiconductor material, or a
liquid insulating material, and the light preferably includes light
at a wavelength in the range of 200 nm to 450 nm.
[0018] A sixth aspect of the present invention is a compound
represented by the following General formula (f).
##STR00003##
[0019] In General formula (f), R.sup.1 represents a hydrogen atom
or a linear, branched, or cyclic alkyl group having 1 to 10 carbon
atoms, and
[0020] R.sup.f1 and R.sup.f2 are each independently a fluorinated
alkoxy group.
Advantageous Effects of Invention
[0021] According to the present invention, it is possible to
provide a fluorine-containing compound useful as a coupling agent,
which has a large difference in contact angles between before and
after light irradiation and has superior sensitivity; a substrate
for patterning using the fluorine-containing compound; a
photodegradable coupling agent using the fluorine-containing
compound; a patterning method; and a compound useful as an
intermediate in the production of the fluorine-containing
compound.
BRIEF DESCRIPTION OF DRAWINGS
[0022] FIG. 1 is a schematic view showing the entire configuration
of a suitable substrate-treating apparatus in the patterning method
of the present invention.
[0023] FIG. 2 is a view showing the measured results of a change in
static contact angles of water with lapse of time in Examples of
the present invention.
DESCRIPTION OF EMBODIMENTS
[0024] <<Fluorine-Containing Compound>>
[0025] The first aspect of the present invention is a
fluorine-containing compound represented by the following General
formula (1).
##STR00004##
[0026] wherein X represents a halogen atom or an alkoxy group,
[0027] R.sup.1 represents a hydrogen atom or a linear, branched, or
cyclic alkyl group having 1 to 10 carbon atoms,
[0028] R.sup.f1 and R.sup.f2 are each independently a fluorinated
alkoxy group, and n represents an integer of 0 or more.
[0029] In General formula (1), X is a halogen atom or an alkoxy
group.
[0030] Examples of the halogen atom of X include a fluorine atom, a
chlorine atom, a bromine atom, and an iodine atom.
[0031] The alkoxy group of X preferably has 1 to 20 carbon atoms,
more preferably 1 to 10 carbon atoms, still more preferably 1 to 5
carbon atoms, desirably 1 to 3 carbon atoms, and most desirably 1
or 2 carbon atoms.
[0032] X is preferably an alkoxy group rather than a halogen
atom.
[0033] n represents an integer of 0 or more. In terms of easy
availability of starting raw materials, n is preferably an integer
of 1 to 20, and more preferably an integer of 2 to 15. Further, n
is preferably 3 or more, and more preferably 4 or more.
[0034] In General formula (1), R.sup.1 is a hydrogen atom, or a
linear, branched, or cyclic alkyl group having 1 to 10 carbon
atoms.
[0035] As the alkyl group of R.sup.1, a linear or branched alkyl
group having 1 to 5 carbon atoms is preferable, and specific
examples thereof include a methyl group, an ethyl group, a propyl
group, an isopropyl group, an n-butyl group, an isobutyl group, a
tert-butyl group, a pentyl group, an isopentyl group, and a
neopentyl group.
[0036] Examples of the cyclic alkyl group include a group in which
1 or more hydrogen atoms are removed from a monocycloalkane; or a
polycycloalkane such as bicycloalkane, tricycloalkane, and
tetracycloalkane.
[0037] In the present invention, R.sup.1 is preferably a hydrogen
atom, a methyl group, an ethyl group, an n-propyl group, or an
isopropyl group.
[0038] In General formula (1), R.sup.f1 and R.sup.f2 are each
independently a fluorinated alkoxy group.
[0039] In General formula (1), the fluorinated alkoxy group of
R.sup.f1 or R.sup.f2 is preferably an alkoxy group having 3 or more
carbon atoms, and may be partially fluorinated or may be a
perfluoroalkoxy group. In the present invention, the fluorinated
alkoxy group is preferably a fluorinated alkoxy group which is
partially fluorinated.
[0040] In the present invention, examples of the fluorinated alkoxy
group of R.sup.f1 or R.sup.f2 include groups represented by
--O--(CH.sub.2).sub.n.sup.f1--(C.sub.n.sup.f2F.sub.2n+1.sup.f2).
n.sup.f1 is an integer of 0 or more and n.sup.f2 is an integer of 1
or more.
[0041] In the present invention, n.sup.f1 is preferably 0 to 30,
more preferably 0 to 15, and most preferably 0 to 5.
[0042] Furthermore, in the present invention, n.sup.f2 is
preferably 1 to 30, more preferably 1 to 15, still more preferably
1 to 10, and most preferably 1 to 6.
[0043] Specific examples of the fluorine-containing compound
represented by General formula (1) are shown below.
##STR00005##
[0044] <<Compound>>
[0045] The sixth aspect of the present invention is a compound
represented by the following General formula (f).
##STR00006##
[0046] wherein R.sup.1 represents a hydrogen atom or a linear,
branched, or cyclic alkyl group having 1 to 10 carbon atoms, and
R.sup.f1 and R.sup.f2 are each independently a fluorinated alkoxy
group.]
[0047] In General formula (f), the descriptions of R.sup.1,
R.sup.f1, and R.sup.f2 are each the same as those of R.sup.1,
R.sup.f1, and R.sup.f2 in aforementioned General formula (1).
[0048] <Method for Producing Fluorine-Containing
Compound>
[0049] The fluorine-containing compound of the present invention is
preferably produced using the compound according to the sixth
aspect of the present invention as a raw material
(intermediate).
[0050] Examples of the solvent used in the following steps include
such as ethyl acetate, butyl acetate, acetone, methyl ethyl ketone,
methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane,
N,N-dimethylformamide, N,N-dimethylacetamide, benzene, toluene,
acetonitrile, methylene chloride, chloroform, dichloroethane,
methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol. These may
be used alone or in combination of two or more kinds thereof.
[0051] The compound according to the sixth aspect of the present
invention can be obtained, for example, through the following
respective steps.
##STR00007##
[0052] In the above formulae R.sup.1, R.sup.f1, and R.sup.f2 are
the same as R.sup.1, R.sup.f1, and R.sup.f2 in aforementioned
General formula (1). R.sup.f1' and R.sup.f2' in I--R.sup.f1' and
I--R.sup.f2' are the same as R.sup.f1 and R.sup.f2,
respectively.
##STR00008##
[0053] In the above formulae, R.sup.1, R.sup.f1, and R.sup.f2 are
the same as R.sup.1, R.sup.f1, and R.sup.f2 in aforementioned
General formula (1), respectively.
##STR00009##
[0054] In the above formulae, R.sup.1, R.sup.f1, and R.sup.f2 are
each the same as R.sup.1, R.sup.f1, and R.sup.f2 in General formula
(1).
##STR00010##
[0055] In the above reaction scheme, the explanations of R.sup.1,
R.sup.f1, and R.sup.f2 are the same as those of R.sup.1, R.sup.f1,
and R.sup.f2 in aforementioned General formula (1),
respectively.
