U.S. patent application number 15/433314 was filed with the patent office on 2017-06-08 for fluorine-containing compound, substrate for pattern formation, photodegradable coupling agent, pattern formation 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 Kazuo YAMAGUCHI.
Application Number | 20170158606 15/433314 |
Document ID | / |
Family ID | 50237188 |
Filed Date | 2017-06-08 |
United States Patent
Application |
20170158606 |
Kind Code |
A1 |
YAMAGUCHI; Kazuo |
June 8, 2017 |
FLUORINE-CONTAINING COMPOUND, SUBSTRATE FOR PATTERN FORMATION,
PHOTODEGRADABLE COUPLING AGENT, PATTERN FORMATION METHOD, AND
COMPOUND
Abstract
A compound represented by formula (e): ##STR00001## where
R.sup.1 represents a branched chain or cyclic alkyl group having 3
to 10 carbon atoms, and R.sup.f1 and R.sup.f2 represent fluorinated
alkoxy groups.
Inventors: |
YAMAGUCHI; Kazuo; (Yokohama,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
KANAGAWA UNIVERSITY
NIKON CORPORATION |
Yokohama
Tokyo |
|
JP
JP |
|
|
Assignee: |
KANAGAWA UNIVERSITY
Yokohama
JP
NIKON CORPORATION
Tokyo
JP
|
Family ID: |
50237188 |
Appl. No.: |
15/433314 |
Filed: |
February 15, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14635583 |
Mar 2, 2015 |
9606437 |
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15433314 |
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PCT/JP2013/073771 |
Sep 4, 2013 |
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14635583 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 205/37 20130101;
G03F 7/0002 20130101; H01L 21/0274 20130101; G03F 7/0046 20130101;
G03F 7/0755 20130101; G03F 7/20 20130101; C07C 49/84 20130101; C07C
205/56 20130101; G03F 7/2002 20130101; G03F 7/16 20130101; C07C
49/825 20130101; C07F 7/1804 20130101; C07C 205/45 20130101 |
International
Class: |
C07C 205/37 20060101
C07C205/37 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 4, 2012 |
JP |
2012-194531 |
Claims
1. A compound represented by formula (e): ##STR00031## where
R.sup.1 represents a branched chain or cyclic alkyl group having 3
to 10 carbon atoms, and R.sup.f1 and R.sup.f2 represent fluorinated
alkoxy groups.
2. The compound according to claim 1, wherein R.sup.l represents an
isopropyl group, an isobutyl group, or a tert-butyl group.
3. The compound according to claim 1, wherein R.sup.f1 or R.sup.f2
represent fluorinated alkoxy groups having 5 or more carbon
atoms.
4. The compound according to claim 1, wherein R.sup.f1 or R.sup.f2
represent fluorinated alkoxy groups having 6 to 10 carbon atoms.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisonal of U.S. application Ser. No.
14/635,583, filed Mar. 2, 2015, allowed, which is a continuation
application of International Patent Application PCT/JP2013/073771,
filed on Sep. 4, 2013, and which claims benefit of foreign priority
to Japanese Patent Application No. 2012-194531, filed on Sep. 4,
2012, and the contents of all of these applications being
incorporated herein by reference.
BACKGROUND
Technical Field
[0002] The present invention relates to a fluorine-containing
compound, a substrate for pattern formation, a photodegradable
coupling agent, a pattern formation method, and a compound.
[0003] In recent years, in the manufacture of micro devices such as
a semiconductor device, an integrated circuit, and a device for an
organic EL display, a method in which a pattern having different
surface characteristics is formed on a substrate, and a micro
device is made by using the difference in the surface
characteristics has been proposed.
[0004] As a pattern formation method using the difference in the
surface characteristics of 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 functional material is
applied to the hydrophilic region.
[0005] In this method, the aqueous solution of functional material
is wet and spread only in the hydrophilic region. Therefore, it is
possible to form a thin film pattern of the functional
material.
[0006] As the material capable of forming a hydrophilic region and
a water repellent region on a substrate, in recent years, a
coupling agent has been used. In Japanese Unexamined Patent
Application, First Publication No. 2008-50321, a photodegradable
coupling agent of which the contact angle before and after light
irradiation can be significantly changed is described.
SUMMARY
[0007] 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
sensitivity.
[0008] Aspects of the present invention are to provide a
fluorine-containing compound useful as a coupling agent which has a
large difference in contact angles before and after light
irradiation and has more favorable sensitivity, a substrate for
pattern formation using the fluorine-containing compound, a
photodegradable coupling agent using the fluorine-containing
compound, a pattern formation method, and a compound useful as an
intermediate when preparing the fluorine-containing compound.
[0009] A first aspect of the present invention is a
fluorine-containing compound represented by a following general
formula (1).
##STR00002##
[In the general formula (1), X represents a halogen atom or an
alkoxy group, R.sup.1 represents a branched chain or cyclic alkyl
group having 3 to 10 carbon atoms, and R.sup.f1 and R.sup.f2 are
fluorinated alkoxy groups. n represents an integer of 0 or
greater.]
[0010] A second aspect of the present invention is a substrate for
pattern formation having a surface chemically modified with the
fluorine-containing compound according to the first aspect.
[0011] A third aspect of the present invention is a photodegradable
coupling agent formed of the fluorine-containing compound according
to the first aspect.
[0012] A fourth aspect of the present invention is a pattern
formation method for forming a pattern on a work surface of an
object, which includes a first step of chemically modifying the
work surface using the fluorine-containing compound according to
the first aspect, a second step of generating a latent image formed
of a hydrophilic region and a water repellent region by irradiating
the chemically modified work surface with light having a
predetermined pattern, and a third step of disposing a pattern
formation material in the hydrophilic region or the water repellent
region.
[0013] A fifth aspect of the present invention is a compound
represented by a following general formula (f).
##STR00003##
[In the general formula (f), R.sup.1 represents a branched chain or
cyclic alkyl group having 3 to 10 carbon atoms, R.sup.f1 and
R.sup.f2 represent fluorinated alkoxy groups, and n represents an
integer of 0 or greater.]
[0014] A sixth aspect of the present invention is a compound
represented by a following general formula (e).
##STR00004##
[In the general formula (e), R.sup.1 represents a branched chain or
cyclic alkyl group having 3 to 10 carbon atoms, and R.sup.f1 and
R.sup.f2 are fluorinated alkoxy groups.]
[0015] A seventh aspect of the present invention is a compound
represented by a following general formula (d).
##STR00005##
[In the general formula (d), R.sup.1 represents a branched chain or
cyclic alkyl group having 3 to 10 carbon atoms, and R.sup.f1 and
R.sup.f2 are fluorinated alkoxy groups.]
[0016] An eighth aspect of the present invention is a compound
represented by a following general formula (c).
##STR00006##
[In the general formula (c), R.sup.1 represents a branched chain or
cyclic alkyl group having 3 to 10 carbon atoms, and R.sup.f1 and
R.sup.f2 are fluorinated alkoxy groups.]
[0017] According to the aspects of the present invention, a
fluorine-containing compound useful as a coupling agent which has a
large difference in contact angles before and after light
irradiation and has more favorable sensitivity, a substrate for
pattern formation using the fluorine-containing compound, a
photodegradable coupling agent using the fluorine-containing
compound, a pattern formation method, and a compound useful as an
intermediate when preparing the fluorine-containing compound are
provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a schematic view showing a first step in a pattern
formation method of the present invention.
[0019] FIG. 2 is a schematic view showing a second step in the
pattern formation method of the present invention.
[0020] FIG. 3 is a schematic view showing an entire configuration
of a preferable substrate processing apparatus in the pattern
formation method of the present invention.
DESCRIPTION OF EMBODIMENTS
<<Fluorine-Containing Compound>>
[0021] A first aspect of the present invention is a
fluorine-containing compound represented by the following general
formula (1).
##STR00007##
[In the general formula (1), X represents a halogen atom or an
alkoxy group, R.sup.1 represents a branched chain or cyclic alkyl
group having 3 to 10 carbon atoms, and R.sup.f1 and R.sup.f2 are
fluorinated alkoxy groups. n represents an integer of 0 or
greater.]
[0022] In the formula (1), X represents a halogen atom or an alkoxy
group. Examples of the halogen atom represented by X include a
fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Here, X in the formula (1) is preferably an alkoxy group rather
than a halogen atom. In the formula (1), n represents an integer.
