U.S. patent application number 12/204847 was filed with the patent office on 2009-01-08 for treated substrate having hydrophilic region and water repellent region, and process for producing it.
This patent application is currently assigned to ASAHI GLASS COMPANY, LIMITED. Invention is credited to Yutaka FURUKAWA.
Application Number | 20090011227 12/204847 |
Document ID | / |
Family ID | 38474914 |
Filed Date | 2009-01-08 |
United States Patent
Application |
20090011227 |
Kind Code |
A1 |
FURUKAWA; Yutaka |
January 8, 2009 |
TREATED SUBSTRATE HAVING HYDROPHILIC REGION AND WATER REPELLENT
REGION, AND PROCESS FOR PRODUCING IT
Abstract
To provide a treated substrate having a hydrophilic region and a
water repellent region, of which contrast is high on its surface.
Further, to provide a process for producing a treated substrate,
wherein a specific equipment, light having a high energy or light
irradiation for a long time is not required, and the treated
substrate can be produced with a low amount of light for a short
time. A treated substrate having a hydrophilic region and a water
repellent region on a surface of a substrate, characterized in that
the water repellent region is made of a water repellent film formed
by curing the composition (A) comprising a photopolymerization
initiator and a compound (a) having at least one (meth)acryloyl
group, and a water repellent moiety and having a film thickness of
from 0.1 to 100 nm. A process for producing a treated substrate,
characterized by using a hydrophilic substrate or carrying out a
hydrophilic treatment on a surface of a substrate to make the
surface hydrophilic, then forming a film containing the composition
(A) on the surface, then forming a water repellent film having a
film thickness of from 0.1 to 100 nm by irradiating light on a part
of the film surface to cure the composition (A) and then removing
an uncured composition (A) present on the surface of the substrate
in order to expose the hydrophilic surface.
Inventors: |
FURUKAWA; Yutaka; (Tokyo,
JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
ASAHI GLASS COMPANY,
LIMITED
Tokyo
JP
|
Family ID: |
38474914 |
Appl. No.: |
12/204847 |
Filed: |
September 5, 2008 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP07/54290 |
Mar 6, 2007 |
|
|
|
12204847 |
|
|
|
|
Current U.S.
Class: |
428/336 ;
427/256; 427/508 |
Current CPC
Class: |
H01L 21/02118 20130101;
Y10T 428/265 20150115; Y10T 428/3154 20150401; G03F 7/0755
20130101; Y10T 428/31663 20150401; G03F 7/027 20130101; H01L 21/312
20130101; G03F 7/0757 20130101; Y10T 428/31667 20150401 |
Class at
Publication: |
428/336 ;
427/508; 427/256 |
International
Class: |
B32B 33/00 20060101
B32B033/00; B32B 27/00 20060101 B32B027/00; C08F 2/48 20060101
C08F002/48; B05D 5/00 20060101 B05D005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 6, 2006 |
JP |
2006-059495 |
Claims
1. A treated substrate having a hydrophilic region and a water
repellent region on a surface of a substrate, characterized in that
the water repellent region is made of a water repellent film formed
by curing the following composition (A) and having a film thickness
of from 0.1 to 100 nm: composition (A): a composition comprising a
photopolymerization initiator and a compound (a) having at least
one polymerizable functional group selected from the group
consisting of an acryloyl group and a methacryloyl group, and a
water repellent moiety.
2. The treated substrate according to claim 1, wherein the compound
(a) is a compound represented by the following formula (11), (12),
(21) or (22): ##STR00003## where each of Q.sup.1 and Q.sup.2 which
are independent of each other, is a monovalent organic group,
Q.sup.3 is an alkyl group having at least four carbon atoms, a
monovalent organic group having the above alkyl group as a partial
structure, a fluoroalkyl group having at least one carbon atom,
which may contain an etheric oxygen atom, or a monovalent organic
group having the above fluoroalkyl group as a partial structure,
Q.sup.4 is an alkylene group having at least four carbon atoms, a
bivalent organic group having the above alkylene group as a partial
structure, a fluoroalkylene group having at least two carbon atoms,
which may contain an etheric oxygen atom, or a bivalent organic
group having the above fluoroalkylene group as a partial structure,
R.sup.1 is a hydrogen atom or a methyl group, n is an integer of at
least 0, and k is an integer of from 1 to 5.
3. The treated substrate according to claim 1, wherein the
composition (A) contains a compound (b) having at least three
polymerizable functional groups selected from the group consisting
of an acryloyl group and a methacryloyl group, provided that the
compound (b) may be the same as the compound (a) or a compound
other than the compound (a).
4. The treated substrate according to claim 1, wherein the contact
angle of the hydrophilic region to water is at most 50.degree., and
the contact angle of the water repellent region to water is at
least 80.degree..
5. The treated substrate according to claim 1, wherein the
hydrophilic region and the water repellent region have a
predetermined pattern.
6. A process for producing a treated substrate, characterized by
using a hydrophilic substrate or carrying out a hydrophilic
treatment on a surface of a substrate to make the surface
hydrophilic, then forming a film containing the following
composition (A) on the surface, then forming a water repellent film
having a film thickness of from 0.1 to 100 nm by applying light on
a part of the film surface to cure the composition (A) and then
removing an uncured composition (A) present on the surface of the
substrate in order to expose the hydrophilic surface, to obtain a
treated substrate having a hydrophilic region and a water repellent
region made of a water repellent film formed by curing the compound
(A) on the surface of the substrate: composition (A): a composition
comprising a photopolymerization initiator and a compound (a)
having at least one polymerizable functional group selected from
the group consisting of an acryloyl group and a methacryloyl group,
and a water repellent moiety.
7. The process according to claim 6, wherein the surface of the
substrate is subjected to the hydrophilic treatment by subjecting
the surface of the hydrophilic substrate to wet-washing or
photo-washing, or by applying a hydrophilic compound on the surface
of the substrate.
8. A process for producing a treated substrate, characterized by
forming a film containing a hydrophilic compound and the following
composition (A) on a surface of a substrate, leaving it to stand
still to make the hydrophilic compound move to the substrate side,
then applying light on a part of the film surface to cure the
composition (A) to form a water repellent film having a film
thickness of from 0.1 to 100 nm, and then removing an uncured
composition (A) present on the surface of the substrate in order to
expose a hydrophilic surface, to obtain a treated substrate having
a hydrophilic region and a water repellent region made of a water
repellent film formed by curing the composition (A) on the surface
of the substrate: composition (A): a composition comprising a
photopolymerization initiator and a compound (a) having at least
one polymerizable functional group selected from the group
consisting of an acryloyl group and a methacryloyl group, and a
water repellent moiety.
9. The process according to claim 6, wherein light having a
wavelength of at least 200 nm is applied.
10. The process according to claim 8, wherein light having a
wavelength of at least 200 nm is applied.
11. A process for producing a member on which a pattern of a film
made of a functional material is formed, characterized by applying
a hydrophilic liquid containing a functional material on a surface
of the treated substrate as defined in claim 5 in order to coat the
hydrophilic region having a pattern of the treated substrate with
the hydrophilic liquid, followed by drying to form a pattern of a
film made of the functional material.