[0056] The fluorine-containing compound according to the first
aspect of the present invention can be obtained by the following
steps, for example. In the following formulae, the explanations of
X, R.sup.1, R.sup.f1, R.sup.f2, and n are the same as those of X,
R.sup.1, R.sup.f1, R.sup.f2, and n in aforementioned General
formula (1), respectively.
##STR00011##
[0057] <Surface Modification in 2-Steps>
[0058] A case of performing a surface modification in 2-steps using
the fluorine-containing compound of the present invention will be
described. First, a substrate surface is subjected to surface
modification of the substrate using the fluorine-containing
compound of the present invention, as shown in [First Step],
thereby making the substrate surface water-repellent. Thereafter,
the contact angle of the substrate surface is reduced by carrying
out light irradiation, thereby making the substrate surface of the
water-repellent substrate hydrophilic.
[0059] Furthermore, a terminal carbonate compound or the like is
reacted with the substrate which has been made hydrophilic in the
first step, as shown in the following second step, thereby
significantly increasing the contact angle of the substrate surface
which has been made hydrophilic in the first step, and thus, making
the surface water-repellent.
[0060] In the following formulae, R.sup.f is a fluorine
atom-containing group for imparting water repellency on the
substrate surface and examples thereof include the fluorinated
alkoxy groups of aforementioned R.sup.f1 and R.sup.f2.
##STR00012##
[0061] <<Substrate for Patterning>>
[0062] The second aspect of the present invention is a substrate
for patterning, which has a surface chemically modified with the
fluorine-containing compound.
[0063] The material for the substrate is not particularly limited
and preferred examples thereof include glass, quartz glass, a
silicon wafer, a plastic plate, and a metal plate. In addition, a
substrate on which a metal thin film has been formed may be
used.
[0064] The shape of the substrate is not particularly limited, but
a planar surface, a curved surface, or a planar surface having
partially a curved surface is preferable, and a planar surface is
more preferable. Further, the surface area of the substrate is also
not particularly limited, but a substrate having a large surface
within a range in which applying methods in the related art can be
used may be employed. In addition, the surface chemically modified
with the fluorine-containing compound is preferably formed on one
side of the planner substrate.
[0065] When modifying the surface of the substrate, it is
preferable to subject the substrate surface a pretreatment. As the
pretreatment method, a pretreatment in a piranha solution or a
pretreatment by a UV-ozone cleaner is preferable.
[0066] The method for modifying the surface of the substrate is not
particularly limited as long as it is a method in which at least a
part of X bonded to reactive Si in General formula (1) is
dissociated and thereby, the substrate is bonded to the
fluorine-containing compound after the dissociation. Thus, known
methods such as a dipping method and a chemical treatment method
can be used.
[0067] <<Photodegradable Coupling Agent>>
[0068] The third aspect of the present invention is a
photodegradable coupling agent consisted of the fluorine-containing
compound.
[0069] The photodegradable coupling agent according to the present
aspect has a photodegradable group having a liquid repellent group
and an attaching group X linked to the photodegradable group
through a functional group, in which the liquid repellent group has
fluorinated alkoxy chains R.sup.f1 and R.sup.f2 at the terminal
thereof and the functional group has an amino group as a residue
after photodegradation. Therefore, in the photodegradable coupling
agent of the present invention, a large difference in contact
angles between before and after light irradiation can be
secured.
[0070] <<Patterning Method>>
[0071] The fourth aspect of the present invention is a patterning
method for forming a pattern on a surface to be treated of an
object, which includes a first step of chemically modifying a
surface to be treated using the fluorine-containing compound
according to the first aspect; a second step of producing a latent
image formed of a hydrophilic region and a water-repellent region
by irradiating the surface to be treated which has been chemically
treated with light having a predetermined pattern, and a third step
of disposing a patterning material on the hydrophilic region or the
water-repellent region.
[0072] [First Step]
[0073] In the patterning method for forming a pattern on a surface
to be treated of an object, the first step is a step of chemically
modifying the surface to be treated using the fluorine-containing
compound according to the first aspect.
[0074] The object is not particularly limited. Examples thereof
include a metal, a crystalline material (for example, a single
crystalline material, a polycrystalline material, and a partially
crystalline material), an amorphous material, a conductor, a
semiconductor, an insulator, an optical element, a coated
substrate, fiber, glass, ceramics, zeolite, plastic, a
thermosetting and thermoplastic material (for example, doped in
some cases: such as polyacrylate, polycarbonate, polyurethane,
polystyrene, a cellulose polymer, polyolefin, polyamide, polyimide,
a resin, polyester, and polyphenylene), a film, a thin film, and a
foil.
[0075] The patterning method according to the present aspect is
preferably a patterning method in which a circuit pattern for an
electronic device is formed on a flexible substrate. That is, the
object is preferably a flexible substrate.
[0076] Here, the term flexibility refers to a property capable of
flexing the substrate without being broken or fractured even when a
force of about its own weight is applied to the substrate. Further,
properties of bending by force of about its own weight are also
included in the flexibility. Moreover, the flexibility varies
depending on such as the material, the size, the thickness of the
substrate, and the environment such as a temperature. In addition,
as the substrate, a single belt-shape substrate may be used, or the
substrate may be configured to be formed in the belt shape by
connecting a plurality of unit substrates.
[0077] As the flexible substrate (object), for example, a resin
film or a foil of stainless steel or the like can be used. For
example, as the resin film, materials such as a polyethylene resin,
a polypropylene resin, a polyester resin, an ethylene vinyl
copolymer resin, a polyvinyl chloride resin, a cellulose resin, a
polyamide resin, a polyimide resin, a polycarbonate resin, a
polystyrene resin, and a vinyl acetate resin can be used.
[0078] In the first step, the entire surface to be treated of an
object may be chemically modified by using the fluorine-containing
compound; however it is preferable that a specific region of an
object be chemically modified by using the fluorine-containing
compound.
[0079] The method for modifying the surface to be treated of an
object is not particularly limited as long as it is a method in
which at least a part of X bonded to reactive Si in aforementioned
General formula (1) is dissociated and thus, the substrate is
bonded to the fluorine-containing compound after the dissociation.
Therefore, known methods such as a dipping method and a chemical
treatment method can be used.
[0080] An example of the chemical modification in the first step is
shown below. In the following formulae, the explanations of X,
R.sup.1, R.sup.f1, R.sup.f2, and n are the same as those of X,
R.sup.1, R.sup.f1, R.sup.f2, and n in aforementioned General
formula (1), respectively.
##STR00013##
[0081] [Second Step]
[0082] The second step is a step of producing a latent image formed
of a hydrophilic region and a water-repellent region by irradiating
the chemically modified surface to be treated with light having a
predetermined pattern.
[0083] As the light to be irradiated, ultraviolet rays are
preferable. The light to be irradiated preferably includes light
having a wavelength included in a range of 200 nm to 450 nm, more
preferably includes light having a wavelength included in a range
of 320 nm to 450 nm. In addition, it is also preferable that light
including light having a wavelength of 365 nm be irradiated. Light
having these wavelengths can efficiently degrade the
photodegradable group according to the aspects of the present
invention. Examples of a light source include a low-pressure
mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure
mercury lamp, a xenon lamp, and a sodium lamp; a laser of a gas
such as nitrogen, a liquid laser of an organic dye solution, and a
solid laser in which rare earth ions are contained in inorganic
single crystals.
