U.S. patent application number 10/579093 was filed with the patent office on 2007-03-22 for production process and production apparatus of three-dimensionally structure material.
This patent application is currently assigned to CANON KABUSHIKI KAISHA. Invention is credited to Ryuji Higashi, Masayuki Ikegami, Ikuo Nakazawa, Koichi Sato, Sakae Suda, Keiichiro Tsubaki.
Application Number | 20070063371 10/579093 |
Document ID | / |
Family ID | 34805581 |
Filed Date | 2007-03-22 |
United States Patent
Application |
20070063371 |
Kind Code |
A1 |
Sato; Koichi ; et
al. |
March 22, 2007 |
Production process and production apparatus of three-dimensionally
structure material
Abstract
Disclosed herein is a process for producing a
three-dimensionally structured material, which comprises the steps
of preparing a liquid composition comprising a block polymer and a
liquid medium, and imparting a stimulus to the liquid composition
to modify the block polymer, thereby forming the
three-dimensionally structured material.
Inventors: |
Sato; Koichi; (Kanagawa-ken,
JP) ; Nakazawa; Ikuo; (Kanagawa-ken, JP) ;
Higashi; Ryuji; (Kanagawa-ken, JP) ; Suda; Sakae;
(Kanagawa-ken, JP) ; Ikegami; Masayuki;
(Kanagawa-ken, JP) ; Tsubaki; Keiichiro;
(Kanagawa-ken, JP) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
US
|
Assignee: |
CANON KABUSHIKI KAISHA
TOKYO
JP
1468501
|
Family ID: |
34805581 |
Appl. No.: |
10/579093 |
Filed: |
January 25, 2005 |
PCT Filed: |
January 25, 2005 |
PCT NO: |
PCT/JP05/01312 |
371 Date: |
May 12, 2006 |
Current U.S.
Class: |
264/113 ;
264/484; 526/287 |
Current CPC
Class: |
C08F 293/005 20130101;
C08L 53/00 20130101; C08L 2666/02 20130101; C08L 51/003 20130101;
B29C 64/135 20170801; C08F 8/44 20130101; C09D 11/30 20130101; C08F
297/02 20130101; G03F 7/0037 20130101; C08F 8/44 20130101; C08F
8/12 20130101; C08F 293/005 20130101; C08L 53/00 20130101; C08L
2666/02 20130101; C08L 51/003 20130101; C08L 2666/02 20130101; C08F
293/005 20130101 |
Class at
Publication: |
264/113 ;
264/484; 526/287 |
International
Class: |
D04H 1/16 20060101
D04H001/16 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 27, 2004 |
JP |
2004-018877 |
Claims
1. A process for producing a three-dimensionally structured
material, which comprises the steps of preparing a liquid
composition comprising a block polymer and a liquid medium, and
imparting a stimulus to the liquid composition to modify the block
polymer, thereby forming the three-dimensionally structured
material.
2. The production process according to claim 1, which further
comprises a step of solidifying the liquid composition after the
modification of the block copolymer.
3. The production process according to claim 1, wherein the block
polymer is amphiphilic and forms micelles.
4. The production process according to claim 1, wherein the
stimulus to the liquid composition is selected from temperature
change, application of an electric field, exposure to
electromagnetic wave, pH change, addition of a chemical substance,
and concentration change.
5. The production process according to claim 1, which further
comprises a step of ejecting the liquid composition to form the
three-dimensionally structured material.
6. The production process according to claim 1, wherein a
functional substance is included in the block polymer.
7. The production process according to claim 6, wherein the
functional substance is selected from an agricultural chemical, a
medicament and a coloring material.
8. The production process according to claim 7, wherein the
coloring material includes a pigment.
9. The production process according to claim 1, wherein the block
polymer has a repeating structure of a monomer unit composed of an
alkenyl ether.
10. An apparatus for producing a three-dimensionally structured
material, which comprises a means for imparting a stimulus to a
liquid composition comprising a block polymer and a liquid medium
to modify the block polymer, thereby forming the
three-dimensionally structured material.
11. A liquid composition suitable for use in producing a
three-dimensionally structured material, which comprises a block
polymer modifiable by stimulus and a liquid medium.
12. The liquid composition according to claim 11, wherein the block
polymer is amphiphilic and forms micelles.
13. The liquid composition according to claim 11, wherein the block
polymer has a repeating structure of a monomer unit composed of an
alkenyl ether.
14. A three-dimensionally structured material formed by a block
polymer modifiable by stimulus.