12. A process for producing a member on which a pattern of a film
made of a functional material is formed, characterized by applying
a hydrophilic liquid containing a functional material on a surface
of the treated substrate as defined in claim 5 in order to coat the
hydrophilic region having a pattern of the treated substrate with
the hydrophilic liquid, followed by drying to form a pattern of a
film made of the functional material, and removing the water
repellent film formed by curing the composition (A).
Description
TECHNICAL FIELD
[0001] The present invention relates to a treated substrate having
a hydrophilic region and a water repellent region on a surface of a
substrate, a process for producing it and a process for producing a
member on which a pattern of a film made of a functional material
is formed by using the treated substrate.
BACKGROUND ART
[0002] Many functional thin films are practically used in the
fields of semiconductor devices, displays and luminescent elements.
Functional thin films are formed by disposing a material having a
desired property at a desired position, followed by patterning. The
functional thin films are used as wiring, electrodes, insulating
layers, luminescence layers, optical thin films, etc.
[0003] For example, a photoresist pattern obtained by
photolithography may be mentioned. However, processes of the
photolithography are complex, and utilization efficiency of energy,
material, etc. is low. Further, there is a problem such that since
the processes of the photolithography are carried out in a clean
room, cost of facilities is expensive.
[0004] As a method to solve the problems of the photolithography,
an ink-jet print method has been proposed. However, in the ink-jet
print method, position accuracy is low, and it is difficult to form
a fine pattern. Under the circumstance, the following methods (1)
and (2) have been proposed to improve the position accuracy by
preliminarily forming on a substrate surface a base film having a
water repellent region which repels ink and a hydrophilic region
which accepts ink.
[0005] (1) A method wherein a photocatalyst such as titanium oxide
is activated at a time of exposure to change a wet property of a
surfactant, or a photocatalyst decomposable substance is decomposed
and removed, thereby to form a pattern which accepts or repels
printing ink or a toner (Patent Document 1). Paten Document 1
discloses that in a silicon resin having a siloxane bond
(--Si--O--) as a main skeleton to be used as a binder for a
photocatalyst, an organic group bonded to a silicon atom is
substituted with an oxygen-containing group by action of the
photocatalyst, whereby the wet property is improved.
[0006] (2) A method wherein a surface of a substrate is subjected
to a hydrophilic treatment, and then a pattern of an organic
monomolecular film of a fluorinated alkylsilane is formed by
chemical vapor deposition, whereby the monomolecular film becomes a
resist film for etching (Patent Document 2). Patent document 2
discloses a method wherein hydrophilic treatment is carried out by
irradiating a surface of a substrate such as a single crystal
silicon (natural oxidation surface SiO.sub.2), a polyethylene film
or glass with ultraviolet light of Xe.sub.2 excimer laser (172 nm)
or oxygen plasma. Further, it is disclosed that the organic
monomolecular film of a fluorinated alkylsilane is formed by
applying ultraviolet light (172 nm) or electron beam.
[0007] Patent Document 1 JP-A-11-344804
[0008] Patent Document 2 JP-A-2000-282240
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0009] In such conventional methods, high energy light having a
wavelength of lower than 200 nm is required, and light irradiation
for a long time is required. Further, special equipments such as a
large facility, a vacuum apparatus and a high energy light source
are required in such conventional methods. Further, since a high
energy light having a wavelength of at most 200 nm is used, an
organic compound in a thin film of a pattern is also decomposed,
and the contrast between a hydrophilic region and a water repellent
region in the pattern tends to be low.
[0010] It is an object of the present invention to provide a
treated substrate having a hydrophilic region and a water repellent
region, of which the contrast is high on a surface of a substrate.
It is also an object of the present invention to provide a process
for producing the treated substrate, wherein a special equipment,
high energy light or light irradiation for a long time is not
required, and the treated substrate can be produced with a low
amount of light for a short time. Further, it is an object of the
present invention to provide a member on which a pattern of a film
made of a functional material is formed by employing the treated
substrate.
Means to Accomplish the Objects
[0011] The above objects can be accomplished by the following
invention.
(1) A treated substrate having a hydrophilic region and a water
repellent region on a surface of a substrate, characterized in that
the water repellent region is made of a water repellent film formed
by curing the following composition (A) and having a film thickness
of from 0.1 to 100 nm:
[0012] composition (A): a composition comprising a
photopolymerization initiator and a compound (a) having at least
one polymerizable functional group selected from the group
consisting of an acryloyl group and a methacryloyl group, and a
water repellent moiety.
(2) The treated substrate according to the above (1), wherein the
compound (a) is a compound represented by the following formula
(11), (12), (21) or (22):
##STR00001##
where each of Q.sup.1 and Q.sup.2 which are independent of each
other, is a monovalent organic group, Q.sup.3 is an alkyl group
having at least four carbon atoms, a monovalent organic group
having the above alkyl group as a partial structure, a fluoroalkyl
group having at least one carbon atom, which may contain an etheric
oxygen atom, or a monovalent organic group having the above
fluoroalkyl group as a partial structure, Q.sup.4 is an alkylene
group having at least four carbon atoms, a bivalent organic group
having the above alkylene group as a partial structure, a
fluoroalkylene group having at least two carbon atoms, which may
contain an etheric oxygen atom, or a bivalent organic group having
the above fluoroalkylene group as a partial structure, R.sup.1 is a
hydrogen atom or a methyl group, n is an integer of at least 0, and
k is an integer of from 1 to 5. (3) The treated substrate according
to the above (1) or (2), wherein the composition (A) contains a
compound (b) having at least three polymerizable functional groups
selected from the group consisting of an acryloyl group and a
methacryloyl group, provided that the compound (b) may be the same
as the compound (a) or a compound other than the compound (a). (4)
The treated substrate according to any one of the above (1) to (3),
wherein the contact angle of the hydrophilic region to water is at
most 50.degree., and the contact angle of the water repellent
region to water is at least 80.degree.. (5) The treated substrate
according to any one of the above (1) to (4), wherein the
hydrophilic region and the water repellent region have a
predetermined pattern. (6) A process for producing a treated
substrate, characterized by using a hydrophilic substrate or
carrying out a hydrophilic treatment on a surface of a substrate to
make the surface hydrophilic, then forming a film containing the
following composition (A) on the surface, then forming a water
repellent film having a film thickness of from 0.1 to 100 nm by
applying light on a part of the film surface to cure the
composition (A) and then removing an uncured composition (A)
present on the surface of the substrate in order to expose the
hydrophilic surface, to obtain a treated substrate having a
hydrophilic region and a water repellent region made of a water
repellent film formed by curing the compound (A) on the surface of
the substrate:
[0013] composition (A): a composition comprising a
photopolymerization initiator and a compound (a) having at least
one polymerizable functional group selected from the group
consisting of an acryloyl group and a methacryloyl group, and a
water repellent moiety.