[0084] In addition, as a light source other than lasers, from which
monochromatic light is obtained, light at a specific wavelength
extracted with a broadband line spectrum or a continuous spectrum
using an optical filter such as a band-pass filter and a cut-off
filter may be used. The high-pressure mercury lamp or the
ultrahigh-pressure mercury lamp is preferable as a light source
from the viewpoint that a large area can be irradiated using the
mercury lamp by one irradiation.
[0085] In the patterning method of the present invention, a surface
to be treated can be irradiated with light arbitrarily within the
above range. However, in particular, a surface to be treated is
preferably irradiated with light energy having a distribution
corresponding to a circuit pattern.
[0086] In the second step, a residue (amino group) having
hydrophilicity is generated due to dissociation of a group having
water-repellency by irradiating the chemically modified surface to
be treated with light having a predetermined pattern. Therefore,
after light irradiation, it is possible to form a latent image
consisted of a hydrophilic region and a water-repellent region.
[0087] In the second step, it is possible to produce a latent image
of a circuit pattern by using a difference in the hydrophilicity
and the water repellency on the surface of a flexible substrate by
irradiation with light corresponding to the circuit pattern.
[0088] An example of the steps in which a residue (amino group)
having hydrophilicity generated by the irradiating the chemically
modified surface to be treated with light having a predetermined
pattern and the dissociation of a group having water-repellency is
produced is shown below. In the following formulae, the
descriptions of R.sup.1, R.sup.f1, R.sup.f2, and n are the same as
those of R.sup.1, R.sup.f1, R.sup.f2, and n in aforementioned
General formula (1), respectively.
##STR00014##
[0089] [Third Step]
[0090] The third step is a step of disposing a patterning material
in the hydrophilic region or the water-repellent region, each of
which has been produced in the second step.
[0091] Examples of the patterning material include wiring materials
(metal solutions) in which particles of gold, silver, copper, an
alloy of these, or the like are dispersed in a predetermined
solvent, electronic materials in which a precursor solution
including the above-described metals, an insulator (resin), a
semiconductor, an organic EL light-emitting material, or the like
is dispersed in a predetermined solvent, or resist solutions.
[0092] In the patterning method according to the present aspect,
the patterning material is preferably a liquid conductive material,
a liquid semiconductor material, or a liquid insulating
material.
[0093] Examples of the liquid conductive material include a
patterning material formed of a dispersion in which conductive fine
particles are dispersed in a dispersion medium. As the conductive
fine particles, for example, in addition to metal fine particles
containing any one of gold particles, silver particles, copper
particles, palladium particles, nickel particles, and ITO
particles, fine particles of oxides thereof or of a conductive
polymer or a superconductor are used.
[0094] These conductive fine particles can also be used after the
surfaces thereof are coated with an organic material in order to
improve dispersibility.
[0095] The dispersion medium is not particularly limited as long as
it can disperse the above-described conductive fine particles and
does not cause aggregation of the fine particles. In addition to
water, examples of the dispersion medium include alcohols such as
methanol, ethanol, propanol, and butanol; hydrocarbon-based
compounds such as n-heptane, n-octane, decane, dodecane,
tetradecane, toluene, xylene, cymene, durene, indene, dipentene,
tetrahydronaphthalene, decahydronaphthalene, cyclohexyl benzene;
ether-based compounds such as ethylene glycol dimethyl ether,
ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether,
diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane,
bis(2-methoxyethyl)ether, and p-dioxane; and polar compounds such
as propylene carbonate, .gamma.-butyrolactone,
N-methyl-2-pyrrolidone, dimethyl formamide, dimethyl sulfoxide, and
cyclohexanone. Among these, from the viewpoint of dispersibility of
fine particles and stability of a dispersion and ease of
application to a liquid droplet discharge method (ink jet method),
water, alcohols, a hydrocarbon-based compound, and an ether-based
compound are preferable, and more preferred examples of the
dispersion medium include water and a hydrocarbon-based
compound.
[0096] As the liquid semiconductor material, an organic
semiconductor material dispersed or dissolved in a dispersion
medium can be used. Examples of the organic semiconductor material
include a .pi.-electron conjugated system polymer material of which
the skeleton is configured of conjugated double bonds is
preferable. Representative examples of the organic semiconductor
material include soluble polymeric materials such as polythiophene,
poly(3-alkylthiophene), polythiophene derivatives, and
pentacene.
[0097] Examples of the liquid insulating material include
insulating materials in which polyimide, polyamide, polyester,
acryl, phosphorus glass (PSG), boron phosphorus glass (BPSG),
polysilazane-based SOG, silicate-based. Spin on Glass (SOG), alkoxy
silicate-based SOG, SiO.sub.2 having a Si--CH.sub.3 bond
represented by a siloxane polymer, or the like is dispersed or
dissolved in a dispersion medium.
[0098] In the third step, as a method for disposing a patterning
material on the hydrophilic region or the water-repellent region of
the surface to be treated, a liquid droplet discharge method, an
ink jet method, a spin coating method, a roll coating method, a
slot coating method, or the like can be applied.
[0099] Hereinafter, the patterning method according to the aspect
of the present invention will be described with reference to a
drawing.
[0100] In the patterning method according to the present aspect, in
the case where a flexible substrate able to be used in a so-called
roll-to-roll process is used, a pattern may be formed by using a
substrate-treating apparatus 100 which is a roll-to-roll apparatus,
as shown in FIG. 1. FIG. 1 shows a configuration of the
substrate-treating apparatus 100.
[0101] As shown in FIG. 1, the substrate-treating apparatus 100 has
a substrate-supplying unit 2 that supplies a belt-shape substrate
(for example, a belt-shape film member) S, a substrate-treating
unit 3 that performs a treatment to the surface (surface to be
treated) Sa of the substrate S, a substrate-retrieving unit 4 that
retrieves the substrate S, an applying unit 6 of a
fluorine-containing compound, an exposing unit 7, a mask 8, a
patterning material material-applying unit 9, and a controlling
unit CONT, that controls each of these parts. In the
substrate-treating unit 3, various treatments can be performed on
the surface of the substrate S between from the time when the
substrate S is sent from the substrate-supplying unit 2 to the time
when the substrate S is retrieved by the substrate-retrieving unit
4.
[0102] The substrate-treating apparatus 100 can be suitably used in
the case where a display element (electronic device) such as an
organic EL element and a liquid crystal display element is formed
on the substrate S.
[0103] Moreover, FIG. 1 is an illustration of a method using a
photomask to produce a desired pattern light. However, the present
invention can also be suitably applied to a maskless exposure
method in which a photomask is not used. Examples of the maskless
exposure method in which a pattern light is produced without using
a photomask include a method in which a spatial light modulation
element such as a DMD is used and a method in which a spot light is
scanned, such as a laser beam printer.