From the viewpoint of easy availability of starting materials, n is
preferably an integer of 1 to 20, and more preferably an integer of
2 to 15.
[0023] In the general formula (1), R.sup.1 represents a branched
chain or cyclic alkyl group having 3 to 10 carbon atoms.
[0024] Examples of a branched chain alkyl group having 3 to 10
carbon atoms of R.sup.1 in the formula (1) include such as an
isobutyl group, an isopentyl group, a 2-methylbutyl group, a
2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl
group, a 2-ethylbutyl group, a 2-methylhexyl group, a 3-methylhexyl
group, a 4-methylhexyl group, a 5-methylhexyl group, a
2-ethylpentyl group, a 3-ethylpentyl group, a 2-methylheptyl group,
a 3-methylheptyl group, a 4-methylheptyl group, a 5-methylheptyl
group, a 2-ethylhexyl group, a 3-ethylhexyl group, an isopropyl
group, a sec-butyl group, a 1-ethylpropyl group, a 1-methylbutyl
group, a 1,2-dimethylpropyl group, a 1-methylheptyl group, a
1-ethylbutyl group, a 1,3-dimethylbutyl group, a 1,2-dimethylbutyl
group, a 1-ethyl-2-methylpropyl group, a 1-methylhexyl group, a
1-ethylheptyl group, a 1-propylbutyl group, a
1-isopropyl-2-methylpropyl group, a 1-ethyl-2-methylbutyl group, a
1-propyl-2-methylpropyl group, a 1-ethylhexyl group, a
1-propylpentyl group, a 1-isopropylpentyl group, a
1-isopropyl-2-methylbutyl group, a 1-isopropyl-3-methylbutyl group,
a 1-methyloctyl group, a 1-propylhexyl group, a
1-isobutyl-3-methylbutyl group, a tert-butyl group, a tert-hexyl
group, a tert-pentyl group, and a tert-octyl group.
[0025] In the formula (1), examples of a cyclic alkyl group having
3 to 10 carbon atoms of R.sup.1 include such as a cyclopropyl
group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group,
a cycloheptyl group, a cyclooctyl group, and an adamantyl
group.
[0026] In the formula (1), R.sup.1 is preferably a group having 3
to 8 carbon atoms, more preferably a group having 3 to 6 carbon
atoms, and particularly preferably a group having 3 to 5 carbon
atoms.
[0027] In the formula (1), R.sup.1 is preferably an isopropyl
group, an isobutyl group, or a tert-butyl group, among the
above-described branched chain or cyclic alkyl groups.
[0028] In the formula (1), R.sup.f1 or R.sup.f2 is a fluorinated
alkoxy group. R.sup.f1 or R.sup.f2 is preferably a fluorinated
alkoxy group having 5 or more carbon atoms. R.sup.f1 or R.sup.f2
may be the same as or different from each other, and are preferably
the same.
[0029] Examples of the fluorinated alkoxy group of R.sup.f1 or
R.sup.f2 include such as
--O--(CH.sub.2).sub.3(CF.sub.2).sub.3CF.sub.3,
--O--(CH.sub.2).sub.3(CF.sub.2).sub.4CF.sub.3,
--O--(CH.sub.2).sub.4(CF.sub.2).sub.4CF.sub.3,
--O--(CH.sub.2).sub.4(CF.sub.2).sub.5CF.sub.3, and
--O--(CH.sub.2).sub.2(CF.sub.2).sub.3CF.sub.3.
[0030] <<Compound>>
[0031] A fifth aspect of the present invention is a compound
represented by the following general formula (f).
##STR00008##
[In the general formula (f), R.sup.1 represents a branched chain or
cyclic alkyl group having 3 to 10 carbon atoms, R.sup.f1 and
R.sup.f2 are fluorinated alkoxy groups, and m represents an integer
of 0 or greater.]
[0032] In the above general formula (f), 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 the
general formula (1). m in the above formula (f) represents an
integer. From the viewpoint of easy availability of starting
materials, m is preferably an integer of 1 to 20, and more
preferably an integer of 2 to 15.
[0033] A sixth aspect of the present invention is a compound
represented by the following general formula (e).
##STR00009##
[In the general formula (e), R.sup.1 represents a branched chain or
cyclic alkyl group having 3 to 10 carbon atoms, and R.sup.f1 and
R.sup.f2 are fluorinated alkoxy groups.]
[0034] In the above general formula (e), 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 the
general formula (1).
[0035] A seventh aspect of the present invention is a compound
represented by the following general formula (d).
##STR00010##
[In the general formula (d), R.sup.1 represents a branched chain or
cyclic alkyl group having 3 to 10 carbon atoms, and R.sup.f1 and
R.sup.f2 are fluorinated alkoxy groups.]
[0036] In the above general formula (d), 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 the
general formula (1).
[0037] An eighth aspect of the present invention is a compound
represented by the following general formula (c).
##STR00011##
[In the general formula (c), R.sup.1 represents a branched chain or
cyclic alkyl group having 3 to 10 carbon atoms, and R.sup.f1 and
R.sup.f2 are fluorinated alkoxy groups.]
[0038] In the above general formula (c), R.sup.1, R.sup.f1, and
R.sup.2 are the same as R.sup.1, R.sup.f1, and R.sup.f2 in the
general formula (1).
[0039] The compounds according to the fifth to the eighth aspects
of the present invention are useful as a raw material
(intermediate) of the fluorine-containing compound according to the
first aspect of the present invention.
[0040] <Preparation Method of Fluorine-Containing
Compound>
[0041] The fluorine-containing compound of the present invention is
preferably prepared using the compounds according to the fifth to
the eighth aspects of the present invention as a raw material
(intermediate).
[0042] 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.
[Step of Obtaining Compound According to Eighth Aspect]
[0043] The compound according to the eighth aspect of the present
invention can be obtained by the following step.
##STR00012##
[0044] In the above reaction formula, 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 the
general formula (1), --O--R.sup.f1' is R.sup.f1, and --O--R.sup.f2'
is R.sup.f2.
[0045] [Step of Obtaining Compound According to Seventh Aspect]
[0046] The compound according to the seventh aspect of the present
invention can be obtained by the following step.
##STR00013##
[0047] In the above reaction formula, 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 the
general formula (1).
[0048] [Step of Obtaining Compound According to Sixth Aspect]
[0049] The compound according to the sixth aspect of the present
invention can be obtained by the following step.
##STR00014##
[0050] In the above reaction formula, 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 the
general formula (1).
[0051] [Step of Obtaining Compound According to Fifth Aspect]
[0052] The compound according to the fifth aspect of the present
invention can be obtained by the following step.
##STR00015##
[0053] In the above reaction formula, 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 the
general formula (1), and m is an integer of 0 or greater.
[0054] [Step of Obtaining Flourine-Containing Compound According to
First Aspect]
[0055] The fluorine-containing compound according to the first
aspect of the present invention is obtained by a reaction of
trimethoxysilane and the compound (f). In the following steps, a
catalyst is preferably used, and a platinum-carbonylvinylmethyl
complex (Ossko catalyst) or a platinum-divinyltetramethyldisiloxane
complex (Karstedt catalyst) and the like can be used.
##STR00016##
[0056] In the above reaction formula, 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 the
general formula (1), and m and n are integers of 0 or greater.
[0057] In the above reaction formula, X, R.sup.1, R.sup.f1,
R.sup.f2, and n are the same as those in the general formula
(1).
[0058] <<Substrate for Pattern Formation>>
[0059] A second aspect of the present invention is a substrate for
pattern formation having a surface chemically modified with the
fluorine-containing compound.
[0060] The substrate is not particularly limited, however, glass,
quartz glass, a silicon wafer, a plastic plate, a metal plate, and
the like are preferable. In addition, a substrate on which a metal
thin film was formed may be used.
[0061] The shape of the substrate is not particularly limited,
however, a plane surface, a curved surface, or a plane surface
having partially a curved surface is preferable, and a plane
surface is more preferable. In addition, the area of the substrate
is also not particularly limited, however, a substrate having a
large surface within a range in which applying methods in the
related art can be applied can be employed. In addition, a surface
chemically modified with the fluorine-containing compound is
preferably formed on one side of the substrate on the plane
surface.
[0062] When modifying the surface of a substrate, the substrate
surface is preferably subjected to a pretreatment in advance. As
the pretreatment method, a pretreatment in a piranha solution or a
pretreatment by a UV-ozone cleaner is preferable.