(7) The process according to the above (6), wherein the surface of
the substrate is subjected to the hydrophilic treatment by
subjecting the surface of the hydrophilic substrate to wet-washing
or photo-washing, or by applying a hydrophilic compound on the
surface of the substrate. (8) A process for producing a treated
substrate, is characterized by forming a film containing a
hydrophilic compound and the following composition (A) on a surface
of a substrate, leaving it to stand still to make the hydrophilic
compound move to the substrate side, then applying light on a part
of the film surface to cure the composition (A) to form a water
repellent film having a film thickness of from 0.1 to 100 nm, and
then removing an uncured composition (A) present on the surface of
the substrate in order to expose a hydrophilic surface, to obtain a
treated substrate having a hydrophilic region and a water repellent
region made of a water repellent film formed by curing the
composition (A) on the surface of the substrate:
[0014] composition (A): a composition comprising a
photopolymerization initiator and a compound (a) having at least
one polymerizable functional group selected from the group
consisting of an acryloyl group and a methacryloyl group, and a
water repellent moiety.
(9) The process according to any one of the above (6) to (8),
wherein light having a wavelength of at least 200 nm is applied.
(10) A process for producing a member on which a pattern of a film
made of a functional material is formed, characterized by applying
a hydrophilic liquid containing a functional material on a surface
of the treated substrate as defined in the above (5) in order to
coat the hydrophilic region having a pattern of the treated
substrate with the hydrophilic liquid, followed by drying to form a
pattern of a film made of the functional material. (11) A process
for producing a member on which a pattern of a film made of a
functional material is formed, characterized by applying a
hydrophilic liquid containing a functional material on a surface of
the treated substrate as defined in the above (5) in order to coat
the hydrophilic region having a pattern of the treated substrate
with the hydrophilic liquid, followed by drying to form a pattern
of a film made of the functional material, and removing the water
repellent film formed by curing the composition (A).
EFFECT OF THE INVENTION
[0015] By the present invention, a treated substrate having a
hydrophilic region and a water repellent region, of which the
contrast is high on its surface can be obtained. Further, without
using a large facility, a vacuum apparatus and a high energy light
source, the treated substrate can be produced. Namely, the treated
substrate can be produced by using a simple apparatus and a simple
light source with a low light amount in a short time.
[0016] Further, by using the treated substrate of the present
invention, a member on which a pattern of a film made of a
functional material is formed can be obtained, and the treated
substrate of the present invention can be used for various
applications.
BEST MODE FOR CARRYING OUT THE INVENTION
[0017] Hereinafter, a polymerizable functional group selected from
the group consisting of an acryloyl group and a methacryloyl group
is referred to as "(meth)acryloyl group". Further, a (meth)acrylate
means an acrylate or a methacrylate
[0018] In the present specification, a compound represented by the
formula (11) is referred to as "compound (11)". Compounds
represented by other formulae are also referred to in the same
manner.
[0019] A substrate used in the present invention can be selected
from substrates made of glass; a silicon wafer; a metal such as Pd,
Pt, Ru, Ag, Au, Ti, In, Cu, Cr, Fe, Zn, Sn, Ta, W or Pd; a metal
oxide such as PdO, SnO.sub.2, In.sub.2O.sub.3, PbO, or
Sb.sub.2O.sub.3; a boride such as HfB.sub.2, ZrB.sub.2, LaB.sub.2,
CeB.sub.6, YB.sub.4 or GdB.sub.4; a carbide such as TiC, ZrC, HfC,
TaC, SiC or WC; a nitride such as TiN, ZrN or HfN; a semiconductor
such as Si or Ge; and a resin such as a polyimide, a polystyrene, a
polyethylene terephtalate or a polytetrafluorethylene. The
substrate may be a substrate made of a hydrophilic material, of
which the surface is hydrophilic or a substrate made of a
non-hydrophilic (hydrophobic) material, of which the surface is not
hydrophilic. The glass, the silicon wafer, the metal oxide and the
polyimide are preferred. Among them, the glass, the silicon wafer
and the metal oxide are usually hydrophilic materials.
[0020] The shape of the substrate is not particularly limited and
it preferably has a flat surface, a curved surface or a flat
surface having a partially curved surface, and a flat surface is
more preferred. Further, the area of the substrate is not
particularly limited, and as far as conventional coating methods
can be applied, the area of a substrate is not limited. Further,
the surface treatment of the substrate of the present invention is
preferably carried out on one surface of a flat substrate.
[0021] The process for producing the treated substrate of the
present invention contains the following step (1) or (2).
[0022] (1) Step of using a hydrophilic substrate or carrying out a
hydrophilic treatment on a surface of a substrate to make the
surface hydrophilic and then forming on the surface a film
containing the composition (A) comprising a photopolymerization
initiator and a compound (a) having at least one (meth)acryloyl
group, and a water repellent moiety.
[0023] (2) Step of forming a film containing a hydrophilic compound
and the following composition (A) on a surface of a substrate and
leaving it to stand still to make the hydrophilic compound move to
the substrate side.
[0024] After the above step (1) or (2), a part of the film surface
is irradiated with light to cure the composition (A) to form a
water repellent film having a film thickness of from 0.1 to 100 nm,
and then an uncured composition (A) present on the surface of the
substrate is removed to expose a hydrophilic surface, whereby the
treated substrate of the present invention can be obtained.
[0025] First, the above step (1) will be explained. It is preferred
to clean the surface of a substrate by washing or the like before
use. A substrate made of a hydrophilic material and having a
hydrophilic surface can be used as it is. A substrate having a
non-hydrophilic surface is subjected to hydrophilic treatment
before use. The hydrophilic treatment can also be carried out on a
surface of a substrate having a hydrophilic surface before use. As
a method for washing the surface of a substrate, conventional
methods for washing the surface of plastics, metals, glass,
ceramics, etc. can be employed. As the washing method, a method of
wet-washing the surface of a substrate, a method of photo-washing
the surface of a substrate or the like is preferred. As a method
for the hydrophilic treatment of the surface of a substrate,
conventional methods for hydrophilic treatment of the surface of
plastics, metals, glass, ceramics, etc. can be employed. As the
hydrophilic treatment method, a method wherein a compound which
reacts on the surface to form a hydrophilic surface is used, a
method wherein the surface of a substrate is coated with a
hydrophilic compound to form a layer of the hydrophilic compound or
a method wherein the above methods are combined may, for example,
be mentioned.
[0026] For the wet-washing of a substrate, water, a water type
detergent or a non-water type detergent (an organic solvent, a
fluorine type solvent, etc.) may be used. Particularly, a method is
preferred wherein a substrate is washed with water or a water type
detergent containing a surfactant, and then the substrate is dried,
while contaminates, moisture, etc. on a surface are removed by
using an organic solvent having a low boiling point such as
isopropyl alcohol or ethyl alcohol. Further, depending on the type
of a substrate, or the type or degree of stain, a step may be
added, or a part of step may be omitted. It is preferred that in
order to wet-wash a substrate with an organic stain, the substrate
is preliminarily washed with an organic solvent such as
dichloropentafluoropropane (AK-225, manufactured by Asahi Glass
Company, Limited: a mixture of CF.sub.3CF.sub.2CHCl.sub.2 and
CF.sub.2CHClF) to remove the stain, and then the substrate is
immerse-washed with a water type detergent or an organic detergent.
At the time of the immerse-washing, ultrasonic washing may be
carried out in combination. In the case of glass, instead of the
immerse-washing or with the immerse-washing, a method of polish
washing with an abrasive containing cerium oxide fine particles,
followed by rinsing the substrate with pure water and then by
air-drying may be employed.