Description
TECHNICAL FIELD
[0001] The present invention relates to a production process and a
production apparatus of a three-dimensionally structured material,
and particularly to a three-dimensional pattern-forming process or
a three-dimensional shaping process used in a functional
device-fabricating step, rapid prototyping or the like, and
materials and apparatus thereof.
BACKGROUND ART
[0002] In fabrication of devices making good use of micromechanics
or fabrication of active devices heretofore used in semiconductors
and display elements, a step of etching using spin coating and
patterned exposure is conducted as a process for forming a steric
three-dimensional pattern. It has also been recently known to
directly form a three-dimensional pattern using minute ink-jet
technology.
[0003] Technological development mainly for rapid prototyping with
three-dimensional shaping technology using a stereolithographic
technique or liquid-jet technique (see Japanese Patent Application
Laid-Open No. H05-279436) is also increasingly conducted to develop
technology for producing a larger molded object without using the
so-called mold.
[0004] However, the above-described production process of a
three-dimensionally structured material, such as the conventional
three-dimensional pattern-forming process or three-dimensional
shaping process, may be not yet sufficient in some cases from the
viewpoint of cost or performance, and its use is limited to limited
users. There is thus a demand for more improvement in technical
level under these circumstances.
DISCLOSURE OF THE INVENTION
[0005] The present invention has been made in view of the foregoing
background art and has achieved as its object the provision of a
process for easily producing a three-dimensionally structured
material by modifying a liquid composition comprising a block
polymer and a liquid medium.
[0006] Another object of the present invention is to provide an
apparatus for producing a three-dimensionally structured material
by modifying a liquid composition comprising a block polymer and a
liquid medium.
[0007] A further object of the present invention is to provide a
liquid composition comprising a modifiable block polymer and a
liquid medium, and a three-dimensionally structured material formed
from this composition.
[0008] In a first aspect of the present invention, there is thus
provided a process for producing a three-dimensionally structured
material, which comprises the steps of preparing a liquid
composition comprising a block polymer and a liquid medium, and
imparting a stimulus to the liquid composition to modify the block
polymer, thereby forming the three-dimensionally structured
material.
[0009] The process may preferably further comprise a step of
solidifying the liquid composition after the modification of the
block copolymer.
[0010] The block polymer may preferably be amphiphilic and form
micelles.
[0011] The process may preferably further comprise a step of
ejecting the liquid composition to form the three-dimensionally
structured material.
[0012] A functional substance may preferably be included in the
block polymer.
[0013] The block polymer may preferably have a repeating structure
of a monomer unit composed of an alkenyl ether.
[0014] In a second aspect of the present invention, there is
provided an apparatus for producing a three-dimensionally
structured material, which comprises a means for imparting a
stimulus to a liquid composition comprising a block polymer and a
liquid medium to modify the block polymer, thereby forming the
three-dimensionally structured material.
[0015] In a third aspect of the present invention, there is
provided a liquid composition suitable for use in producing a
three-dimensionally structured material, which comprises a block
polymer modifiable by stimulus and a liquid medium.
[0016] In a fourth aspect of the present invention, there is
provided a three-dimensionally structured material formed by a
block polymer modifiable by stimulus.
[0017] According to the present invention, there can be provided a
process for easily producing a three-dimensionally structured
material by modifying a liquid composition comprising a block
polymer and a liquid medium.
[0018] According to the present invention, there can also be
provided an apparatus for producing a three-dimensionally
structured material by modifying a liquid composition comprising a
block polymer and a liquid medium.
[0019] According to the present invention, there can further be
provided a liquid composition comprising a modifiable block polymer
and a liquid medium, and a three-dimensionally structured material
formed from this composition.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 schematically illustrates a three-dimensional
pattern-forming process by a liquid-jet method according to the
present invention.
[0021] FIG. 2 is a block diagram illustrating the construction of a
liquid-jet recording apparatus.
BEST MODE FOR CARRYING OUT THE INVENTION
[0022] The present invention will hereinafter be described in
detail.
[0023] In the first aspect of the present invention, there is
provided a process for shaping a three-dimensionally structured
material using a modifiable liquid composition, which comprises
modifying the liquid composition comprising a block polymer in a
liquid medium.