[0063] The method for modifying the surface of a substrate is not
particularly limited as long as it is a method in which X bonded to
reactive Si, in the general formula (1), bonds to a substrate,
however, known methods such as a dipping method and a chemical
treatment method can be used.
[0064] <<Photodegradable Coupling Agent>>
[0065] A third aspect of the present invention is a photodegradable
coupling agent formed of the fluorine-containing compound.
[0066] The photodegradable coupling agent of the aspects of the
present invention has a photodegradable group with a liquid
repellent group and an attaching group X linked to the
photodegradable group through a functional group. The liquid
repellent group has fluorinated alkoxy chains R.sup.f1 and R.sup.f2
at the terminal thereof. The functional group has a carboxy group
as a residue after photodegradation. Therefore, in the
photodegradable coupling agent of the present invention, a large
difference in contact angles before and after light irradiation can
be secured. That is, on the surface on which the photodegradable
coupling agent was disposed, wettability (liquid
repellency/hydrophilicity) significantly changes, and a
comparatively large difference value between a contact angle (angle
between the tangent line and the surface of a droplet) of the
liquid (for example, water) on the surface before light irradiation
and a contact angle of the liquid on the surface after light
irradiation can be provided.
[0067] <<Pattern Formation Method>>
[0068] A fourth aspect of the present invention is a pattern
formation method for forming a pattern on a work surface of an
object, which includes a first step of chemically modifying the
work surface using the fluorine-containing compound according to
the first aspect, a second step of generating a latent image formed
of a hydrophilic region and a water repellent region by irradiating
the chemically modified work surface with light having a
predetermined pattern, and a third step of disposing a pattern
formation material in the hydrophilic region or the water repellent
region.
[0069] [First Step]
[0070] The first step in the pattern formation method for forming a
pattern on a work surface of an object is a step of chemically
modifying the work surface using the fluorine-containing compound
according to the first aspect.
[0071] The object is not particularly limited. In the present
invention, examples thereof include a metal, a crystalline material
(for example, single crystalline, polycrystal, and 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, polyphenylene), a film, a thin film, and a
foil.
[0072] In the pattern formation method according to the aspects of
the present invention, a circuit pattern for an electronic device
is preferably formed on a substrate having flexibility.
[0073] In the present invention, as the substrate having
flexibility which is an 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.
[0074] Here, the flexibility refers to properties capable of
flexing the substrate without being broken or fractured even in a
case where a force of about its own weight is added to the
substrate. In addition, properties of bending by force of about its
own weight are also included the flexibility. 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. Moreover, as the substrate, a single belt-shape substrate
may be used, or the substrate may be configured to be formed in a
belt-shape by connecting a plurality of unit substrates.
[0075] In the first step, the entire surface on a work surface of
an object or a specific region is preferably chemically modified by
using the fluorine-containing compound.
[0076] The method for chemically modifying a work surface of an
object is not particularly limited as long as it is a method in
which X bonded to reactive Si, in the general formula (1), bonds to
a substrate, however, known methods such as a dipping method and a
chemical treatment method can be used.
[0077] An example of the chemical modification in the first step is
shown in FIG. 1.
[0078] [Second Step]
[0079] The second step is a step of generating a latent image
formed of a hydrophilic region and a water repellent region by
irradiating the chemically modified work surface with light having
a predetermined pattern.
[0080] As the irradiation light, ultraviolet rays are preferable.
The irradiation light 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 to be irradiated with light
including light having a wavelength of 365 nm. 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, a
sodium lamp, a laser of a gas such as nitrogen, a liquid laser of
organic dye solution, and a laser of a solid in which rare earth
ions are contained in inorganic single crystals.
[0081] In addition, as a light source in which monochromatic light
is obtained, other than the above lasers, light having a specific
wavelength extracted from a broadband line spectrum or a continuous
spectrum using an optical filter such as a band-pass filter or a
cut-off filter may be used. The high-pressure mercury lamp or the
ultrahigh-pressure mercury lamp is preferable as a light source
since a large area can be irradiated with the mercury lamp at
once.
[0082] In the pattern formation method of the present invention, a
work surface can be irradiated with light arbitrarily in the above
range. However, in particular, a work surface is preferably
irradiated with light energy having a distribution corresponding to
a circuit pattern.
[0083] In the second step, a residue (carboxy group) having
hydrophilicity due to dissociation of a group having a water
repellent performance by irradiating the chemically modified work
surface with light having a predetermined pattern is produced.
Therefore, after light irradiation, it is possible to generate a
latent image formed of a hydrophilic region and a water repellent
region.
[0084] In the second step, a latent image of a circuit pattern due
to the difference in hydrophilicity and water repellency is
preferably generated on the surface of a substrate having
flexibility.
[0085] FIG. 2 shows an example of a step in which a residue
(carboxy group) having hydrophilicity due to dissociation of a
group having a water repellent performance by irradiating the
chemically modified work surface with light having a predetermined
pattern is produced.
[0086] [Third Step]
[0087] A third step is a step of disposing a pattern formation
material in a hydrophilic region or a water repellent region which
is generated in the second step.
[0088] Examples of the pattern formation material include such as
wiring materials (metal solution) in which particles of gold,
silver, copper, or an alloy of these 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 a resist
solution.
[0089] In the pattern formation method according to the aspects of
the present invention, the pattern formation material is preferably
a liquid conductive material, a liquid semiconductor material, or a
liquid insulating material.
[0090] Examples of the liquid conductive material include a pattern
formation 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 of gold particles, silver particles, copper
particles, palladium particles, nickel particles, and ITO
particles, fine particles of oxides of the above metals, a
conductive polymer, or superconductor can be used.
[0091] These conductive fine particles can also be used after the
surfaces thereof are coated with an organic material in order to
improve dispersibility.
[0092] The dispersion medium is not particularly limited as long as
it can disperse the above-described conductive fine particles and
does not aggregate. In addition to water, examples thereof 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 droplet discharge method (ink-jet method), water,
alcohols, a hydrocarbon-based compound, and an ether-based compound
are preferable, and as more preferable dispersion media, water and
a hydrocarbon-based compound can be exemplified.
[0093] As the liquid semiconductor material, an organic
semiconductor material dispersed or dissolved in a dispersion
medium can be used. As the organic semiconductor material, a
.pi.-electron conjugated polymer material of which the skeleton is
configured of conjugated double bonds is desired. Representative
examples include soluble high-molecular materials such as
polythiophene, poly(3-alkylthiophene), polythiophene derivatives,
and pentacene.
[0094] As the liquid insulating material, an insulating material in
which polyimide, polyamide, polyester, acryl, PSG (phosphorus
glass), BPSG (boron phosphorus glass), polysilazane-based SOG,
silicate-based SOG (Spin on Glass), alkoxy silicate-based SOG, or
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 can be exemplified.
[0095] In the third step, as a method for disposing a pattern
formation material, a 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.
[0096] Hereinafter, the pattern formation method according to the
aspects of the present invention will be described with reference
to a drawing.
[0097] In the pattern formation method according to the aspects of
the present invention, in a case where a substrate having
flexibility corresponding to a so-called roll-to-roll process is
used, a pattern may be formed by using a substrate processing
apparatus 100 which is a roll-to-roll apparatus, as shown in FIG.
3. FIG. 3 shows a configuration of the substrate processing
apparatus 100.
[0098] As shown in FIG. 3, the substrate processing apparatus 100
has a substrate supplying part 2 that supplies a belt-shape
substrate (for example, a belt-shape film member) S, a substrate
processing part 3 that performs a treatment with respect to the
surface (work surface) Sa of the substrate S, a
substrate-retrieving part 4 that retrieves the substrate S, an
applying part 6 of a fluorine-containing compound, an exposing part
7, a mask 8, a patterning material-applying part 9, and a
controller CONT that controls each of these parts. In the substrate
processing part 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 part 2 to the time when the
substrate S is retrieved by the substrate-retrieving part 4.
[0099] The substrate processing apparatus 100 can be suitably used
in a case where a display element (electronic device) such as an
organic EL element or a liquid crystal display element is formed on
the substrate S.
[0100] Moreover, FIG. 3 is an illustration of a method using a
photomask to generate a desired pattern light. However, the aspects
of the present invention can also be suitably applied to a maskless
exposure method in which a photomask is not used. As the maskless
exposure method in which a desired pattern light is generated
without using a photomask, 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 as a laser beam printer can be
exemplified.