[0027] As the method of photo-washing a substrate, UV/O.sub.3
washing (photo-washing with ultraviolet light, ozone or their
combination) is preferred. The mechanism of the UV/O.sub.3 washing
is such that washing is carried out by (1) cleaving bonds of the
main component (organic matter) of stain by ultraviolet light
having high photon energy, so that the bonds of the stain become
fragile and (2) in such a state, reacting ozone or active oxygen,
so that the organic matter is oxidized to carbon dioxide, water,
etc, and evaporated. Thus, the later method is preferred, since
ultraviolet light and ozone may be used alone or in combination to
clean the surface. A commercially available UV/O.sub.3 washing
apparatus may be used.
[0028] Further, only by the wet-washing, fine organic stains (for
example, residues of the surfactant in a detergent or suspended
matters in the clean room) are likely to remain. On the other hand,
the above photo-washing is free from the problem of the fine
organic stains. Accordingly, a method is preferred wherein at
first, relatively large stains are removed by the wet-washing, and
then washing is carried out by the photo-washing.
[0029] The hydrophilic compound which may be used in the
hydrophilic treatment of the surface of a substrate may, for
example, be a hydrophilic polymer such as a poly(vinyl alcohol), a
poly(vinyl pyrrolidone) or a poly(ethylene glycol) or a polyhydric
alcohol such as glycerin, pentaerythritol or sorbitol. The compound
which reacts on the surface to make the surface hydrophilic may,
for example, be a hydrolyzable silane compound such as
H--Si(OCH.sub.2CH.sub.3).sub.3 or
NH.sub.2CH.sub.2CH.sub.2CH.sub.2--Si(OCH.sub.2CH.sub.3).sub.3, a
compound having said compound partially or entirely hydrolyzed or a
hydrolytic condensate of the above compound.
[0030] It is preferred that the hydrophilic compound is applied in
the form of a solution dissolved in a solvent and dried to form a
layer of the hydrophilic compound. The hydrophilic polymer and the
polyhydric alcohol are preferably dissolved in water and used as an
aqueous solution. The hydrolyzable silane compound is preferably
dissolved in an alcohol solvent such as isopropyl alcohol for use.
The concentration of the hydrophilic polymer or the hydrolyzable
silane compound in the solution is preferably from 0.01 to 10 mass
%, more preferably from 0.1 to 1 mass %.
[0031] The coating method of a substrate is not particularly
limited, and a spin coating method, a dip coating method, a spray
coating method, a roll coating method, a meniscus coating method
and a screen printing method may be employed.
[0032] In a case where the surface of a substrate is made of
various different materials, it is preferred to employ a method of
subjecting the surface of a substrate to hydrophilic treatment.
Because, the same hydrophilic property can be imparted to the
surface made of various materials.
[0033] Next, a film containing the composition (A) is formed on the
hydrophilic surface of the substrate. The composition (A) contains
a photopolymerization initiator and a compound (a) having at least
one (meth)acryloyl group and a water repellent moiety. The
(meth)acryloyl group of the compound (a) may be at any position in
the molecule, however, it is preferably present at a terminal of
the molecule. If it is present at a terminal of the molecule,
reactivity is high.
[0034] The water repellent moiety of the compound (a) is preferably
a monovalent or bivalent water repellent group. The monovalent
water repellent group is preferably a monovalent group having an
organopolysiloxane skeleton, an alkyl group having at least four
carbons or a C.sub.1-12 fluoroalkyl group which may contain an
etheric oxygen atom. The bivalent water repellent group is
preferably a bivalent group having an organopolysiloxane skeleton,
an alkylene group having at least four carbons or a C.sub.2-12
fluoroalkylene group which may contain an etheric oxygen atom.
[0035] The organopolysiloxane skeleton has a polysiloxane skeleton
and an organic group bonded to a silicon atom which forms the
skeleton. The organic group bonded to a silicon atom is bonded by a
carbon-silicon bond. Namely, a terminal atom of the organic group,
which is bonded to a silicon atom is a carbon atom. At least one
organic group is bonded to the silicon atom in the
organopolysiloxane skeleton, and in many cases, except for a
terminal silicon atom, one or two organic groups are bonded to the
silicon atom. In the case of the monovalent group having an
organopolysiloxane skeleton, at most three organic groups are
bonded to a terminal silicon atom. In the present invention, the
organopolysiloxane skeleton preferably has a linear structure
having no branch or a linear structure having a few branches.
[0036] The organic group bonded to the above silicon atom is
preferably a hydrocarbon group or a fluoroorganic group. The
hydrocarbon group is preferably an alkyl group, an alkenyl group,
an alkynyl group or an aryl group. From the viewpoint of
availability, the organic group bonded to a silicon atom is
preferably an alkyl group having at most four carbon atoms, an
alkenyl group having at most four carbon atoms, an alkynyl group
having at most four carbon atoms or an aryl group having at most 8
carbon atoms. Among them, a methyl group, an ethyl group and a
phenyl group are preferred, and the methyl group is particularly
preferred. Further, from the viewpoint of improving the water
repellent property of the organopolysiloxane skeleton, the organic
group bonded to a silicon atom is preferably a C.sub.5-20 linear
alkyl group or a C.sub.5-20 linear alkenyl group, particularly
preferably a C.sub.6-16 linear alkyl group. Further, from the
viewpoint of improving the water repellent property of the
organopolysiloxane skeleton, the organic group bonded to a silicon
atom is preferably a fluoroorganic group, and a polyfluoroalkyl
group which may contain an etheric oxygen is more preferred.
Particularly preferred are a polyfluoroalkyl group having a
difluororoethylene chain and a polyfluoroalkyl group having a
perfluorooxyalkylene group.
[0037] The compound (a) may, for example, be a compound having one
(meth)acryloyl group and a monovalent water repellent group or a
compound having two (meth)acryloyl groups and a bivalent water
repellent groups. The former compound may, for example, be the
compound (11) or the compound (12), and the latter compound may,
for example, be the compound (21) or the compound (22). The symbols
in the formulae are the same as defined above.
##STR00002##
[0038] In the case of the compound (11), the water repellent moiety
is a monovalent group having an organopolysiloxane skeleton, in the
case of the compound (12), the water repellent moiety is Q.sup.3,
in the case of the compound (21), the water repellent moiety is a
bivalent group having an organopolysiloxane skeleton, and in the
case of the compound (22), the water repellent moiety is
Q.sup.4.
[0039] In the above formulae, each of Q.sup.1 and Q.sup.2 which are
independent of each other, is a monovalent organic group,
preferably a monovalent hydrocarbon group which may contain a
fluorine atom, more preferably a C.sub.1-4 alkyl group,
particularly preferably a methyl group. In a case where a plurality
of Q.sup.1 are present (in a case where n is at least 2), the
plurality of Q.sup.1 may be different from one another. The same
applies to Q.sup.2.
[0040] R.sup.1 is a hydrogen atom or a methyl group. n is an
integer of at least 0, preferably an integer of at least 1, and
preferably an integer such that the molecular weight of a compound
will be from 500 to 1,000,000. k is an integer of from 1 to 5,
preferably an integer of from 2 to 4, more preferably 3.