[0104] In the patterning method according to the present aspect, a
XYZ coordinate system is set as shown in FIG. 1. Hereinafter,
description is made using the XYZ coordinate system as appropriate.
In the XYZ coordinate system, for example, an X-axis and a Y-axis
are set along a horizontal plane, and a Z-axis is set upward along
the vertical direction. In addition, the substrate-treating
apparatus 100 transports the substrate S from the minus side
(-X-axis side) to the plus side (+X-axis side), along the X-axis as
a whole. At this time, the width direction (short direction) of the
belt-shape substrate S is set along the Y-axis direction.
[0105] As the substrate S which is a surface to be treated in the
substrate-treating apparatus 100, for example, a resin film or a
foil of stainless steel or the like can be used. For example, for
the resin film, materials such as a polyethylene resin, a
polypropylene resin, a polyester resin, an ethylene vinyl copolymer
resin, a polyvinyl chloride resin, a cellulose resin, a polyamide
resin, a polyimide resin, a polycarbonate resin, a polystyrene
resin, and a vinyl acetate resin can be used.
[0106] For example, the substrate S preferably has a small thermal
expansion coefficient such that the size is not changed even in the
case of receiving heat of about 200.degree. C. For example, the
thermal expansion coefficient can be reduced by mixing inorganic
filler with a resin film. Examples of the inorganic filler include
such as titanium oxide, zinc oxide, alumina, and silicon oxide. In
addition the substrate S may be a single body of ultrathin glass
having a thickness of about 100 .mu.m, prepared by a float method
or the like, or a laminate formed by adhering the resin film or
aluminum foil on the ultrathin glass.
[0107] The size of the width direction (short direction) of the
substrate S, for example, is formed to be about 1 m to 2 m, and the
size of the length direction (long direction), for example, is
formed to be 10 m or more. Needless to say, the sizes are only
examples and are not limited thereto. For example, the size of the
Y-axis direction of the substrate S may also be 50 cm or less, or
may also be 2 m or greater. In addition, the size of the X-axis
direction of the substrate S may also be 10 m or less.
[0108] The substrate S is preferably formed so as to have
flexibility. Here, the term flexibility refers to properties
capable of flexing the substrate without being broken or fractured
even in the case where a force of about its own weight is added to
the substrate. In addition, properties of bending by a force of
about its own weight are also included in the flexibility.
[0109] In addition, the flexibility varies depending on such as the
material, the size, the thickness of the substrate, the environment
such as temperature, or the like. Further, as the substrate S, a
single belt-shape substrate may be used, or the substrate S may be
configured to be formed in a belt-shape by connecting a plurality
of unit substrates.
[0110] The substrate-supplying unit 2, for example, supplies the
substrate S wound in a roll shape by sending the substrate S to the
substrate-treating unit 3. In this case, in the substrate-supplying
unit 2, a rotation driving device or the like that rotates a shaft
portion winding the substrate S or the shaft portion is provided.
In addition, the substrate-supplying unit 2 may have a
configuration in which a cover portion that covers the substrate
Sin the state of being wound in a roll shape or the like is
provided. Moreover, the substrate-supplying unit 2 is not limited
to the mechanism for sending the substrate S wound in a roll shape,
and may include a mechanism (for example, a nip-type driving
roller) for sequentially sending the belt-shape substrate S in the
length direction.
[0111] The substrate-retrieving unit 4 retrieves the substrate S
that has passed through the substrate-treating apparatus 100, for
example, by winding in a roll shape. In the substrate-retrieving
unit 4, in the same manner as in the substrate-supplying unit 2, a
rotation driving source that rotates a shaft portion for winding
the substrate S or the shaft portion, a cover portion that covers
the retrieved substrate S, or the like is provided. Moreover, in
the case where the substrate S is cut into a panel shape or the
like in the substrate-treating unit 3, for example, the
substrate-treating unit 3 may have a configuration in which the
substrate S is retrieved in a different state from the state of
being wound in a roll shape, as a configuration in which the
substrate S is retrieved in a stacked state.
[0112] The substrate-treating unit 3 transports the substrate S
supplied from the substrate-supplying unit 2 to the
substrate-retrieving unit 4, and performs a step of chemically
modifying the surface Sa to be treated of the substrate S in a
process of transporting using a fluorine-containing compound, a
step of irradiating a chemically modified surface to be treated
with light having a predetermined pattern, and a step of disposing
a patterning material. The substrate-treating unit 3 has the
fluorine-containing compound-applying unit 6 that applies a
fluorine-containing compound to the surface Sa to be treated of the
substrate S, the exposing unit 7 that irradiates with light, the
mask 8, the patterning material-applying unit 9, and a transporting
device 20 that includes a driving roller R or the like to send the
substrate S under the conditions corresponding to the form of the
processing treatment.
[0113] Examples of the fluorine-containing compound-applying unit 6
or the patterning material material-applying unit 9 include liquid
droplet application devices (for example, a liquid droplet
discharge type application device, an ink jet type application
device, a spin coating type application device, a roll coating type
application device, and a slot coating type application
device).
[0114] Each of these devices is suitably provided along the
transport path of the substrate S, and is configured to be able to
produce a flexible display panel or the like by a so-called
roll-to-roll method. In the present embodiment, the exposing unit 7
is provided, and devices performing the steps before and after
thereof (a photosensitive layer-forming step, a photosensitive
layer-developing step, or the like) are also provided in an in-line
type, if desired.
[0115] Since the fluorine-containing compound of the present
invention has a photodegradable group with a water-repellent group
having a fluorinated alkoxy chain at the terminal, in the case
where the fluorine-containing compound is attached on the substrate
surface, the contact angle between the surface thereof and a liquid
can be increased. In addition, a residue (amino group) having
hydrophilicity can be generated by dissociating a group having a
water-repellency by irradiating with light. Therefore, before and
after light irradiation, the substrate surface exhibits good
hydrophilicity, and the contact angle can be reduced.
[0116] The fluorine-containing compound of the present invention
can be suitably used for, for example, formation of an organic
thin-film layer (also referred to as a "self-organized
monomolecular layer") which is used for an organic thin-film
transistor.
[0117] In the self-organized monomolecular layer, the organic
semiconductor material enhances wettability to improve the
crystallinity (the size and the array of crystals) of the organic
semiconductor material, and further, to improve the electrical
connection of a source electrode and a drain electrode constituting
the organic thin-film transistor with the organic semiconductor
layer.
[0118] In particular, it is presumed that the applicability of the
organic semiconductor material can be improved by forming a
self-organized monomolecular layer using the fluorine-containing
compound of the present invention on an insulating layer
constituting an organic thin-film transistor and changing the
wettability by exposure and also it may contribute to improving the
mobility of the organic semiconductor.
EXAMPLES
[0119] Hereinafter, the present invention will be described in more
detail with reference to Examples, although the present invention
is not limited to the following Examples.