[0101] In the pattern formation method according to the aspects of
the present invention, a XYZ coordinate system is set as shown in
FIG. 3. 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 processing 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 in the
Y-axis direction.
[0102] As the substrate S which is a work surface in the substrate
processing apparatus 100, 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.
[0103] For example, the substrate S preferably has a small thermal
expansion coefficient such that the size is not changed even in a
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 um manufactured by a float method
or the like or a laminate formed by adhering the resin film or
aluminum foil on the ultrathin glass.
[0104] 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 greater. 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.
[0105] The substrate S is preferably formed so as to have
flexibility. Here, the flexibility refers to properties capable of
flexing the substrate without being broken or fractured even in a
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.
[0106] 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. Moreover, 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.
[0107] The substrate supplying part 2, for example, supplies the
substrate S wound in a roll shape by sending the substrate S to the
substrate processing part 3. In this case, in the substrate
supplying part 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 part 2
may have a configuration in which a cover portion that covers the
substrate S in the state of being wound in a roll shape or the like
is provided. Moreover, the substrate supplying part 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 or the like) for sequentially sending the belt-shape
substrate S in the length direction.
[0108] The substrate-retrieving part 4 retrieves the substrate S
passed through the substrate processing apparatus 100, for example,
by winding in a roll shape. In the substrate-retrieving part 4, the
same as in the substrate supplying part 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 a case where the
substrate S is cut into a panel shape or the like in the substrate
processing part 3, for example, the substrate processing part 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.
[0109] The substrate processing part 3 transports the substrate S
supplied from the substrate supplying part 2 to the
substrate-retrieving part 4, and performs a step of chemically
modifying the work surface Sa of the substrate S in a process of
transporting using a fluorine-containing compound, a step of
irradiating a chemically modified work surface with light having a
predetermined pattern, and a step of disposing a pattern formation
material. The substrate processing part 3 has the
fluorine-containing compound-applying part 6 that applies a
fluorine-containing compound to the work surface Sa of the
substrate S, the exposing part 7 that irradiates with light, the
mask 8, the patterning material-applying part 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
processing.
[0110] As the fluorine-containing compound-applying part 6 or the
patterning material-applying part 9, droplet application devices
(for example, a 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) can be exemplified.
[0111] 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 part 7
is provided, and devices performing the steps before and after
thereof (photosensitive layer-forming step, photosensitive
layer-developing step, or the like) are also provided in an in-line
type, if necessary.
[0112] Since the fluorine-containing compound according to the
aspects of the present invention has a photodegradable group with a
water repellent group having a fluorinated alkoxy chain at the
terminal, in a 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 (carboxy group) having hydrophilicity can be produced by
dissociating a group having a water repellent performance by
irradiating with light. Therefore, before and after light
irradiation, the substrate surface exhibits excellent
hydrophilicity, and the contact angle can be reduced.
[0113] In addition, it is considered that in a case where a
branched chain alkyl group having 3 to 5 carbons is present near
the photodegradable group, a group having a water repellent
performance can be dissociated with less energy (exposure
amount).
EXAMPLES
[0114] Hereinafter, the present invention will be specifically
described by the examples, and the present invention is not limited
to the following examples.
[0115] [Synthesis of Fluorine-Containing Compound (1)]
[0116] 9.02 g (65.4 mmol) of 1,2-dimethoxybenzene, 0.311 g (2.45
mmol) of iodine crystals, and 20.7g (131 mmol) of isobutyric acid
anhydride were put into a 100 mL recovery flask, the recovery flask
was refluxed at 170.degree. C. for 6 hours, and after the
temperature in the recovery flask was returned to room temperature,
stirring was performed for 31 hours. Thereafter, 80 mL of H.sub.2O
was added to the recovery flask, and the organic layer was
extracted with diethyl ether (80 mL.times.3). The extracted organic
layer was washed with 5% NaHCO.sub.3 (80 mL), a saturated saline
solution (80 mL), and H.sub.2O (80 mL), dried over anhydrous
MgSO.sub.4, filtered, and concentrated. Thereafter, the organic
layer subjected to the above treatment was isolated and purified by
column chromatography (hexane:ethyl acetate=4:1), and concentration
and vacuum drying were performed, thereby obtaining a compound (a)
(1-(3,4-dimethoxyphenyl)-2-methyl-1-propanone) as a pale yellow
viscous matter.
##STR00017##
[0117] Identification results of the above-synthesized compound (a)
are shown below. [0118] Yield 3.90 g (18.7 mmol, 29%) [0119]
R.sub.f 0.27 (hexane:ethyl acetate=4:1) [0120] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0120] .delta. = 1.22 ( 6 H , d , J = 6.8 Hz ) ( CH 3 ) 2 = 3.55 (
1 H , sep , J = 6.8 Hz ) ( CH 3 ) 2 = 3.94 and 3.95 ( 6 H , s , s )
Ar--OCH 3 .times. 2 = 6.90 ( 1 H , d , J = 8.4 Hz ) Ar--H = 7.55 (
1 H , d , J = 2.0 Hz ) Ar--H = 7.60 ( 1 H , d , d , J = 8.4 Hz )
Ar--H ##EQU00001## [0121] IR (NaCl)
TABLE-US-00001 [0121] 1674 cm.sup.-1 (C.dbd.O)
[0122] Next, 2.73 g (13.1 mmol) of the compound (a) was put into a
100 mL two-neck recovery flask, and 50 mL of
dry-N,N-dimethylformamide (hereinafter, referred to as dry-DMF) and
11.2 g (262 mmol: 20 eq) of LiCl were added thereto in a nitrogen
atmosphere. The two-neck recovery flask was refluxed at 170.degree.
C. for 29 hours, and the inside of the two-neck recovery flask was
stirred at 100.degree. C. for 32 hours. Thereafter, 200 mL of a
saturated saline solution and 50 mL of 2 N HCl were added to the
two-neck recovery flask, and the organic layer was extracted with
ethyl acetate (150 mL.times.3). The extracted organic layer was
dried over anhydrous MgSO.sub.4, filtered, concentrated, and
vacuum-dried. Thereafter, the organic layer subjected to the above
treatment was isolated and purified by column chromatography
(hexane:ethyl acetate=2:1), and concentration and vacuum drying
were performed, thereby obtaining a compound (b)
(1-(3,4-dihydroxyphenyl)-2-methyl-1-propanone) as a yellow viscous
matter.
##STR00018##
[0123] Identification results of the above-synthesized compound (b)
are shown below. [0124] Yield 1.50 g (hexane:ethyl acetate=2:1)
[0125] R.sub.f 0.20 (hexane:ethyl acetate=2:1) [0126] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0126] .delta. = 1.21 ( 6 H , d , J = 6.8 Hz ) ( CH 3 ) 2 = 3.53 (
1 H , sep , J = 6.9 Hz ) --CH = 6.35 ( 1 H , s ) Ar--OH = 6.94 ( 1
H , d , J = 8.4 Hz ) Ar--H = 7.39 ( 1 H , s ) Ar--OH = 7.52 ( 1 H ,
d , d , J = 8.4 Hz ) Ar--H = 7.83 ( 1 H , d , J = 2.0 Hz ) Ar--H
##EQU00002## [0127] IR (NaCl)
TABLE-US-00002 [0127] 3349 cm.sup.-1 (OH) 1656 cm.sup.-1
(C.dbd.O)
[0128] 1.02 g (5.67 mmol) of the compound (b), 15 mL of dry DMF,
and 1.57 g (11.3 mmol: 2 eq) of K.sub.2CO.sub.3 were put into a 100
mL two-neck recovery flask, and the resultant product was stirred
at room temperature for 2 hours. Thereafter, 7 mL of dry DMF was
added to 4.64 g (12.0 mmol: 2.1 eq) of
1-iodine-1H,1H,2H,2H,3H,3H-perfluoroheptane, then, this was added
dropwise to the two-neck recovery flask, and the inside of the
two-neck recovery flask was stirred at 60.degree. C. for 14 hours.
After the reaction solution was distilled off under reduced
pressure, 60 mL of H.sub.2O and 20 mL of 2 N HCl were added
thereto, and the organic layer was extracted with ethyl acetate (60
mL.times.4). The extracted organic layer was washed with a
saturated saline solution (60 mL.times.5). The organic layer was
dried over anhydrous MgSO.sub.4, filtered, concentrated, and
vacuum-dried, thereby obtaining a compound (c)
(1-(3,4-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2-methyl-1-propan-
one) as an orange solid.