[0041] In the above formulae, Q.sup.3 is an alkyl group having at
least four carbon atoms, a monovalent organic group having the
above alkyl group as a partial structure, a fluoroalkyl group
having at least one carbon atom, which may contain an etheric
oxygen atom or a monovalent organic group having the above
fluoroalkyl group as a partial structure.
[0042] In a case where Q.sup.3 is an alkyl group having at least
four carbon atoms or a monovalent organic group having the above
alkyl group as a partial structure, an alkyl group having at least
four carbon atoms is preferred, and a C.sub.4-18 alkyl group is
more preferred. In a case where the number of carbon atoms is
within the above range, an excellent water repellent property can
be obtained. The alkyl group may have a linear structure, a
branched structure, a ring structure or a partial ring structure,
and the linear structure is preferred.
[0043] As examples of Q.sup.3 which is the alkyl group having at
least four carbon atoms, the following may be mentioned.
[0044] H(CH.sub.2).sub.4--, H(CH.sub.2).sub.6--,
H(CH.sub.2).sub.8--, H(CH.sub.2).sub.10--, H(CH.sub.2).sub.12--,
H(CH.sub.2).sub.14--, H(CH.sub.2).sub.16--,
H(CH.sub.2).sub.18--
[0045] In a case where Q.sup.3 is a fluoroalkyl group having at
least one carbon atom, which may contain an etheric oxygen atom or
a monovalent organic group having the above fluoroalkyl group as a
partial structure, a group represented by R.sup.f1--Y-- is
preferred (R.sup.f1 is a fluoroalkyl group having at least one
carbon atom, which may contain an etheric oxygen atom, and Y is a
bivalent coupling group containing no fluorine atom).
[0046] R.sup.f1 is preferably a C.sub.1-12 fluoroalkyl group which
may contain an etheric oxygen atom, more preferably a C.sub.1-12
perfluoroalkyl group which may contain an etheric oxygen atom,
particularly preferably a C.sub.3-12 perfluoroalkyl group which may
contain an etheric oxygen atom. The structure of R.sup.f1 may be a
linear structure, a branch structure, a ring structure or a partial
ring structure, and the linear structure is preferred.
[0047] As specific examples of R.sup.f1, the following groups may
be mentioned.
[0048] F(CF.sub.2).sub.4--, F(CF.sub.2).sub.6--,
F(CF.sub.2).sub.8--, H(CF.sub.2).sub.4--, H(CF.sub.2).sub.6--,
H(CF.sub.2).sub.8--; CF.sub.3CF.sub.2OCF.sub.2CF.sub.2OCF.sub.2--,
CF.sub.3CF.sub.2OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2--,
CF.sub.3CF.sub.2OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF.su-
b.2--,
CF.sub.3CF.sub.2OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2-
OCF.sub.2CF.sub.2--; CF.sub.3CF.sub.2CF.sub.2OCF.sub.2--,
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--,
CF.sub.3CF.sub.2CF.sub.2OCF (CF.sub.3)--,
CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2--,
CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF.sub.2CF.sub.2--,
CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF (CF.sub.3)--,
CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF(CF.sub.3)CF.sub.2--.
[0049] Y is preferably a group represented by --(CF.sub.2).sub.m--,
--SO.sub.2NR.sup.2--(CH.sub.2).sub.m-- or
--(C.dbd.O)--NR.sup.2--(CH.sub.2).sub.m--. m is an integer of from
1 to 5, and R.sup.2 is a hydrogen atom, a methyl group or an ethyl
group.
[0050] Q.sup.4 may be an alkylene group having at least four carbom
atoms, a bivalent organic group having the above alkylene group as
a partial structure, a fluoroalkylene group having at least two
carbon atoms, which may contain an etheric oxygen atom, or a
bivalent organic group having the above fluoroalkylene group as a
partial structure.
[0051] In a case where Q.sup.4 is an alkylene group having at least
four carbon atoms or a bivalent organic group having the above
alkylene group as a partial structure, an alkylene group having at
least four carbon atoms is preferred, and a C.sub.4-18 alkylene
group is more preferred. Such groups are excellent in the water
repellent property. The alkylene group may have a linear structure,
a branch structure, a ring structure or a partial ring structure,
and the linear structure is preferred.
[0052] As specific examples in a case where Q.sup.4 is an alkylene
group having at least four carbon atoms, the following groups may
be mentioned.
[0053] --(CH.sub.2).sub.4--, --(CH.sub.2).sub.6--,
--(CH.sub.2).sub.8--, --(CH.sub.2).sub.10--, --(CH.sub.2).sub.12--,
--(CH.sub.2).sub.14--, --(CH.sub.2).sub.16--,
--(CH.sub.2).sub.18--.
[0054] In a case where Q.sup.4 is a fluoroalkylene group having at
least two carbon atoms, which may contain an etheric oxygen atom or
a bivalent organic group having the above fluoroalkylene group as a
partial structure, a C.sub.2-12 fluoroalkylene group which may
contain an etheric oxygen atom is preferred, and a C.sub.2-12
perfluoroalkylene group which may contain an etheric oxygen atom is
more preferred.
[0055] The fluoroalkylene group which may contain an etheric oxygen
atom may have a linear structure, a branch structure, a ring
structure or a partial ring structure, and the linear structure is
preferred.
[0056] As specific examples in a case where Q.sup.4 is a
fluoroalkylene group having at least two carbon atoms, which may
contain an etheric oxygen atom, the following groups may be
mentioned.
[0057] --(CF.sub.2).sub.2--, --(CF.sub.2).sub.4--,
--(CF.sub.2).sub.6--, --(CF.sub.2).sub.8--,
--(CF.sub.3)CF[OCF.sub.2CF(CF.sub.3)]OCF.sub.2(CF.sub.2).sub.4CF.sub.2O[C-
F(CF.sub.3)CF.sub.2O]CF(CF.sub.3)--,
--CF.sub.2CF.sub.2OCF.sub.2(CF.sub.3)CF.sub.2[OCF.sub.2CF(CF.sub.3)]OCF.s-
ub.2--,
--(CF.sub.2).sub.4CF.sub.2O[CF(CF.sub.3)CF.sub.2O]CF(CF.sub.3)CF.s-
ub.2OCF.sub.2CF.sub.2--.
[0058] The compound (a) is preferably the compound (11), the
compound (12) or the compound (21). In view of the excellent water
repellent property, it is more preferred to use the compound (11)
wherein each of Q.sup.1 and Q.sup.2 is a methyl group, the compound
(21) wherein Q.sup.1 is a methyl group or the compound (12) wherein
Q.sup.3 is a group represented by R.sup.f1--Y--, and R.sup.f1 is a
C.sub.1-12 perfluoroalkyl group, are preferably used.
[0059] Further, in the case of the compound (11) wherein each of
Q.sup.1 and Q.sup.2 is a methyl group or the compound (21) wherein
Q.sup.1 is a methyl group, a compound having a molecular weight of
from 500 to 1,000,000 is particularly preferred, and the compound
having a molecular weight of from 1,000 to 1,000,000 is especially
preferred. The compound (11) or the compound (21) is usually
available as a mixture of two or more compounds, of which n is
different. n may sometimes be represented by an average value of n
in the mixture, and in such a case, n is a positive number. In the
compound (11) or the compound (21), if the molecular weight is at
least 500, evaporation from the surface of a substrate can be
prevented, and if the molecular weight is lower than 1,000,000, the
solubility of the compound to a solvent is improved, whereby the
work efficiency is improved.