[0024] A process for forming a steric three-dimensional pattern in
fabrication of devices making good use of micromechanics or
fabrication of active devices heretofore used in semiconductors and
display elements, and three-dimensional shaping technology mainly
for rapid prototyping with three-dimensional shaping technology
using a stereolithographic technique or liquid-jet technique
(Japanese Patent Application Laid-Open No. H05-279436) as
technology for producing a larger molded object without using the
so-called mold are representative of a shaping process using a
modifiable liquid composition. In the present invention, a
three-dimensional shaping process using the stereolithographic
technique or liquid-jet technique is also preferably used.
Stereolithographic apparatus, SCS-8000 and SCS-3000 manufactured by
D-MEC LTD., and the like are known as specific examples of such
stereolithographic methods and apparatus. Thermo-Jet 3D Printer,
In-Vision 3D Printer and the like are known as three-dimensional
shaping methods and apparatus by the so-called liquid-ejection
method based on the ink-jet technology.
[0025] In such a three-dimensional object-shaping process using no
mold, a three-dimensional object is formed by modifying and
solidifying a liquid composition by light or any other external
field. As a typical example in the stereolithography, a
photo-curable liquid composition is filled in a bath, a laser beam
or ultraviolet ray is applied to a portion to form an intended
three-dimensional object to cure the liquid composition of this
portion, thereby forming a cured three-dimensional object, and a
peripheral uncured portion of the liquid composition is removed,
whereby the intended three-dimensional object can be obtained. A
feature of the present invention resides in that a liquid
composition comprising a block polymer, which is also called a
block copolymer, as a component in such a liquid composition is
used.
[0026] The block polymer used in the present invention is a polymer
called a block polymer or block copolymer, in which polymers of
different segment structures are bonded into a chain by a covalent
bond. In the present invention, a graft polymer may also be used.
The graft polymer is such a polymer that polymers of different
segment structures are covalently bonded in the form of a character
`T.` Specific examples of the block polymer usable in the present
invention include conventionally known block polymers such as
acrylic or methacrylic block polymers, block polymers composed of
polystyrene and any other addition polymerization system or
condensation polymerization system, and block polymers having
blocks of polyoxyethylene, polyoxyalkylene, polyalkenyl ether or
the like. In the present invention, the block copolymer is more
preferably in a block form of AB, ABA, ABD or the like. A, B and D
indicate block segments different from one another.
[0027] In the present invention, the block copolymer may be such a
graft polymer that another polymer is boned in the form of a
character `T` to a certain polymer chain. Each segment of the block
polymer may be a copolymer segment, and the copolymer form thereof
may be, for example, a random segment or graduation segment.
[0028] The present inventors have carried out an extensive
investigation repeatedly. As a result, it has been found that when
a liquid composition comprising the block polymer is used in the
above-described shaping method, modifiable properties derived from
the block polymer are utilized, a three-dimensional pattern can be
formed with extremely good results. Since the block polymer has
different 2 or more block segments, functional separation between
physical properties or characteristics of respective segments is
clearly made, and so it is suitable for use as various functional
materials. In particular, when the liquid composition is used in
the above-described shaping method, extremely excellent properties
or characteristics can be exhibited, and an excellent
three-dimensional pattern-forming process can be realized.
[0029] It is preferable that an amphiphilic block polymer be used
to use a micelle structure formed by this polymer at least either
before or after the modification. It goes without saying that the
micelle structure may be used both before and after the
modification. The micelle structure is preferably formed at the
time the liquid composition has been modified or solidified into a
three-dimensional object or in the course of conversion into the
three-dimensional object. The present inventors have also found
that when the micelle state is utilized upon the formation of a
three-dimensional object has been formed, its characteristic
viscoelastic properties are extremely suitable for the formation of
the three-dimensional object.
[0030] A preferable range for the viscoelastic properties in
formation of the three-dimensional object is from 10.sup.-1 to
10.sup.8 Pa for G' (storage modulus) and from 10.sup.-1 to 10.sup.8
Pa for G'' (loss modulus), and a more preferable range is from
10.sup.2 to 10.sup.7 Pa for G' and from 10.sup.2 to 10.sup.7 Pa for
G''. If both G' and G'' exceed 10.sup.8 Pa in formation of the
three-dimensional object, only a three-dimensional object in a
distorted form may be formed in some cases. If both G' and G'' are
lower than 10.sup.-1 Pa, no three-dimensional object may be formed
in some cases. Conditions of G'.gtoreq.G'' are preferably used. G'
and G'' may be generally measured by a viscoelastometer, or the
so-called rheometer. These viscoelastic properties appear in the
course of the modification. The liquid composition may have the
viscoelastic properties in all the course of the modification, or a
state having these viscoelastic properties may be temporally
formed. Both G' and G'' of the liquid composition before the
modification are preferably one hundredths or lower, more
preferably one thousandths or lower of the above-described
respective ranges.