##STR00019##
[0129] Identification results of the above-synthesized compound (c)
are shown below. [0130] Yield 3.62 g (5.17 mmol, 91%) [0131]
R.sub.f 0.73 (hexane:ethyl acetate=2:1) [0132] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0132] .delta. = 1.21 ( 6 H , d , J = 6.8 Hz ) ( CH 3 ) 2 = 2.15 to
2.19 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 2.32
to 2.34 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 =
3.53 ( 1 H , sep , J = 6.9 Hz ) --CH-- = 4.13 and 4 .14 ( 4 H , t ,
t ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 6.88 ( 1 H , d ,
J = 8.5 Hz ) Ar--H = 7.52 ( 1 H , d , J = 2.0 Hz ) Ar--H = 7.58 ( 1
H , dd , J = 8.4 Hz ) Ar--H ##EQU00003## [0133] IR (KBr)
TABLE-US-00003 [0133] 722 cm.sup.-1 (CF.sub.3) 1226 cm.sup.-1
(CF.sub.2, CF.sub.3) 1678 cm.sup.-1 (C.dbd.O)
[0134] 0.502 g (0.717 mmol) of the compound (c) was put into a 100
mL recovery flask, and the compound (c) was dissolved in 3 mL of
diethyl ether. 5 mL of 70% NHO.sub.3 was added little by little to
the recovery flask provided in an ice bath, and the inside of the
recovery flask provided in the ice bath was stirred for 1.5 hours.
Next, the reaction solution was poured into ice, then, the organic
layer was extracted with 50 mL of H.sub.2O and ethyl acetate (50
mL.times.3), and the extracted organic layer was washed with 5%
NaHCO.sub.3 (50 mL.times.3). The organic layer was dried over
anhydrous MgSO.sub.4, filtered, and concentrated. Recrystallization
of the compound was performed by dissolving the concentrated
product in 20 mL of ethanol. Suction filtration and vacuum drying
of the crystals were performed, thereby obtaining a compound (d)
1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2-methyl-1-
-propanone) as a light yellow needle-like crystal.
##STR00020##
[0135] Identification results of the above-synthesized compound (d)
are shown below. [0136] Yield 0.256 g (3.43 mmol, 48%) [0137]
R.sub.f 0.40 (hexane:ethyl acetate=6:1) [0138] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0138] .delta. = 1.21 ( 6 H , d , J = 6.8 Hz ) ( CH 3 ) 2 = 2.15 to
2.23 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 2.27
to 2.34 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 =
2.89 ( 1 H , sep ) --CH-- = 4.16 and 4 .17 ( 4 H , t , t ) --O--CH
2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 6.67 ( 1 H , s ) Ar--H = 7.64
( 1 H , s ) Ar--H ##EQU00004## [0139] IR (KBr)
TABLE-US-00004 [0139] 721 cm.sup.-1 (CF.sub.3) 1228 cm.sup.-1
(CF.sub.2, CF.sub.3) 1358 and 1523 cm.sup.-1 (NO.sub.2) 1703
cm.sup.-1 (C.dbd.O)
[0140] 2.96 g (3.97 mmol) of the compound (d), 12 mL of
tetrahydrofuran (hereinafter, referred to as THF), and 8 mL of
methanol were put into a 100 mL recovery flask, then, 0.300 g (7.94
mmol: 2eq) of NaBH.sub.4 was added little by little to the recovery
flask provided in an ice bath, and the inside of the recovery flask
was stirred for 90 minutes. Thereafter, the inside of the recovery
flask was stirred at room temperature for 30 minutes. The reaction
solution was concentrated, and the organic layer was extracted with
60 mL of H.sub.2O, 20 mL of 2 N HCl, and ethyl acetate (50
mL.times.3). The extracted organic layer was dried over anhydrous
MgSO.sub.4, filtered, and concentrated. The organic layer subjected
to the above treatment was isolated and purified by column
chromatography (hexane:ethyl acetate=6:1), and concentration and
vacuum drying were performed, thereby obtaining a compound (e)
(1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2-methyl--
1-propanol) as a yellow viscous matter.
##STR00021##
[0141] Identification results of the above-synthesized compound (e)
are shown below. [0142] Yield 2.17 g (2.90 mmol, 76%) [0143]
R.sub.f 0.20 (hexane:ethyl acetate=6:1) [0144] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0144] .delta. = 0.94 and 0.96 ( 6 H , d , J = 6.8 Hz ) ( CH 3 ) 2
= 1.97 to 2.03 ( 1 H , m ) --CH-- = 2.14 to 2.21 ( 5 H , m )
--O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 Ar--CH--OH = 2.27 to 2
.40 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 4.08
to 4 .23 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 =
5.27 ( 1 H , t , J = 4.8 Hz ) Ar--CH--CH-- ( CH 3 ) 2 = 7.20 ( 1 H
, s ) Ar--H = 7.55 ( 1 H , s ) Ar--H ##EQU00005## [0145] IR
(KBr)
TABLE-US-00005 [0145] 742 cm.sup.-1 (CF.sub.3) 1228 cm.sup.-1
(CF.sub.2, CF.sub.3) 1334 and 1522 cm.sup.-1 (NO.sub.2) 3547
cm.sup.-1 (OH)
[0146] 0.803 g (mmol: 1.5 eq) of carbodiimide hydrochloride and 10
mL of THF were put into a 100 mL two-neck recovery flask in a
nitrogen atmosphere, and the resultant product was stirred for 10
minutes in the two-neck recovery flask provided in an ice bath.
Thereafter, 2.09 g (2.79 mmol: 1 eq) of the compound (e), 0.567 g
(5.58 mmol: 2 eq) of 4-pentenoic acid, and 0.412 g (3.35 mmol: 1.2
eq) of N,N-dimethyl-4-aminopyridine (hereinafter, referred to as
DMAP) were dissolved in 10 mL of dry-THF, and the resultant product
was added dropwise to the two-neck recovery flask. After the inside
of the two-neck recovery flask was stirred for 10 minutes, the
two-neck recovery flask was taken out from the ice bath, and the
inside of the two-neck recovery flask was stirred at room
temperature for 14 hours. The reaction solution was concentrated,
and 40 mL of H.sub.2O and 10 mL of 2 N HCl were added thereto. The
organic layer was extracted with ethyl acetate (50 mL.times.3), and
the extracted organic layer was washed with 5% NaHCO.sub.3 (50
mL.times.3). The organic layer was dried over anhydrous MgSO.sub.4,
filtered, and concentrated. The organic layer subjected to the
above treatment was isolated and purified by column chromatography
(hexane:ethyl acetate=6:1), and concentration and vacuum drying
were performed, thereby obtaining a compound (f)
(1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)
phenyl-2-methylpropyl 4-pentenoic acid ester) as a pale yellow
solid.
##STR00022##
[0147] Identification results of the above-synthesized compound (f)
are shown below. [0148] Yield 2.13 g (2.57 mmol, 92%) [0149]
R.sub.f 0.40 (hexane:ethyl acetate=8:1) [0150] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0150] .delta. = 0.98 and 1.00 ( 6 H , d , J = 6.8 Hz ) ( CH 3 ) 2
= 2.13 to 2.21 ( 5 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 --
.times. 2 --CH-- ( CH 3 ) 2 2.26 to 2.52 ( 8 H , m ) --O--CH 2 --CH
2 --CH 2 --CF 2 -- .times. 2 --CH 2 --CH 2 --COO-- = 4.10 to 4 .15
( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 4.98 to 5
.06 ( 2 H , m ) CH 2 -- -- CH-- = 5.74 to 5 .84 ( 1 H , m ) CH 2 --
-- CH-- = 6.31 ( 1 H , d , J = 5.8 Hz ) Ar--CH--CH-- ( CH 3 ) 2 =
6.87 ( 1 H , s ) Ar--H = 7.57 ( 1 H , s ) Ar--H ##EQU00006## [0151]
IR (KBr)
TABLE-US-00006 [0151] 720 cm.sup.-1 (CF.sub.3) 122 cm.sup.-1
(CF.sub.2, CF.sub.3) 1332 and 1525 cm.sup.-1 (NO.sub.2) 1732
cm.sup.-1 (C.dbd.O)
[0152] 1.01 g (1.22 mmol) of the compound (f) was put into a 50 mL
two-neck recovery flask, and vacuum drying was performed for 1.5
hours. Thereafter, 1 mL of dry-THF, 1.49 g (12.2 mmol: 10 eq) of
trimethoxysilane, 7 drops of a Karstedt catalyst were added to the
two-neck recovery flask, and the inside of the two-neck recovery
flask was stirred at room temperature for 2.5 hours. The reaction
solution was concentrated, the obtained organic layer was isolated
by medium pressure column chromatography (hexane:ethyl
acetate:tetramethoxysilane=8:1:0.09), and concentration and vacuum
drying were performed, thereby obtaining a fluorine-containing
compound (1)
(1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl))-2-methyl-
propyl 5-(trimethoxysilyl)pentenoic acid ester) as a pale yellow
solid.