Examples 1
Synthesis of Fluorine-Containing Compound (1)
[0120] 9.02 g (65.4 mmol) of o-dimethoxybenzene, 0.311 g (2.45
mmol) of iodine crystals, and 20.7 g (131 mmol) of isobutyric acid
anhydride were put into a 100-mL recovery flask, the mixture was
refluxed at 170.degree. C. for 6 hours, returned to room
temperature, and then stirred for 31 hours. Thereafter, the mixture
was distilled off under reduced pressure, purified water (80 mL)
was added thereto, and the organic layer was extracted with diethyl
ether (80 mL.times.3). The organic layer was washed with a 5%
aqueous sodium hydrogen carbonate solution (80 mL), saturated
saline (80 mL), and purified water (80 mL), dried over anhydrous
magnesium sulfate, filtered, and concentrated. The residue was
isolated and purified by column chromatography (hexane:ethyl
acetate=4:1), concentrated, and vacuum-dried to obtain 3.90 g (18.7
mmol, 29%) of a pale yellow viscous matter (compound (I1).
[0121] The identification results of the above-synthesized compound
(compound (I1)), 1-(3,4-dimethoxyphenyl)-2-methylpropanone, are
shown below.
[0122] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. 1.22 (6H, d,
J=6.8 Hz), 3.55 (1H, sep, J=6.8 Hz), 3.94 and 3.95 (6H, s, s), 6.90
(1H, d, J=8.4 Hz), 7.55 (1H, d, J=2.0 Hz), 7.60 (1H, d, J=2.0
Hz).
[0123] IR (NaCl): 1674 (C.dbd.O) cm.sup.-1.
##STR00015##
[0124] Next, 2.73 g (13.1 mmol) of the compound (I1) was put into a
100-mL two-neck recovery flask, and 50 mL of N,N-dimethylformamide
(hereinafter, referred to as "DMF") as a dry solvent and 11.2 g
(262 mmol:20 eq) of lithium chloride were added thereto in a
nitrogen atmosphere. The mixture was refluxed at 170.degree. C. for
29 hours and stirred at 100.degree. C. for 32 hours. Thereafter,
200 mL of saturated saline and 50 mL of 2 N hydrochloric acid were
added thereto and the mixture was extracted with 150 mL of ethyl
acetate three times. The mixture was dried over anhydrous magnesium
sulfate, filtered, concentrated, and vacuum-dried. The residue was
isolated and purified by column chromatography (hexane:ethyl
acetate=2:1), concentrated, and vacuum-dried to obtain 1.50 g (8.30
mmol, 63%) of a yellow viscous matter (compound (I2)).
[0125] The identification results of the above-synthesized compound
(compound (I2)), 1-(3,4-dihydroxyphenyl)-2-methylpropanone, are
shown below.
[0126] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. 1.21 (6H, d,
J=6.8 Hz), 3.53 (1H, sep, J=6.9 Hz), 6.35 (1H, s), 6.94 (1H, d,
J=8.4 Hz), 7.39 (1H, s), 7.52 (1H, d, J=8.4 Hz), 7.83 (1H, d, J=2.0
Hz).
[0127] IR (NaCl): 1656 (C.dbd.O), 3349 (OH) cm.sup.-1.
##STR00016##
[0128] 1.02 g (5.67 mmol) of the compound (I2), 15 mL of DMF, and
1.57 g (11.3 mmol:2 eq) of potassium carbonate were put into a
100-mL two-neck recovery flask, and the mixture was stirred at room
temperature for 2 hours. Thereafter, 7 mL of DMF was added to 4.64
g (12.0 mmol:2 1 eq) of
1-iodine-1H,1H,2H,2H,3H,3H-perfluoroheptane, the mixture was added
dropwise to the recovery flask, and the mixture was stirred at
60.degree. C. for 14 hours. After the reaction solution was
distilled off under reduced pressure, 60 mL of purified water and
20 mL of 2 N hydrochloric acid were added thereto, and the mixture
was extracted with ethyl acetate (60 mL.times.4) and washed with
saturated saline (60 mL.times.5). The organic layer was dried over
anhydrous magnesium sulfate, filtered, concentrated, and
vacuum-dried to obtain 3.62 g (5.17 mmol, 91%) of an orange solid
(compound (I3)).
[0129] The identification results of the above-synthesized compound
(compound (I3)),
1-(3,4-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2-methylpropanone,
are shown below.
[0130] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. 1.21 (6H, d,
J=6.8 Hz), 2.15-2.19 (4H, m), 2.32-2.34 (4H, m), 3.53 (1H, sep,
J=6.9 Hz), 4.13 and 4.14 (4H, t, t), 6.88 (1H, d, J=8.5 Hz), 7.52
(1H, d, J=2.0 Hz), 7.58 (1H, d, J=8.4 Hz).
[0131] IR (KBr): 722 (CF.sub.3), 1226 (CF.sub.2, CF.sub.3), 1678
(C.dbd.O) cm.sup.-1.
##STR00017##
[0132] 0.502 g (0.717 mmol) of the compound (I3) was put into a
100-mL recovery flask and dissolved in 3 mL of diethyl ether. 5 mL
of 70% nitric acid was poured thereto in an ice bath and the
mixture was stirred for 1.5 hours in an ice bath. Next, the
reaction solution was poured into ice, extracted with 50 mL of
purified water and ethyl acetate (50 mL.times.3), and washed with
5% sodium hydrogen carbonate (50 mL.times.3). The organic layer was
dried over anhydrous magnesium sulfate, filtered, and concentrated.
The residue was recrystallized by dissolving the concentrated
product in 20 mL of ethanol. The crystal was subjected to suction
filtration and vacuum drying to obtain 0.256 g (3.43 mmol, 48%) of
a light yellow needle-like crystal (compound (I4)).
[0133] The identification results of the above-synthesized compound
(compound (I4)),
1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2-methylpr-
opanone, are shown below.
[0134] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. 1.21 (6H, d,
J=6.8 Hz), 2.15-2.23 (4H, m), 2.27-2.34 (4H, m), 2.89 (1H, sep),
4.16 and 4.17 (4H, t, t), 6.67 (1H, s), 7.64 (1H, s).
[0135] IR (KBr): 721 (CF.sub.3), 1228 (CF.sub.2, CF.sub.3), 1358
and 1523 (NO.sub.2), 1703 (C.dbd.O) cm.sup.-1.
##STR00018##
[0136] 2.96 g (3.97 mmol) of the compound (I4), 12 mL of
tetrahydrofuran, and 8 mL of methanol were put into a 100-mL
recovery flask, 0.300 g (7.94 mmol:2 eq) of sodium borohydride was
poured thereto in an ice bath, and the mixture was stirred for 90
minutes. Thereafter, the mixture was stirred at room temperature
for 30 minutes. The reaction solution was concentrated and
extracted with 60 mL of purified water, 20 mL of 2 N hydrochloric
acid, and ethyl acetate (50 mL.times.3). The organic layer was
dried over anhydrous magnesium sulfate, filtered, and concentrated.
The residue was isolated and purified by column chromatography
(hexane:ethyl acetate=6:1), concentrated, and vacuum-dried to
obtain 2.17 g (2.90 mmol, 76%) of a yellow viscous matter (compound
(I5)).