[0031] The micelle referred to in the present invention may be
normal micelles in a water-based solvent or reversed micelles in an
organic solvent. In the present invention, the micelle is defined
as a micelle taken in a wide sense. When a self-accumulating
phase-separated higher-order structured material is formed in a
solvent by having both solvophilic and solvophobic segments, such a
structured material is regarded as a micelle. In other words, when
a block polymer having a segment soluble in, for example, toluene
and a segment insoluble therein is dispersed in toluene, a
structured material, in which a solvophilic portion and a
solvophobic portion undergo phase separation, is formed. Such a
structured material is also regarded as a micelle in the present
invention. In a narrow sense, it may also be interpreted that the
presence of water is indispensable both for the normal micelle and
the reversed micelle. In the present invention, however, such a
standpoint is not taken. The form of the micelle referred to in the
present invention may be any of spherical, elliptical, cylindrical
and lamellar forms.
[0032] A structured material in which a functional substance is
adsorbed on and coated with a solvophilic portion of an amphiphilic
block polymer, i.e., a coated functional substance structured
material is also suitably used in the present invention. This
coated functional substance structured material may be considered a
micelle in a wide sense. The functional substance in the present
invention may be any form of solid, powder and liquid and means a
compound or composition exhibiting a desired function. As examples
thereof, may be mentioned agricultural chemicals such as herbicides
and insecticides, medicaments such as anti-cancer drugs,
anti-allergic drugs and antiphlogistics, and coloring materials,
typically, dyes and pigments. Examples of the agricultural
chemicals include active compounds having a herbicidal effect and
active compounds having an insecticidal effect. Examples of the
medicaments include compounds easing or remitting a target
condition. The present invention is particularly effective when the
functional substance is a coloring material. When such a
three-dimensional object as described above is produced,
multi-color, preferably full-color representation becomes feasible,
and so the use of the coloring material as the functional substance
is highly useful. As specific examples of the coloring material,
may be mentioned particulate solids such as pigments, and dye
compounds.
[0033] As described above, examples of the coloring material
include pigments. Examples of the pigments include inorganic
achromatic pigments and organic or inorganic chromatic pigments.
Colorless or light-colored pigments and metalescent pigments may
also be used. Pigments newly synthesized for the present invention
may also be used. Examples of the pigments are mentioned below.
[0034] As examples of black pigments, may be mentioned Raven 1060
(trade name, product of Columbian Carbon Co.), Black Pearls L,
MOGUL-L, Regal 400R, Regal 660R and Regal 330R (trade name,
products of Cabot Company), Color Black FW1 and Printex 140V (trade
name, products of Degussa AG), and MA100 (trade name, product of
Mitsubishi Chemical Corporation). However, the present invention is
not limited thereto.
[0035] As examples of cyan pigments, may be mentioned C.I. Pigment
Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3 and C.I. Pigment
Blue 15. However, the present invention is not limited thereto.
[0036] As examples of magenta pigments, may be mentioned C.I.
Pigment Red 5, C.I. Pigment Red 7 and C.I. Pigment Red 12. However,
the present invention is not limited thereto.
[0037] As examples of yellow pigments, may be mentioned C.I.
Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14,
C.I. Pigment Yellow 16, C.I. Pigment Yellow 17 and C.I. Pigment
Yellow 74. However, the present invention is not limited
thereto.
[0038] In the present invention, dyes may also be used like the
pigments.
[0039] The dyes usable in the present invention may be either
publicly known or novel, and water-soluble dyes such as direct
dyes, acid dyes, basic dyes, reactive dyes and food dyes,
fat-soluble (oil-soluble) dyes, and insoluble colorants such as
disperse dyes as described below may be used. These dyes may also
be used in a solid state. Regarding this, for example, oil-soluble
dyes are preferably used.
[0040] Examples thereof include C.I. Solvent Blue 33, 38, 42, 45,
53, 65, 67, 70, 104, 114, 115 and 135; C.I. Solvent Red 25, 31, 86,
92, 97, 118, 132, 160, 186, 187 and 219; C.I. Solvent Yellow 1, 49,
62, 74, 79, 82, 83, 89, 90, 120, 121, 151, 153 and 154.