[0060] The photopolymerization initiator is a substance which
absorbs light and generates radicals to initiate the polymerization
reaction and is selected from substances which initiate the
polymerization of a (meth)acryloyl group.
[0061] For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one
(Dalocure 1173, manufactured by Merck Ltd.),
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by
CIBA-GEIGY Limited),
1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one (Dalocure
1116, manufactured by Merck Ltd.), benzodimethyl ketal (Irgacure
651, manufactured by CIBA-GEIGY Limited),
2-methyl-1-(4-methylthio)phenyl-2-morphorlinopropanon-1-one
(Irgacure 907, manufactured by CIBA-GEIGY Limited),
2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone-1
(Irgacure 369, manufactured by CIBA-GEIGY Limited) or 2,4-diethyl
thioxanthone (KAYACURE DETX, manufactured by Nippon Kayaku Co.,
Ltd.) may preferably mentioned. They may be used alone or as a
mixture of two or more. The amount of the photopolymerization
initiator is preferably from 0.1 to 50 mass %, more preferably from
1 to 10 mass %, based on the total amount of the compound (a).
[0062] The compound (A) preferably contains a compound (b) having
at least three (meth)acryloyl groups, provided that the compound
(b) may be the same as the compound (a) or a compound other than
the compound (a). Namely, the compound (b) which is the compound
(a) means a compound having at least three (meth)acryloyl groups
and a water repellent moiety, and the compound (b) which is other
than the compound (a) means a compound having at least three
(meth)acryloyl groups and no water repellent moiety. Use of the
compound (b) having at least three (meth)acryloyl groups is
effective to accelerate the curing of the composition (A).
[0063] The compound (b) which is other than the compound (a) is
preferably a poly(meth)acrylate which is a tri or more valent
polyol. The number of the (meth)acryloyl groups in one molecule is
preferably at most 8. Specifically, pentaerythritol
tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,
dipentaerythritol penta(meth)acrylate, dipentaerythritol
hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate,
ditrimethylolpropane tetra(meth)acrylate or the like may be
mentioned. The amount of the compound (b) which is other than the
compound (a) in the composition (A) is preferably from 0.1 to 100
mass %, more preferably from 5 to 50 mass %, based on the total
amount of the compound (a). If the amount of the compound (b) is
excessive, the water repellent property of a water repellent region
of a film formed by curing the composition (A) may sometimes
deteriorate.
[0064] Next, the above step (2) will be explained. The composition
(A) is mixed with the above hydrophilic compound, and the surface
of a substrate is coated with the mixture to form a film, followed
by leaving it to stand still to make the hydrophilic compound move
to the substrate side. Since the compound having a hydrophilic
moiety is a material of a high energy surface, it orientates to the
substrate side, and since the compound having a water repellent
moiety is a material of a low energy surface, it tends to orientate
to the gas phase interface. By utilizing such characteristics, it
is possible to form a bilayer structure of the hydrophilic compound
and the compound (a).
[0065] The amount of the hydrophilic compound is preferably from
0.1 to 100 mass %, more preferably from 1 to 60 mass %, based on
the amount of the compound (a). Condition to leave the substrate to
stand still is changed, depending on the type of the compound (a),
the type of the hydrophilic compound and the film thickness. A
substrate coated with a material may be heated to accelerate this
phenomenon. By heating an applied hydrophilic compound and/or
compound (a) to at least a glass transition temperature, a bilayer
structure can be formed in a short time at a level of from a few
seconds to a few minutes.
[0066] Instead of the hydrophilic compound, a compound which reacts
to a surface to make the surface hydrophilic may be used, and the
compound is made to be moved to the surface of the substrate in the
same manner and reacted with the substrate surface so that the
substrate surface becomes hydrophilic. The amount of the compound
or condition to use the compound is the same as in the case of the
hydrophilic compound.
[0067] The composition (A) in the step (1) and the hydrophilic
compound, the composition(A), etc. in the step (2) are applied
preferably in the form of a solution containing a solvent. The
solvent is preferably an alcohol such as methanol, ethanol or
isopropanol, an ester such as ethyl acetate or butyl acetate or a
hydrocarbon such as hexane. The solid component concentration in
the solution is preferably from 0.01 to 50 mass %, more preferably
from 0.1 to 10 mass %.
[0068] As a method to form a film, a method to coat a substrate
surface with the above solution is preferred, and a spin coating
method, a dip coating method, a wire bar coating method, a blade
coating method or a roll coating method may be employed. The
coating may be carried out at room temperature or under heating.
Further, a substrate on which a film has been formed is preferably
dried under nitrogen stream or the like. The drying is preferably
carried out at room temperature. In a case where the drying is
carried out under heating, it is preferred that temperature and
time are adjusted, depending on the heat resistance of the material
of a substrate.
[0069] After a film is formed, a part of the film is irradiated
with light. Light used for irradiation preferably has a wavelength
of at least 200 nm, more preferably a wavelength of at least 300
nm. Further, light having a wavelength of at most 380 nm is
preferred, and light having a wavelength of at most 365 nm is more
preferred. When the wavelength of light is at least 200 nm,
decomposition of a substrate can be prevented in most cases.
Further, a photopolymerization initiator which initiate
polymerization with light having a wavelength of at most 380 nm is
easily available, and the light source is also not expensive.
Irradiation time is properly changed, depending on the wavelength
of light, the intensity of light, the type of light, the type of
the composition (A), etc. In a case of an ultrahigh-pressure
mercury lamp, irradiation time is from 5 to 120 seconds with from 2
to 100 mw/cm.sup.2. In general, irradiation time with a
high-pressure mercury lamp is shorter than that with an
ultrahigh-pressure mercury lamp.
[0070] As the light source, a low-pressure mercury lamp, a
high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a
xenon lamp, a sodium lamp, a gas laser such as nitrogen, a liquid
laser of an organic dye solution or a solid-state laser having a
rare earth element ion contained in an inorganic single crystal
may, for example, be mentioned. Further, as a light source other
than a laser capable of providing a monochromatic light, an
ultraviolet light having a desired wavelength, which is obtained by
subjecting a broadband line spectrum or a continuous spectrum to an
optical filter such as a band-pass filter and a cut-off filter, may
be used. Since a large area can be irradiated with light at once, a
high-pressure mercury lamp or an ultrahigh-pressure mercury lamp is
preferred as the light source.
[0071] Light irradiation is preferably carried out through a
photomask. By this method, the curing reaction can be carried out
only at a desired region on a film surface, and a treated substrate
on which a desired pattern of a hydrophilic region and a water
repellent region is formed can be obtained.
[0072] The atmosphere for light irradiation can be optionally
selected. In a case where a water repellent film having a thickness
of at most 100 nm is formed by curing the composition (A), since
cure inhibition due to oxygen may sometimes occur, light
irradiation is preferably carried out under an inert gas atmosphere
such as nitrogen. The inert gas may, for example, be a gas selected
from nitrogen, argon, helium and carbon dioxide, and nitrogen gas
is preferred, since it is inexpensive.