[0137] The identification results of the above-synthesized compound
(compound (I5)),
1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2-methylpr-
opan-1-ol, are shown below.
[0138] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. 0.94 and 0.96
(6H, d, d, J=6.8 Hz), 1.97-2.03 (1H, m), 2.14-2.21 (5H, m),
2.27-2.40 (4H, m), 4.08-4.23 (4H, m), 5.27 (1H, t, J=4.8 Hz), 7.20
(1H, s), 7.55 (1H, s).
[0139] IR (NaCl): 742 (CF.sub.3), 1228 (CF.sub.2, CF.sub.3), 1334
and 1522 (NO.sub.2), 3547(OH) cm.sup.-1.
##STR00019##
[0140] 1.43 g (1.91 mmol:1 eq.) of the (compound (I5)), 0.580 g
(5.73 mmol:3 eq.) of triethylamine, 20 mL, of dry-acetonitrile, and
0.735 g (2.87 mmol:1.5 eq.) of N-succinimidyl carbonate were put
into a 100-mL two-neck recovery flask in a nitrogen atmosphere, and
the mixture was stirred at room temperature for 40 hours.
Thereafter, the reaction solution was concentrated, 30 mL of
purified water and 5 mL of 2 N hydrochloric acid were added
thereto, and the mixture was extracted with ethyl acetate (30
mL.times.3) and washed with 5% saline (30 mL.times.3). The organic
layer was dried over anhydrous magnesium sulfate, filtered, and
concentrated. The residue was isolated and purified by column
chromatography (hexane:ethyl acetate=3:1), concentrated, and
vacuum-dried to obtain 1.55 g (1.74 mmol, 91%) of a yellow viscous
matter (compound (I6)).
[0141] The identification results of the above-synthesized compound
(compound (I6)),
1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2-methylpr-
opyl N-succinimidyl carbonate, are shown below.
[0142] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. 1.03 and 1.11
(6H, d, d, J=7.2 Hz), 2.05-2.40 (9H, m), 2.79 (4H, s), 4.12-4.37
(4H, m), 6.38 (1H, d, J=4.8 Hz), 6.96 (1H, s), 7.65 (1H, s).
[0143] IR (NaCl): 720 (CF.sub.3), 1227 (CF.sub.2, CF.sub.3), 1336
and 1524 (NO.sub.2), 1746 (C.dbd.O) cm.sup.-1.
##STR00020##
[0144] 0.603 g (0.680 mmol) of the (compound (I6)), 10 mL of
dry-tetrahydrofuran (hereinafter referred to as "THF"), and 0.136 g
(0.759 mmol:1.1 eq) of 3-aminopropyltrimethoxysilane were put into
a 30-mL two-neck recovery flask, and the mixture was stirred at
room temperature for 3.5 hours. Thereafter, the reaction solution
was concentrated and isolated by medium-pressure column
chromatography (hexane:ethyl acetate:tetramethoxysilane=3:1:0.04),
concentrated, and vacuum-dried to obtain 0.451 g (0.473 mmol, 70%)
of a pale yellow solid (compound (1)).
[0145] The identification results of the above-synthesized compound
(1),
1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2-methylpr-
opyl N-(3-trimethoxysilyl)propylcarbamate, are shown below.
[0146] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. 0.58-0.67 (2H,
m), 0.98 (6H, dd, J=6.8, 4.0 Hz), 1.56-1.63 (2H, m), 2.10-2.20 (5H,
m), 2.26-2.41 (4H, m), 3.09-3.16 (2H, m), 3.56 (9H, s), 4.10-4.15
(4H, m), 5.00 (1H, t, J=5.8 Hz), 6.20 (1H, d, J=5.2 Hz), 6.87 (1H,
s), 7.57 (1H, s).
[0147] IR (KBr):720 (CF.sub.3), 1227 (CF.sub.2, CF.sub.3), 1336 and
1524 (NO.sub.2), 1746 (C.dbd.O) cm.sup.-1.
##STR00021##
Example 2
Synthesis of Fluorine-Containing Compound (2)
[0148] As the Example,
1-(2-nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)oxy)phen-
yl)ethyl(3-(triethoxysilyl)propyl)carbamate (fluorine-containing
compound (2)) is shown. The compound was synthesized by the step
shown in [Chem. 25], which will be described later.
Synthesis of
1-(3,4-Bis((4,4,5,5,6,6,7,7,8,8,8-undecafluorooctyl)oxy)phenyl)ethanone
(Step 1)
[0149]
1-(3,4-Bis((4,4,5,5,6,6,7,7,8,8,8-undecafluorooctyl)oxy)phenyl)etha-
none (compound (I21)) was synthesized by the step shown below.
[0150] 1.11 g (8.03 mmol) of potassium carbonate was metered into a
100-mL three-neck recovery flask, 10 mL of DMF and 0.61 g (4.01
mmol) of 1-(3,4-dihydroxyphenyl)ethanone were added thereto while
purging the inside of the reactor with nitrogen, and the mixture
was stirred at room temperature for 10 minutes. Thereafter, 4.00 g
(8.20 mmol) of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-9-iodonate
which had been dissolved in 8 mL of DMF was added dropwise thereto
and the mixture was stirred at room temperature for 24 hours.
Thereafter, the mixture was warmed to 60.degree. C. and stirred for
1 hour. The reaction solution was distilled off under reduced
pressure, 20 mL of purified water, 60 mL of a saturated aqueous
ammonium chloride solution, and 40 mL of 1.2 N hydrochloric acid
were added thereto, and the mixture was extracted with ethyl
acetate (50 mL.times.6) and washed with a saturated aqueous sodium
chloride solution (40 mL.times.3). The organic layer was dried over
anhydrous sodium sulfate, filtered, concentrated, and vacuum-dried
to obtain 3.46 g (3.97 mmol, 99%) of a white solid (compound
(I21)).
[0151] The identification results of the compound obtained by the
above synthesis (compound (I21)) are shown below.
[0152] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. (ppm) 2.10-2.19
(4H, m), 2.26-2.40 (4H, m), 3.05 (3H, s), 4.12 and 4.13 (4H, t, t,
J=7.2 Hz), 6.88 (1H, d, J=10.5 Hz), 7.50 (1H, d, J=2.5 Hz), 7.56
(1H, dd, J=2.5, 14.8 Hz).
[0153] .sup.13C-NMR (100 MHz, CDCl.sub.3): .delta. (ppm) 20.63,
26.29, 27.88, 67.35, 111.64, 112.21, 123.69, 130.91, 148.35,
152.74, 196.78.
[0154] .sup.19F-NMR (376 MHz, CDCl.sub.3): .delta. (ppm) -126.29
(4F), -123.53 (4F), -123.01 (4F), -122.04 (4F), -114.62 (4F),
-80.92 (6F).
##STR00022##
Synthesis of
1-(2-Nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)oxy)phen-
yl)ethanone (Step 2)
[0155]
1-(2-Nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)ox-
y)phenyl)ethanone (compound (I22)) was synthesized by the step
shown below.