[0041] Water-soluble dyes may also be used. Examples thereof
include direct dyes such as C.I. Direct Black 17; C.I. Direct
Yellow 12 and 24; C.I. Direct Red 1, 4 and 13; C.I. Direct Blue 6,
22 and 25; C.I. Direct Orange 34 and 39; C.I. Direct Violet 47 and
48; C.I. Direct Brown 109; and C.I. Direct Green 59,
[0042] acid dyes such as C.I. Acid Black 2 and 7; C.I. Acid Yellow
11 and 17; C.I. Acid Red 1, 6 and 8; C.I. Acid Blue 9 and 22; C.I.
Acid Orange 7 and 19; and C.I. Acid Violet 49,
[0043] reactive dyes such as C.I. Reactive Black 1 and 5; C.I.
Reactive Yellow 2 and 3; C.I. Reactive Red 3 and 13; C.I. Reactive
Blue 2 and 3; C.I. Reactive Orange 5 and 7; C.I. Reactive Violet 1,
4 and 5; C.I. Reactive Green 5 and 8; and C.I. Reactive Brown 2 and
7, and
[0044] C.I. Basic Black 2; C.I. Basic Red 1 and 2; C.I. Basic Blue
1, 3 and 5; C.I. Basic Violet 7, 14 and 27; and C.I. Food Black 1
and 2.
[0045] Incidentally, the examples of the coloring materials
mentioned above are particularly preferred for the compositions
according to the present invention. However, the coloring materials
used in the present invention are not particularly limited to the
coloring materials mentioned above.
[0046] When a functional substance is used, the functional
substance is preferably contained in the liquid composition in a
range of from 0.01 to 80% by mass based on the whole mass of the
liquid composition. When two or more functional substances are
used, the total amount thereof is preferably set so as to fall
within the above-described range. When the amount of the functional
substances is not less than 0.01% by mass, a sufficient function is
achieved. When the amount is not more than 80% by mass, good
dispersibility is achieved. The amount is preferably within a range
of from 0.1% by mass to 50% by mass, more preferably from 0.3% by
mass to 30% by mass. In a preferred embodiment of the present
invention, the functional substance is used in such a state as
being coated with and included in the amphiphilic block polymer.
However, it may not be necessarily coated and included.
[0047] In the present invention, it is a preferred use mode to use
a micelle state formed by the amphiphilic block polymer. In this
state, a very preferable effect can be exhibited in the formation
of the three-dimensional object as described above. However, it is
particularly preferably used in conducting three-dimensional
imaging of a multi-color object using plural kinds of liquid
compositions containing a coloring material. In other words, an
excellent multi-color three-dimensionally imaged object can be
provided. There have heretofore arisen such problems that color
mixing occurs upon conducting multi-color imaging and that when
different colors overlap with each other, a portion of a first
color must be subjected to a solidifying treatment over a
sufficient period of time before the next color is formed for the
purpose of preventing color mixing. According to the present
invention, however, the color mixing can be inhibited very well. In
the case of stereolithography, a bath treatment must be typically
conducted for every color. In a direct shaping process such as the
liquid-jet, a color is subjected to a solidifying treatment over a
sufficient period of time, and a three-dimensional object of a next
color is then formed. However, the present invention is applied,
whereby multi-color imaging improved in color mixing can be
preferably conducted without taking such a too excess time in a
liquid-jet process in particular. On the other hand, such effect to
inhibit color mixing cannot be explained by the viscoelastic
properties alone. However, it is considered to relate to the fact
that a coloring material is formed by uniform micelle particles of
from several tens nanometers to submicrons.
[0048] In the present invention, a block polymer containing a
polyalkenyl ether structure is preferably used as a block polymer
compound. A block polymer containing a polyvinyl ether structure is
particularly preferred. A great number of synthetic processes of
the block polymer containing the polyalkenyl ether structure used
preferably in the present invention have been reported. A process
by cationic living polymerization by Aoshima et al. (Journal of
Polymer Bulletin, Vol. 15, p. 417, 1986; Japanese Patent
Application Laid-Open No. H11-322942) is representative thereof. By
conducting polymer synthesis by the cationic living polymerization,
various polymers such as homopolymers, copolymers composed of two
or more monomers, block polymers, graft polymers and graduation
polymers can be synthesized with their chain lengths (molecular
weights) exactly made uniform. In the polyalkenyl ether, various
functional groups may be introduced in its side chains. Besides,
the cationic polymerization may also be conducted in an HI/I.sub.2
system, HCl/SnCl.sub.4 system or the like.