##STR00023##
[0153] Identification results of the above-synthesized
fluorine-containing compound (1) are shown below. [0154] Yield
0.775 g (0.814 mmol, 67%) [0155] R.sub.f 0.23 (hexane:ethyl
acetate=8:1) [0156] .sup.1H-NMR (CDCl.sub.3/TMS) 400 MHz
[0156] .delta. = 0.61 to 0.67 ( 2 H , m ) --CH 2 -- = 0.97 and 0.99
( 6 H , d , J = 6 .8 Hz ) -- ( CH 3 ) 2 = 1.39 to 1.47 ( 2 H , m )
--Si--CH 2 --CH 2 -- = 1.66 ( 2 H , quint , J = 7.6 Hz ) --CH 2
--CH 2 --COO-- = 2.12 to 2 .21 ( 5 H , m ) --O--CH 2 --CH 2 --CH 2
--CF 2 -- .times. 2 --CH-- ( CH 3 ) 2 = 2.26 to 2 .39 ( 6 H , m )
--O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 --CH 2 --COO-- = 3.55 (
9 H , s ) ( CH 3 O ) 3 --Si-- = 4.08 to 4 .17 ( 4 H , m ) --O--CH 2
--CH 2 --CH 2 --CF 2 -- .times. 2 = 6.30 ( 1 H , d , J = 5.8 Hz )
Ar--CH--CH-- ( CH 3 ) 2 = 6.87 ( 1 H , s ) Ar--H = 7.57 ( 1 H , s )
Ar--H ##EQU00007## [0157] IR (KBr)
TABLE-US-00007 [0157] 720 cm.sup.-1 (CF.sub.3) 1227 cm.sup.-1
(CF.sub.2, CF.sub.3) 1332 and 1525 cm.sup.-1 (NO.sub.2) 1729
cm.sup.-1 (C.dbd.O)
[0158] [Synthesis of Fluorine-containing Compound (2)]
[0159] 10.1 g (72.4 mmol) of 1,2-dimethoxybenzene, 0.553 g (4.36
mmol) of iodine crystals, and 20.4 g (109 mmol) of pivalic acid
anhydride were put into a 100 mL recovery flask, and the inside of
the recovery flask was refluxed at 170.degree. C. for 9 hours, and
at 100.degree. C. for 17 hours. Thereafter, H.sub.2O (80 mL) was
added to the recovery flask, and the organic layer was extracted
with diethyl ether (80 mL.times.3). The extracted organic layer was
washed with a 5% aqueous sodium hydrogen carbonate solution (80
mL), a saturated saline solution (80 mL.times.2), and H.sub.2O (80
mL.times.3), dried over anhydrous MgSO.sub.4, filtered, and
concentrated. The organic layer subjected to the above treatment
was isolated and purified by column chromatography (hexane:ethyl
acetate=4:1), and concentration and vacuum drying were performed,
thereby obtaining a compound (a1)
(1-(3,4-dimethoxyphenyl)-2,2-dimethyl-1-propanone) as a pale yellow
viscous matter.
##STR00024##
[0160] Identification results of the above-synthesized compound
(a1) are shown below. [0161] Yield 3.89 g (17.4 mmol, 24%) [0162]
R.sub.f 0.33 (hexane:ethyl acetate=4:1) [0163] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0163] .delta. = 1.39 ( 9 H , s ) ( CH 3 ) 3 = 3.92 and 3.93 ( 6 H
, s , s ) Ar--OCH 3 .times. 2 = 6.90 ( 1 H , d , J = 8.4 Hz ) Ar--H
= 7.55 ( 1 H , d , J = 2.0 Hz ) Ar--H = 7.60 ( 1 H , d , J = 8.4 Hz
) Ar--H ##EQU00008## [0164] IR (NaCl)
TABLE-US-00008 [0164] 1663 cm.sup.-1 (C.dbd.O)
[0165] 3.01 g (13.5 mmol) of the compound (a1) was put into a 100
mL two-neck recovery flask, and 35 mL of dry-DMF and 11.5 g (271
mmol: 20 eq) of LiCl were added to the two-neck recovery flask in a
nitrogen atmosphere. The inside of the two-neck recovery flask was
refluxed at 170.degree. C. for 46 hours. Thereafter, 150 mL of a
saturated saline solution, 100 mL of H.sub.2O, and 50 mL of 2 N HCl
were added to the two-neck recovery flask, then, the organic layer
was extracted with ethyl acetate (100 mL.times.3), and the
extracted organic layer was dried over anhydrous MgSO.sub.4,
filtered, and concentrated. Thereafter, the organic layer subjected
to the above treatment was isolated and purified by column
chromatography (hexane:ethyl acetate=6:1), and concentration and
vacuum drying were performed, thereby obtaining a compound (b1)
(1-(3,4-dihydroxyphenyl)-2,2-dimethyl-1-propanone) as a brown
solid.
##STR00025##
[0166] Identification results of the above-synthesized compound
(b1) are shown below. [0167] Yield 2.12 g (10.9 mmol, 81%) [0168]
R.sub.f 0.33 (hexane:ethyl acetate=2:1) [0169] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0169] .delta. = 1.39 ( 9 H , s ) ( CH 3 ) 3 = 6.27 ( 1 H , s )
Ar--OH = 6.88 ( 1 H , d , J = 8.4 Hz ) Ar--H = 7.25 ( 1 H , s )
Ar--OH = 7.47 ( 1 H , d , J = 8.4 Hz ) Ar--H = 7.68 ( 1 H , d , J =
2.1 Hz ) Ar--H ##EQU00009## [0170] IR (KBr)
TABLE-US-00009 [0170] 3321 cm.sup.-1 (OH) 1642 cm.sup.-1
(C.dbd.O)
[0171] 1.75 g (9.00 mmol) of the compound (b1), 20 mL of dry DMF,
and 2.50 g (18.0 mmol: 2 eq) of K.sub.2CO.sub.3 were put into a 100
mL two-neck recovery flask, and the inside of the two-neck recovery
flask was stirred at room temperature for 2 hours. Thereafter, 10
mL of dry DMF was added to 7.39 g (18.9 mmol: 2.1 eq) of
1-iodine-1H,1H,2H,2H,3H,3H-perfluoroheptane, then, this was added
dropwise to the two-neck recovery flask, and the inside of the
two-neck recovery flask was stirred at 60.degree. C. for 21 hours.
The reaction solution was distilled off under reduced pressure,
then, 60 mL of H.sub.2O and 20 mL of 2 N HCl were added to the
two-neck recovery flask, and the organic layer was extracted with
ethyl acetate (60 mL.times.3). The extracted organic layer was
washed with a saturated saline solution (60 mL.times.5). The
organic layer was dried over anhydrous MgSO.sub.4, filtered,
concentrated, and vacuum-dried, thereby obtaining a compound (c1)
(1-(3,4-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2,2-dimethyl-
-1-propanone) as an orange solid.
##STR00026##
[0172] Identification results of the above-synthesized compound
(c1) are shown below. [0173] Yield 4.99 g (6.98 mmol, 78%) [0174]
R.sub.f 0.78 (hexane:ethyl acetate=2:1) [0175] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0175] .delta. = 1.38 ( 9 H , s ) ( CH 3 ) 3 = 2.10 to 2.19 ( 4 H ,
m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 2.27 to 2.40 ( 4
H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 4.10 and 4.12
( 4 H , t , t ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 6.83
( 1 H , d , J = 8.6 Hz ) Ar--H = 7.40 ( 1 H , d , J = 2.0 Hz )
Ar--H = 7.53 ( 1 H , d , J = 8.5 Hz ) Ar--H ##EQU00010## [0176] IR
(KBr)
TABLE-US-00010 [0176] 721 cm.sup.-1 (CF.sub.3) 1228 cm.sup.-1
(CF.sub.2, CF.sub.3) 1669 cm.sup.-1 (C.dbd.O)
[0177] 4.55 g (6.37 mmol) of the compound (c1) was put into a 300
mL recovery flask, and the compound (c1) was dissolved in 25 mL of
diethyl ether. 40 mL of 70% HNO.sub.3 was added little by little to
the recovery flask provided in an ice bath, and the inside of the
recovery flask provided in the ice bath was stirred for 20 minutes.