[0156] 100 g (1.15 mmol) of
1-(3,4-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)oxy)phenyl)ethan-
one was put into a 50-mL three-neck recovery flask and dissolved in
3 mL of acetic acid. Further, 3 mL of 60% nitric acid which had
been dissolved in 2 ml of acetic acid was added dropwise thereto,
and the mixture was warmed to 50.degree. C. and stirred for 4
hours. Thereafter, 100 ml of ice water was added to the inside of
the reactor, and the mixture was extracted with ethyl acetate (50
mL.times.6) and washed with a saturated aqueous sodium hydrogen
carbonate solution (50 mL.times.3). The organic layer was dried
over anhydrous sodium sulfate, filtered, and concentrated. The
residue was isolated and purified by flash column chromatography
(hexane:ethyl acetate=5:1 to 0:1), concentrated, and vacuum-dried
to obtain 0.84 g (0.92 mmol, 80%) of an off-white solid (compound
(I22)).
[0157] The identification results of the compound obtained by the
above synthesis (compound (I22)) are shown below.
[0158] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. (ppm) 2.15-2.21
(4H, m), 2.27-2.39 (4H, 2.48 (3H, s), 4.16 and 4.16 (4H, t), 6.64
(1H, s), 7.59 (1H, s).
[0159] .sup.13C-NMR (100 MHz, CDCl.sub.3): .delta. (ppm) 20.46,
27.68, 30.47, 67.80, 108.15, 109.78, 133.16, 138.65, 148.82,
153.29, 199.93.
[0160] .sup.19F-NMR (376 MHz, CDCl.sub.3): .delta. (ppm) -126.28
(4F), -123.52 (4F), -123.01 (4F), -122.03 (4F), -114.64 (4F),
-80.84 (6F).
##STR00023##
Synthesis of
1-(2-Nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)oxy)phen-
yl)ethanol (Step 3)
[0161]
1-(2-Nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)ox-
y)phenyl)ethanol (compound (I23)) was synthesized by the step shown
below.
[0162] 0.080 g (2.11 mmol) of sodium borohydride, 1 mL of
tetrahydrofuran, and 1 mL of methanol were put into a 50-mL
recovery flask, and the mixture was stirred for 5 minutes. 2 mL of
tetrahydrofuran, and 0.84 g (0.92 mmol) of
1-(2-nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)oxy)phen-
yl)ethanone which had been dissolved in 2 mL of methanol were put
into another container and added dropwise slowly at 0.degree. C.
After 15 minutes, the mixture was warmed to room temperature and
stirred for 45 minutes. The reaction solution was concentrated and
extracted with 5 mL of purified water, 20 ml of a saturated aqueous
ammonium chloride solution, and ethyl acetate (50 mL.times.4). The
organic layer was dried over anhydrous sodium sulfate, filtered,
and concentrated. The residue was isolated and purified by flash
column chromatography (hexane:ethyl acetate=10:1 to 3:1),
concentrated, and vacuum-dried to obtain 0.40 g (0.43 mmol, 80%) of
a yellowish green viscous matter (compound (I23)).
[0163] The identification results of the compound obtained by the
above synthesis (compound (I23)) are shown below.
[0164] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. (ppm) 2.12-2.20
(4H, m), 2.27-2.40 (5H, m), 4.10-4.20 (3H, m), 7.29 (1H, s), 7.55
(1H, s).
[0165] .sup.13C-NMR (100 MHz, CDCl.sub.3): .delta. (ppm) 20.05,
24.45, 27.76, 65.81, 67.59, 109.34, 109.84, 137.25, 139.84, 146.96,
153.17.
[0166] .sup.19F-NMR (376 MHz, CDCl.sub.3): .delta. (ppm) -126.27
(4F), -123.52 (4F), -123.00 (4F), -122.02 (4F), -114.62 (4F),
-80.86 (6F).
##STR00024##
Synthesis of
1-(2-Nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)oxy)phen-
yl)ethyl(3-(triethoxysilyl)propyl)carbamate (Step 4)
[0167]
1-(2-Nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)ox-
y)phenyl)ethyl
(3-(triethoxysilyl)propyl)carbamate(fluorine-containing compound
(2)) was synthesized by the step shown below.
[0168] 0.24 g (0.26 mmol) of
1-(2-nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)oxy)phen-
yl)ethanol, 3 mL of tetrahydrofuran, and 0.17 g (0.71 mmol) of
triethoxy(3-isocyanatopropyl)silane were added to a 30-mL recovery
flask under nitrogen, and dibutyl tin dilaurate which had been
dissolved in 2 mL of tetrahydrofuran was added dropwise thereto.
After stirring at room temperature for 30 minutes, the mixture was
heated and refluxed, and stirred for 21 hours. The reaction
solution was concentrated, isolated by flash silica gel column
chromatography (hexane:ethyl acetate=10:1 to 3:1), concentrated,
and vacuum-dried to obtain. 0.29 g (0.25 mmol, 93%) of a pale
yellow solid (fluorine-containing compound (2)).
[0169] The identification results of the compound obtained by the
above synthesis (fluorine-containing compound (2)) are shown
below.
[0170] .sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. (ppm) 0.56-0.64
(4H, m), 1.18-1.24 (12H, m), 1.55-1.65 (5H, m), 2.11-2.19 (4H, m),
2.24-2.40 (4H, m), 3.05-3.50 m), 3.77-3.83 (6H, m), 4.08-4.16 (4H,
m), 5.03 (1H, t), 6.33 (1H, q), 6.97 (1H, s), 7.56 (1H, s).
[0171] .sup.13C-NMR (100 MHz, CDCl.sub.3): .delta. (ppm) 7.67,
18.13, 20.49, 22.14, 23.20, 27.72, 43.34, 58.42, 67.53, 67.65,
68.55, 109.45, 109.54, 134.63, 140.06, 147.10, 152.95, 155.23.
[0172] .sup.19F-NMR (376 MHz, CDCl.sub.3): .delta. (ppm) -126.27
(4F), -123.54 (4F), -123.01 (4F), -122.03 (4F), -114.64 (4F),
-80.88 (6F).
##STR00025##
[0173] The synthesis route of
1-(2-nitro-4,5-bis((4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro
phenyl)oxy)phenyl)ethyl(3-(triethoxysilyl)propyl)carbamate
(fluorine-containing compound (2)) is shown below.
##STR00026##
Example 3
Surface Modification of Substrate with Fluorine-Containing Compound
(1)
[0174] The substrate was subjected to surface modification using
the fluorine-containing compound (1) obtained by the above
synthesis method.
[0175] With respect to the modified substrate obtained, the static
contact angle of water was measured and the surface density was
calculated using UV. The photodegradation was tracked by a change
in the static contact angle of water, and a comparison between
before and after light irradiation by X-ray photoelectron
spectroscopy (hereinafter referred to as "XPS") and X-ray
reflectometer (hereinafter referred to as "XRR") was carried
out.