[0073] Light irradiation may be carried out from either side of a
substrate, as long as light has a wavelength which can transmit
through a substrate. Usually, it is preferred to apply light from
the side of a film containing the composition (A).
[0074] After a water repellent film is formed by curing the
composition (A), an uncured composition (A) remained on the
substrate surface is removed. By removing the uncured composition
(A), a hydrophilic surface is exposed. As a method for removing the
uncured composition (A), in a case where the molecular weight of
the composition (A) is low, it is preferred to remove the uncured
composition (A) by blowing nitrogen stream. In a case where the
molecular weight of the composition (A) is high, since the
composition (A) is not likely to evaporate, it is preferred to wash
the surface on which the uncured composition (A) remains with an
organic solvent. The organic solvent to be used for washing is
preferably a solvent which dissolves the composition (a). The
organic solvent may, for example, be an alcohol such as methanol,
ethanol or isopropanol, an ester such as ethyl acetate or butyl
acetate or a hydrocarbon such as hexane.
[0075] The film thickness of the water repellent film is from 0.1
to 100 nm, preferably from 0.1 to 50 nm, more preferably from 0.1
to 10 nm. Particularly, in a case where the treated substrate of
the present invention is used for an electronic member, a thin
water repellent film is preferred. A member on which a pattern of a
film made of a functional material is formed by coating a surface
of the treated substrate of the present invention with a
hydrophilic solution containing a functional material to coat the
hydrophilic region of the treated substrate on which a pattern is
formed with the hydrophilic liquid, followed by drying to form a
pattern of a film made of the functional material, and removing the
water repellent film formed by curing the composition (A). The
member is useful for an electronic element. The water repellent
film formed by curing the composition (A) is removed, because in a
case where the member is used for an electronic element, the water
repellent film may influence the operation of the element.
Accordingly, a thin water repellent film is preferred from the
viewpoint of removing the film easily.
[0076] By the present invention, a treated substrate having a
hydrophilic region and a water repellent region made of a water
repellent film formed by curing the composition (A) on a surface of
a substrate, can be provided. The hydrophilic region can be
distinguished from the water repellent region by contact angle to
water. In the present specification, the contact angle is
represented by a measured value obtained by a sessile drop method.
The contact angle to water of the hydrophilic region is preferably
at most 50.degree., more preferably at most 40.degree.,
particularly preferably at most 20.degree.. The contact angle to
water of the water repellent region is preferably at least
80.degree., more preferably at least 100.degree., particularly
preferably at least 110.degree.. The difference in the contact
angle to water between the water repellent region and the
hydrophilic region is preferably at least 40.degree., more
preferably at least 70.degree.. The larger the difference is, the
higher the contrast of the pattern can be obtained.
[0077] Further, in a case where a fluorine-containing compound is
used as the compound (a), the water repellent region also has an
oil repellent property. The oil repellent region can repel a
lipophilic solvent (such as a hydrocarbon solvent), whereby if a
lipohilic solvent is used as a solvent for a functional material
for forming a functional film, it can be prevented that the water
repellent region is stained with the functional material. Further,
it is possible to impart affinity to a lipophilic solvent to the
hydrophilic region. The oil repellent region can be distinguished
from the hydrophilic region by contact angle to hydrocarbon
compounds. Specifically, in a case where hexadecane is used as a
hydrocarbon compound, the contact angle to hexadecane of the
lipophilic region is preferably at least 40.degree., more
preferably at least 60.degree., particularly preferably at least
70.degree..
[0078] In the production of the treated substrate of the present
invention, if light or laser for photopolymerization is applied
though a photomask at a time of light irradiation, a treated
substrate on which a desired pattern of a hydrophilic region and a
water repellent region is formed can be obtained. Further, it is
possible to form a pattern such that width between the hydrophilic
region and the water repellent region is at most 10 .mu.m.
[0079] A member on which a pattern of a film made of a functional
material is formed can be produced by applying a hydrophilic liquid
containing a functional material on a surface of the treated
substrate of the present invention in order to coat the hydrophilic
region of the treated substrate on which a pattern is formed with
the hydrophilic liquid, followed by drying.
[0080] The functional material may, for example, be a metal
particles-dispersed paste for forming metal wiring, a pigment
material for forming a color filter, a ceramic material for forming
an electronic device or an organic display or a semiconductor
material.
[0081] The hydrophilic liquid containing a functional material
means a liquid wherein a functional material is dissolved in water
or a high polar organic solvent. A high polar organic solvent which
is miscible with water is more preferred.
[0082] The coating method may, for example, be a coating method
such as a spin coating, a dip coating, wire bar coating, blade
coating or roll coating or a printing method for a specific region
such as screen printing or inkjet printing. Among them, from the
viewpoint of selectively coating a non-water repellent region on a
pattern of a water repellent region and a hydrophilic region,
screen printing or inkjet printing is preferred.
[0083] The drying is preferably carried out in atmosphere, nitrogen
stream or the like. Further, the drying is preferably carried out
at room temperature or under heating. In a case where the drying is
carried out under heating, it is preferred that the temperature and
time are optionally changed, depending on the heat resistance of a
material of a substrate.
[0084] As mentioned above, for electronic elements, a member on
which a pattern of a film made of a functional material is formed
and of which water repellent film is removed is useful. It is
preferred that the water repellent film is removed by carrying out
an UV/O.sub.3 treatment on the member. For example, it is preferred
that PL7-200 (manufactured by CENT ENGINEERING CO., LTD.) is used,
and a member is irradiated for from 1 to 3 minutes.
[0085] In a case where the treated substrate of the present
invention is stained with a hydrophilic ink as a functional
material, the member can be used as a stump. Further, in a case
where a pattern of a hydrophilic region and a water repellent
region is preciously formed, it can be used as a stump for
microcontact printing.
[0086] Further, in a case where a flexible substrate such as a
plastic substrate is used as a substrate, by irradiating the
substrate with light by installing plural rolls and an exposure
apparatus between the plural rolls so that Roll to Roll method can
be carried out, a photo-treated substrate can be obtained with a
high throughput.
EXAMPLES
[0087] Now, the present invention will be described in further
detail with reference to Examples, but it should be understood that
the present invention is by no means restricted thereto.
[0088] The contact angle to water was measured by putting water
droplets on 3 different spots on a surface of a substrate to be
measured, and each droplet was measured in accordance with JIS
R3257 "sessile drop test method of a glass substrate surface". The
droplet was 2 .mu.L/droplet, and the measurement was carried out at
20.degree. C. The contact angle is represented by an average value
of 3 droplets (n=3).
Example 1
Substrate Wash
[0089] A 5 cm.sup.2 silicon wafer was washed with ethanol and then
washed with UV/O.sub.3.