Thereafter, ice water was added to the reaction solution, then, the
organic layer was extracted with 80 mL of H.sub.2O and ethyl
acetate (60 mL.times.3), and the extracted organic layer was washed
with an aqueous saturated sodium hydrogen carbonate solution (60
mL.times.6). The organic layer was dried over anhydrous MgSO.sub.4,
filtered, and concentrated, thereby obtaining a yellow solid (d1)
including a by-product. 3.00 g (3.94 mmol) of the yellow solid
(d1), 12 mL of THF, and 8 mL of methanol were put into a 100 mL
recovery flask, then, 0.307 g (8.12 mmol: 2eq) of NaBH.sub.4 was
added little by little to the recovery flask provided in an ice
bath, and the inside of the recovery flask was stirred for 30
minutes. Thereafter, the inside of the recovery flask was stirred
at room temperature for 1 hour. The reaction solution was
concentrated, then, the organic layer was extracted with 50 mL of
H.sub.2O, 20 mL of 2 N HCl, and ethyl acetate (60 mL.times.3), and
the extracted organic layer was washed with a saturated saline
solution (50 mL.times.1) and H.sub.2O (50 mL.times.1). The organic
layer was dried over anhydrous MgSO.sub.4, filtered, and
concentrated. The organic layer subjected to the above treatment
was isolated and purified by column chromatography (hexane:ethyl
acetate=9:1), and concentration and vacuum drying were performed,
thereby obtaining a compound (e1)
(1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2,2-dimet-
hyl-1-propanol) as a yellow viscous matter.
##STR00027##
[0178] Identification results of the above-synthesized compound
(e1) are shown below. [0179] Yield 1.72 g (2.25 mmol, 35%) [0180]
R.sub.f 0.17 (hexane:ethyl acetate=6:1) [0181] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0181] .delta. = 0.892 ( 9 H , s ) -- C-- ( CH 3 ) 3 = 2.03 ( 1 H ,
d , J = 3.9 Hz ) Ar--CH--OH = 2.17 to 2.20 ( 4 H , m ) --O--CH 2
--CH 2 --CH 2 --CF 2 -- .times. 2 = 2.27 to 2.39 ( 4 H , m )
--O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 4.09 to 4.22 ( 4 H ,
m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 5.61 ( 1 H , d ,
J = 3.8 Hz ) Ar--CH--C-- ( CH 3 ) 3 = 7.22 ( 1 H , s ) Ar--H = 7.43
( 1 H , s ) Ar--H ##EQU00011## [0182] sIR (NaCl)
TABLE-US-00011 [0182] 721 cm.sup.-1 (CF.sub.3) 1228 cm.sup.-1
(CF.sub.2, CF.sub.3) 1335 and 1516 cm.sup.-1 (NO.sub.2) 3456
cm.sup.-1 (OH)
[0183] 0.472 g (2.46 mmol: 1.5 eq) of EDC.HCl and 5 mL of THF were
put into a 100 mL two-neck recovery flask in a nitrogen atmosphere,
and the inside of the two-neck recovery flask provided in an ice
bath was stirred for 10 minutes. Thereafter, 1.20 g (1.58 mmol: 1
eq) of the compound (e1), 0.327 g (3.27 mmol: 2 eq) of 4-pentenoic
acid, and 0.251 g (2.05 mmol: 1.2 eq) of DMAP were dissolved in 5
mL of dry-THF, and the resultant product was added dropwise to the
two-neck recovery flask. After the inside of the two-neck recovery
flask was stirred for 10 minutes, the two-neck recovery flask was
taken out from the ice bath, and the inside of the two-neck
recovery flask was stirred at room temperature for 21 hours. The
reaction solution was concentrated, then, 40 mL of H.sub.2O and 10
mL of 2 N HCl were added to the two-neck recovery flask, and the
organic layer was extracted with ethyl acetate (50 mL.times.3). The
extracted organic layer was washed with an aqueous saturated sodium
hydrogen carbonate solution (50 mL.times.3). The organic layer was
dried over anhydrous MgSO.sub.4, filtered, and concentrated. The
organic layer subjected to the above treatment was isolated and
purified by column chromatography (hexane:ethyl acetate=9:1), and
concentration and vacuum drying were performed, thereby obtaining a
compound (f1)
(1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)
phenyl)-2,2-dimethylpropyl 4-pentenoic acid ester) as a pale yellow
solid.
##STR00028##
[0184] Identification results of the above-synthesized compound
(f1) are shown below. [0185] Yield 1.23 g (1.45 mmol, 92%) [0186]
R.sub.f 0.60 (hexane:ethyl acetate=6:1) [0187] .sup.1H-NMR
(CDCl.sub.3/TMS) 400 MHz
[0187] .delta. = 0.958 ( 9 H , s ) ( CH 3 ) 3 = 2.13 to 2 .21 ( 4 H
, m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 2.26 to 2.54 (
8 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 --CH 2 --CH 2
--COO-- = 4.10 to 4.15 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2
-- .times. 2 = 4.98 to 5.07 ( 2 H , m ) CH 2 -- -- CH-- = 5.75 to
5.85 ( 1 H , m ) CH 2 -- -- CH-- = 6.64 ( 1 H , s ) Ar--CH--C-- (
CH 3 ) 3 = 6.89 ( 1 H , s ) Ar--H = 7.54 ( 1 H , s ) Ar--H
##EQU00012## [0188] IR (KBr)
TABLE-US-00012 [0188] 720 cm.sup.-1 (CF.sub.3) 1225 cm.sup.-1
(CF.sub.2, CF.sub.3) 1339 and 1526 cm.sup.-1 (NO.sub.2) 1732
cm.sup.-1 (C.dbd.O)
[0189] 0.986 g (1.02 mmol) of the compound (f1) was put into a 50
mL two-neck recovery flask, and the inside of the two-neck recovery
flask was vacuum-dried for 1 hour. Thereafter, dry-THF, 1.25 g
(10.2 mmol: 10 eq) of trimethoxysilane, 7 drops of a Karstedt
catalyst were added to the two-neck recovery flask in a nitrogen
atmosphere, and the inside of the two-neck recovery flask was
stirred at room temperature for 2.5 hours. The reaction solution
was concentrated, the obtained organic layer was isolated by medium
pressure column chromatography (hexane:ethyl
acetate:tetramethoxysilane=8:1:0.09), and concentration and vacuum
drying were performed, thereby obtaining a fluorine-containing
compound (2)
(1-(2-nitro-4,5-di(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)phenyl)-2,2-dimet-
hylpropyl 5-(trimethoxysilyl)pentenoic acid ester) as a pale yellow
solid.
##STR00029##
[0190] Identification results of the above-synthesized compound (2)
are shown below. [0191] Yield 0.775 g (0.814 mmol, 67%) [0192]
R.sub.f 0.20 (hexane:ethyl acetate:tetramethoxysilane=8:1:0.09)
[0193] .sup.1H-NMR (CDCl.sub.3/TMS) 400 MHz
[0193] .delta. = 0.620 to 0.661 ( 2 H , m ) --Si--CH 2 -- = 0.959 (
9 H , s ) ( CH 3 ) 3 = 1.42 to 1.49 ( 2 H , m ) --Si--CH 2 --CH 2
-- = 1.68 ( 2 H , quint , J = 7.6 Hz ) --CH 2 --CH 2 --COO-- = 2.14
to 2.21 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 =
2.23 to 2.41 ( 6 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times.