[0176] [Pretreatment Step]
[0177] A silicon wafer (3.5 cm.times.1.5 cm) and quartz glass (4
cm.times.1 cm) were subjected to a pretreatment with a UV-ozone
cleaner.
[0178] A silicon wafer and quartz glass were subjected to
ultrasonic washing for 5 minutes with methanol, pure water, and
acetone, respectively. Then, the substrate was taken out and dried
in a stream of nitrogen, the mirror surface of the silicon wafer
was irradiated with UV for 1.5 hours, and both sides of the quartz
glass was pretreated for 1.5 hours, using a UV-ozone cleaner. The
oxygen injection into the UV-ozone cleaner was performed at a flow
rate of 6 L/min for 3 minutes and UV irradiation was performed for
1.5 hours. The generated ozone was discharged by flowing nitrogen
at a flow rate of 6 L/min for 10 minutes.
[0179] [Surface Modification Step]
[0180] Subsequently, 20 mL of a dry toluene solution and 19.1 mg
(20.0 .mu.mol) of the fluorine-containing compound (1) were put
into a 50-mL recovery flask, thereby preparing a 1 mM solution in
the recovery flask. The substrate which had been subjected to the
pretreatment was put into this recovery flask, heated at
100.degree. C., and immersed for 1 hour. The substrate was washed
with methanol and subjected to ultrasonic washing with methanol and
chloroform, respectively, for 10 minutes, and dried in a stream of
nitrogen. This substrate was used in Example 3.
[0181] In Comparative Example 1, the substrate was modified by the
same method as above except that the following compound (I1) was
used as a modifying compound.
##STR00027##
[0182] In Example 3, it is presumed that the chemical modification
of the substrate was carried out as follows.
##STR00028##
[0183] In Example 3, it is presumed that the substrate was modified
from the viewpoints that the static contact angle of water of the
obtained substrate surface was 101.degree. for the silicon wafer
and 100.degree. for the quartz glass, both of which exhibited
hydrophobicity. Further, from the results of the XPS measurement,
it was demonstrated that modifications could be carried out from
the viewpoint that F peaks appeared on the substrate after the
modification. The results are shown in Table 1. In addition, the
surface density calculated from UV in the quartz glass was
1.7.times.10.sup.14 molecules/cm.sup.2.
[0184] <<Light Irradiation onto Modified
Substrate>>
[0185] Thereafter, in order to investigate the photodegradation of
the modified substrate thus obtained, light irradiation at an
intensity of 25 mW/cm.sup.2 was carried out through a copper
sulfate filter that shields light at a wavelength of 320 nm or
less, by an ultrahigh-pressure mercury lamp. The substrate after
the light irradiation was washed with methanol and chloroform,
subjected to ultrasonic washing for 5 minutes with chloroform, and
dried in a stream of nitrogen.
[0186] The photodegradation was performed as in the following
scheme, and when the light was irradiated, a nitroso compound was
dissociated by the photodegradation of a nitrobenzyl group, whereby
an amino group can be introduced into the substrate surface.
##STR00029##
[0187] FIG. 2 shows the results of the measurement of a change in
the static contact angles of water over time by irradiating the
substrates of Example 3 and Comparative Example 1 (both substrates
are silicon wafer substrates) with light. In FIG. 2, the
Comparative Example compound represents Comparative Example 1 and
Example compound represents Example 3.
[0188] From the change in the static contact angles of water by
irradiating the modified substrate shown in FIG. 2 with light, in
Example 3, from the viewpoint that the contact angle decreased
according to the exposure dose and finally, the surface became
hydrophilic at 34.degree., it was confirmed that the
photodegradation proceeded. In addition, it could be also confirmed
that dissociation of the photodegradable group occurred from the
viewpoint that F decreased to a larger extent than that of the
compositional ratio of the respective elements shown in Table
1.
[0189] In addition, the difference in the contact angles between
before and after the light irradiation in Example 3 was larger than
that in Comparative Example 1.
[0190] The compositional ratios of the respective elements when the
elemental compositional ratio of Si--Si determined from the XPS
spectrum before and after the substrates of Example 3 and
Comparative Example 1 (both substrates are silicon wafer
substrates) were irradiated with light was normalized as 1 are
shown in Table 1 below.
TABLE-US-00001 TABLE 1 C.sub.1S N.sub.1S (NO.sub.2) F.sub.1S Si--Si
After After After After After After After After modifi- expo-
modifi- expo- modifi- expo- modifi- expo- cation sure cation sure
cation sure cation sure Example 3 0.81 0.69 0.053 0.0043 0.7 0.013
1 1 Comparative 0.58 0.44 0.016 0.0087 0.54 0.043 1 1 Example 1
[0191] As shown in Table 1, it could be confirmed that the peaks of
the element based on the photodegradable group are lost and the
photodegradable group is dissociated by exposure.
[0192] <<Experimental Examples of Surface Modification in
2-Steps>>
[0193] As shown in the following Experimental Example 1,
Experimental Examples in which the substrate surface is subjected
to a 2-step surface modification using the fluorine-containing
compound of the present invention are described.
[0194] First, the contact angle could be changed from 101.degree.
to 34.degree. by subjecting the silicon wafer substrate to surface
modification using the fluorine-containing compound of the present
invention and performing exposure (.lamda.>320 nm, 25
mW/cm.sup.2), (see (A) and (B) in [First Step] of the following
Experimental Example 1).
[0195] Next, the compound (C) was allowed to undergo a reaction
with the (B) obtained in the first step in 80 .mu.L of
triethylamine and 20 mL of dry DMSO at room temperature for 40
hours. Thus, it could be confirmed that the 2-step surface
modification can be performed since the contact angle of the
substrate surface was changed to 75.degree. (see (D) in [Second.
Step] of the following Experimental Example 1).
##STR00030##
[0196] The XPS measurement results and the XRR measurement results
of (A), (B), and (D) in Experimental Example with the 2-step
surface modification are shown in Tables 2 and 3, respectively.
TABLE-US-00002 TABLE 2 C.sub.1S N.sub.1S F.sub.1S Si--Si (A) 0.81
0.053 0.7 1 (B) 0.69 0.043 0.013 1 (D) 0.63 0.045 0.37 1
TABLE-US-00003 TABLE 3 Thickness (nm) Found value/Calculated value
(A) 1.9/2.1 (B) 0.99/0.6 (D) 1.3/1.3
[0197] As shown from the above results, it could be confirmed that
a surface modification can be performed in 2-steps also from the
XPS measurement results and the XRR measurement results. Thus, it
may be possible that hydrophilic-water-repellent patterns and the
adhesion with an organic semiconductor can also be satisfied.
REFERENCE SIGNS LIST
[0198] S: Substrate [0199] CONT: Controlling unit [0200] Sa:
Surface to be treated [0201] 2: Substrate-supplying unit [0202] 3:
Substrate-treating unit [0203] 4: Substrate-retrieving unit [0204]
6: Fluorine-containing compound-applying unit [0205] 7: Exposing
unit [0206] 8: Mask [0207] 9: Pattern forming material
material-applying unit [0208] 100: Substrate-treating apparatus
* * * * *