Preparation of a Coating Solution
[0090] 2.5 g of isopropanol was added in a sample vessel. 0.1 g of
a 10 mass % isopropanol solution of a polydimethyl siloxane having
methacryloyloxy propyl groups at both terminals (DMS-R18,
manufactured by Gelest, Inc., the compound of the formula (21)
wherein R.sup.1 is a methyl group, Q.sup.1 is a methyl group, k is
3, and the molecular weight is from 4,500 to 5,500) was added to
the sample vessel. 0.2 g of a 1 mass % isopropanol solution of
trimethylol propane triacrylate was added. 0.06 g of a 1%
isopropanol solution of IRGACURE 369 (manufactured by CIBA-GEIGY
Limited) was added as a photopolymerization initiator. The sample
vessel was shaken a few times to mix the solution.
Coating with a Solution
[0091] The silicon wafer was coated with the prepared coating
solution by spin coating under a condition of 3000 rpm for 20
seconds, and a film was formed.
Light Irradiation
[0092] A surface of the obtained film was irradiated with
ultraviolet light of a high-pressure mercury lamp at 5 mw/cm.sup.2
for 15 seconds under nitrogen atmosphere from the film side through
a photomask having a pore pattern of 2.5 cm.times.5 cm.
Substrate Wash
[0093] After the light irradiation, the substrate was rinsed with
isopropanol, then rinsed with ethanol and dried under nitrogen
stream, whereby a treated substrate was obtained.
Film Thickness Measurement
[0094] The film thickness of the obtained treated substrate was
measured by Atomic Force Microscope (AFM), and as a result, the
thickness of the water repellent film was 8 nm.
Measurement of Contact Angle
[0095] With respect to the surface of the treated substrate
obtained by the above step, the contact angle to water was
28.degree. at a non-irradiated part and 100.degree. at an
ultraviolet light irradiated part. Therefore, a water
repellent-hydrophilic pattern having a hydrophilic region (contact
angle: 28.degree.) and a water repellent region (contact angle:
100.degree.) was confirmed. The film thickness of the water
repellent region was 38 nm.
Example 2
[0096] The same operation was carried out as in Example 1, except
that IRAGARACURE 907 (manufactured by CIBA-GEIGY Limited) was used,
instead of IRAGARACURE 369. The thickness of the obtained film was
8 nm.
[0097] The contact angle to water of the obtained treated substrate
was 21.degree. at a non-irradiated part and 100.degree. at an
ultraviolet light irradiated part. Therefore, a water
repellent-hydrophilic pattern having a hydrophilic region (contact
angle: 21.degree.) and a water repellent region (contact angle:
100.degree.) was confirmed.
Example 3
[0098] The same operation was carried out as in Example 2, except
that 0.5 g of a 1% aqueous solution of a polyvinyl alcohol
(molecular weight: 500, manufactured by KANTO CHEMICAL CO., INC.)
was added to a coating solution, and after spin coating, the
substrate was left to stand still for 5 minutes. The thickness of
the obtained film is estimated to be about 12 nm.
[0099] The contact angle to water of the obtained treated substrate
was 29.degree. at a non-irradiated part and 100.degree. at an
ultraviolet light irradiated part. Therefore, a water
repellent-hydrophilic pattern having a hydrophilic region (contact
angle: 29.degree.) and a water repellent region (contact angle:
100.degree.) was confirmed.
Example 4
[0100] The same operation was carried out as in Example 2, except
that before the substrate is coated with a coating solution, the
substrate was coated with 2 mL of a 1 mass % aqueous solution of a
polyvinyl alcohol (molecular weight: 500, manufactured by KANTO
CHEMICAL CO., INC.) by spin coating (3,000 rpm, 20 seconds). The
thickness of the obtained film was estimated to be about 12 nm.
[0101] The contact angle to water of the obtained treated substrate
was 29.degree. at a non-irradiated part and 100.degree. at an
ultraviolet light irradiated part. Therefore, a water
repellent-hydrophilic pattern having a hydrophilic region (contact
angle: 29.degree.) and a water repellent region (contact angle:
100.degree.) was confirmed.
Example 5
[0102] 0.1 g of
NH.sub.2CH.sub.2CH.sub.2CH.sub.2--Si(OCH.sub.2CH.sub.3)H.sub.3
(manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 100
g of isopropanol, and 0.025 g of distilled water was added thereto,
followed by stirring at room temperature for 20 hours to obtain an
amino silicone solution.
[0103] The same operation was carried out as in Example 2, except
that before the substrate is coated with a coating solution, the
substrate was coated with 20 mL of the above prepared amino silicon
solution by spin coating (3,000 rpm, 20 seconds). The thickness of
the obtained film was estimated to be about 15 nm.
[0104] The contact angle to water of the obtained treated substrate
was 11.degree. at a non-irradiated part and 102.degree. at an
ultraviolet light irradiated part. Therefore, a water
repellent-hydrophilic pattern having a hydrophilic region (contact
angle: 11.degree.) and a water repellent region (contact angle:
102.degree.) was confirmed.
Example 6
[0105] The same operation was carried out as in Example 1, except
that instead of IRAGACURE 369, IRAGACURE 907 was used, instead of
trimethylol propane triacrylate, dipentaerythritol hexaacrylate was
used, and instead of the nitrogen atmosphere, light irradiation was
carried out under air atmosphere. The thickness of the obtained
film was about 8 nm.
[0106] The contact angle to water of the obtained treated substrate
was 19.degree. at a non-irradiated part and 100.degree. at an
ultraviolet light irradiated part. Therefore, a water
repellent-hydrophilic pattern having a hydrophilic region (contact
angle: 19.degree.) and a water repellent region (contact angle:
100.degree.) was confirmed.
INDUSTRIAL APPLICABILITY
[0107] According to the production process of the present
invention, a fine pattern having a hydrophilic region and a water
repellent region can be formed without employing a large facility,
a vacuum apparatus and a light source. In a case where a functional
ink is spread on the pattern by using an ink-jet, since only a
hydrophilic region is coated with the functional ink, and a water
repellent region is not coated with the functional ink, patterning
can be carried out on a substrate with a functional ink. Further,
the present invention can also be applied for forming electronic
device circuits. Further, a thin film having a water
repellent-hydrophilic pattern can be used as a stump for micro
contact printing, by dyeing a hydrophilic region with a functional
ink and transcribing it.
[0108] Further, a treated substrate having a hydrophilic region and
a water repellent region on a surface can be used in a medical
field. For example, a mask having a pattern such that a blood
vessel of a capillary vessel corresponds to a hydrophilic part is
prepared, and a pattern of a capillary vessel is printed on a
substrate. Vascular endothelial cells are spread thereon, and the
cells grow only on the hydrophilic region, whereby a pattern of a
capillary vessel can be regenerated.
[0109] Further, in a case where a compound wherein the compound (a)
having a water repellent property and no oil repellent property
(for example, a fluorine-containing hydrocarbon water repellent
compound) is used, since a water repellent region is also a
lipophilic region, an oil ink can be contained at the lipophilic
region, and a substrate can be used as a platemaker for print.
[0110] Further, in the treated substrate of the present invention
having a hydrophilic region and a water repellent region on a
surface of a substrate, by utilizing a reactivity of a hydroxyl
group, etc. on a surface of a hydrophilic region, a compound having
another property can react on the surface of the hydrophilic
region, whereby a substrate having a water repellent property and
another property can be formed.
[0111] The entire disclosure of Japanese Patent Application No.
2006-059495 filed on March 6, including specification, claims and
summary is incorporated herein by reference in its entirety.
* * * * *