2 --CH 2 --COO-- = 3.55 ( 9 H , s ) ( CH 3 O ) 3 --Si-- = 4.10 to
4.13 ( 4 H , m ) --O--CH 2 --CH 2 --CH 2 --CF 2 -- .times. 2 = 6.63
( 1 H , s ) Ar--CH--C-- ( CH 3 ) 3 = 6.90 ( 1 H , s ) Ar--H = 7.54
( 1 H , s ) Ar--H ##EQU00013## [0194] IR (KBr)
TABLE-US-00013 [0194] 720 cm.sup.-1 (CF.sub.3) 1228 cm.sup.-1
(CF.sub.2, CF.sub.3) 1338 and 1528 cm.sup.-1 (NO.sub.2) 1729
cm.sup.-1 (C.dbd.O)
[0195] <<Pretreatment>>
[0196] Four sheets of silicon wafer (3 cm.times.1.5 cm), two sheets
of silicon wafer (2 cm.times.1 cm), and one sheet of quartz glass
(4 cm.times.1 cm) were subjected to a pretreatment with a piranha
solution or a UV-ozone cleaner, respectively.
[0197] Pretreatment in Piranha Solution
[0198] A mixed solution of H.sub.2SO.sub.4:H.sub.2O.sub.2=7:3 (14
mL:6 mL) was adjusted in a 50 mL recovery flask, then, two sheets
of the silicon wafer (2 cm.times.1 cm) back to back were put
thereinto, and the inside of the recovery flask was heated to
100.degree. C. for one hour in an oil bath. Thereafter, the two
sheets of the silicon wafer was washed with pure water, pure water
was put into the recovery flask, ultrasonic cleaning was performed
for 10 minutes, and the silicon wafers were dried in a stream of
nitrogen.
[0199] Pretreatment in UV-ozone Cleaner
[0200] Silicon wafer and quartz glass were subjected to ultrasonic
cleaning for 5 minutes with methanol, water, and acetone,
respectively. The substrate was taken out, dried in a stream of
nitrogen, and pretreated with a UV-ozone cleaner. 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. For quartz glass, in order to uniformly
treat both sides of the substrate, washing was performed twice by
the UV-ozone while turning the substrate.
[0201] <<Surface Modification with Fluorine-Containing
Compound (1)>>
[0202] 40 mL of dry toluene and 38.1 mg (40.0 .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.
From the 1 mM solution, 20 mL of the solution was transferred to
another 50 mL recovery flask. The pretreated silicon wafer and
quartz glass were put into two recovery flasks separately, and the
silicon wafer and the quartz glass were refluxed for 3 hours in
nitrogen, respectively. The substrate was taken out from the
recovery flask, and washed with methanol. Methanol and the
substrate were put into in a sample bottle, and ultrasonic cleaning
was performed (10 minutes). Furthermore, the substrate was washed
with chloroform, then, chloroform and the substrate were put into
in a sample bottle, and ultrasonic cleaning was performed (10
minutes). The surface of the substrate was dried with nitrogen, and
a contact angle thereof was measured. After the measurement of
contact angle, the surface of the substrate was dried with
nitrogen, and the substrate was put into a sample bottle. The
sample bottle was filled with nitrogen, and the substrate was
stored. The following Table 1 shows the contact angles of the
substrates after the surface modification.
[0203] Here, in the following Table 1, No. 7 and No. 8 show the
results of the surface (No. 7) and the rear surface (No. 8) of one
sheet of substrate.
TABLE-US-00014 TABLE 1 Type of Contact Standard No. substrate
Pretreatment angle (.degree.) deviation 1 Silicon wafer Piranha
solution 93.8 1.5 2 Silicon wafer Piranha solution 94.2 1.1 3
Silicon wafer UV-ozone 96.1 0.7 4 Silicon wafer UV-ozone 97.6 1.2 5
Silicon wafer UV-ozone 97.5 0.9 6 Silicon wafer UV-ozone 96.2 0.2 7
Quartz glass UV-ozone 94.8 0.2 8 Quartz glass UV-ozone 95.3 0.2
[0204] As shown in Table 1, regardless of the types of substrate or
pretreatment methods, contact angles after the surface modification
became values with the same degree as 94.degree. to 98.degree..
[0205] <<Surface Modification with Fluorine-Containing
Compound (2)>>
[0206] 40 mL of dry toluene and 38.6 mg (40.0 .mu.mol) of the
fluorine-containing compound (2) were put into a 50 mL recovery
flask, thereby preparing a 1 mM solution in the recovery flask.
From the 1 mM solution, 20 mL of the solution was transferred to
another 50 mL recovery flask. The pretreated silicon wafer and
quartz glass were put into two recovery flasks separately, and the
silicon wafer and the quartz glass were dipped for 3 hours in a
nitrogen atmosphere, respectively. The substrate was taken out from
the inside of the recovery flask, and washed with methanol.
Methanol and the substrate were put into in a sample bottle, and
ultrasonic cleaning was performed (10 minutes). Furthermore, the
substrate was washed with chloroform, then, chloroform and the
substrate were put into in a sample bottle, and ultrasonic cleaning
was performed (10 minutes). The surface of the substrate was dried
with nitrogen, and a contact angle thereof was measured. The
following Table 2 shows the contact angles of the substrates after
the surface modification.
[0207] Here, in the following Table 2, No. 9 and No. 10 show the
results of the surface (No. 9) and the rear surface (No. 10) of one
sheet of substrate.
TABLE-US-00015 TABLE 2 Type of Contact Standard No. substrate
Pretreatment angle (.degree.) deviation 1 Silicon wafer UV-ozone
99.7 0.5 2 Silicon wafer UV-ozone 99.4 0.7 3 Silicon wafer UV-ozone
99.2 1.2 4 Silicon wafer UV-ozone 100.2 0.7 5 Silicon wafer
UV-ozone 99.8 0.6 6 Silicon wafer UV-ozone 100.0 0.7 7 Silicon
wafer UV-ozone 99.6 0.3 8 Silicon wafer UV-ozone 100.4 0.9 9 Quartz
glass UV-ozone 101.1 1.4 10 Quartz glass UV-ozone 98.9 0.7
[0208] As shown in Table 2, contact angles of all substrates after
the surface modification became values near 100.degree..
[0209] <<Light Irradiation onto Modified
Substrate>>
[0210] The position of 50 mW/cm.sup.2 was detected using a
luminometer, then, the pretreatment was performed on that position
by the UV-ozone, and a surface modified substrate was placed. Light
having a wavelength of 320 nm or greater was applied thereto using
an ultrahigh-pressure mercury lamp.
[0211] The modified substrate after the light irradiation was
washed with methanol, and washed with chloroform in the same
manner. The modified substrate and chloroform were put into a
sample bottle, and ultrasonic cleaning was performed (10 minutes).
The modified substrate was taken out using tweezers, then, the
surface of the modified substrate was dried in a stream of
nitrogen, and a contact angle thereof was measured. The results are
shown in Table 3.
TABLE-US-00016 TABLE 3 Contact angle Exposure before exposure/
amount Compound after exposure (J/cm.sup.2) Example 1 1 98/51 18
Example 2 2 100/51 18 Comparative 3 69/55 12 Example 1 Comparative
4 73/50 7.5 Example 2 Comparative 5 97/57 30 Example 3
[0212] In Table 3, the compounds 1 and 2 are the
fluorine-containing compounds (1) and (2), and the compounds 3 to 5
are the following compounds (13) to (15).
##STR00030##
[0213] As shown in the above results, Examples 1 and 2 have larger
differences in the contact angle, and have more favorable
sensitivity with respect to the light irradiation, compared to
Comparative Examples 1 to 3.
[0214] <<Measurement of XPS>>
[0215] An X-ray photoelectron spectrum (XPS) before and after
exposure (exposure amount: 18 J/cm.sup.2) of the substrate in which
the silicon wafer pretreated using UV-ozone cleaner has been
modified with the fluorine-containing compound (1) was measured.
Table 4 shows relative intensity values obtained by setting the
peak area value of a Si--Si bond in the silicon wafer to 1 and
dividing the area of each element by each sensitivity.
TABLE-US-00017 TABLE 4 Relative intensity After Chemical exposure/
Measurement shift Before After before element (eV) exposure
exposure exposure Si--Si 100 1 1 1 C1.sub.S (derived 292, 295 0.11
0 0 from CF.sub.3, CF.sub.2) N1s 407 0.0066 0 0 F1s 681, 690 0.61
0.056 0.091
[0216] As shown in Table 4, it was found that the peak of the
element based on a photodegradable group disappeared or
significantly decreased compared to the peak area before exposure,
and the photodegradable group was detached by exposure.
* * * * *