[0049] The structure of the block polymer containing the
polyalkenyl ether structure may be a copolymer composed of vinyl
ether and another polymer.
[0050] The block polymer containing the polyvinyl ether structure
preferably used preferably has a repeating unit structure
represented by the following general formula (1): ##STR1## wherein
R.sub.1 is selected from a linear, branched or cyclic alkyl group
having 1 to 18 carbon atoms,
--(CH(R.sub.2)--CH(R.sub.3)--O).sub.l--R.sub.4 and
--(CH.sub.2).sub.m--(O).sub.n--R.sub.4, in which l and m are,
independently of each other, selected from integers of from 1 to
12, n is 0 or 1, R.sub.2 and R.sub.3 are, independently of each
other, hydrogen or CH.sub.3, and R.sub.4 is hydrogen, a linear,
branched or cyclic alkyl group having 1 to 6 carbon atoms, -Ph,
-Pyr, -Ph-Ph, -Ph-Pyr, --CHO, --CH.sub.2CHO, --CO--CH.dbd.CH.sub.2,
--CO--C(CH.sub.3).dbd.CH.sub.2 or --CH.sub.2COOR.sub.5, with the
proviso that when R.sub.4 is any other group than hydrogen,
hydrogen bonded to carbon may be substituted by a linear or
branched alkyl group having 1 to 4 carbon atoms, F, Cl, Br,
carboxylic acid, or carboxylic-acid salt, or carbon in the aromatic
ring may be substituted by nitrogen, and R.sub.5 is hydrogen or an
alkyl group having 1 to 5 carbon atoms.
[0051] In the above, -Ph, -Pyr, -Ph-Ph and -Ph-Pyr denote a phenyl,
pyridyl, biphenyl and pyridylphenyl groups, respectively. With
respect to the pyridyl, biphenyl and pyridylphenyl groups, they may
be any possible position isomers.
[0052] An amphiphilic block polymer can be obtained by, for
example, conducting synthesis by selecting a hydrophobic block
segment and a hydrophilic block segment from the repeating unit
structures of the general formula (1). In the case of the graft
polymer, an amphiphilic polymer can be obtained by, for example,
grafting a hydrophobic polymer segment on a hydrophilic
polymer.
[0053] As examples of specific repeating units of the hydrophilic
block segment, the segment preferably has a repeating unit
structure represented by the following general formula (2):
##STR2## wherein R.sub.21 is selected from
--(CH(R.sub.2)--CH(R.sub.3)--O).sub.l--R.sub.4 and
--(CH.sub.2).sub.m--(O).sub.n--R.sub.4, in which l and m are,
independently of each other, selected from integers of from 1 to
12, n is 0 or 1, R.sub.2 and R.sub.3 are, independently of each
other, hydrogen or CH.sub.3, and R.sub.4 is hydrogen, a linear,
branched or cyclic alkyl group having 1 to 6 carbon atoms, or an
aliphatic or aromatic carboxylic acid or carboxylic acid salt.
[0054] Preferable examples of the specific repeating units of the
hydrophilic block segment include the following units: ##STR3##
wherein Ph is 1,4-phenylene or 1,3-phenylene, Np is
2,6-naphthylene, 1,4-naphthylene or 1,5-naphthylene, and M is a
monovalent or polyvalent cation, with the proviso that when M is a
polyvalent cation, a counter anion also takes a form corresponding
to the cation.
[0055] As examples of specific repeating units of the hydrophobic
block segment, the segment preferably has a repeating unit
structure represented by the following general formula (3):
##STR4## wherein R.sub.31 is selected from a linear, branched or
cyclic alkyl group having 1 to 18 carbon atoms,
--(CH(R.sub.2)--CH(R.sub.3)--O).sub.l--R.sub.4 and
--(CH.sub.2).sub.m--(O).sub.n--R.sub.4, in which l and m are,
independently of each other, selected from integers of from 1 to
12, n is 0 or 1, R.sub.2 and R.sub.3 are, independently of each
other, hydrogen or CH.sub.3, and R.sub.4 is a linear, branched or
cyclic alkyl group having 1 to 6 carbon atoms, -Ph, -Pyr, -Ph-Ph,
-Ph-Pyr, --CHO, --CH.sub.2CHO, --CO--CH.dbd.CH.sub.2,
--CO--C(CH.sub.3).dbd.CH.sub.2 or --CH.sub.2COOR.sub.5, with the
proviso that hydrogen bonded to carbon may be substituted by a
linear or branched alkyl group having 1 to 4 carbon atoms, F, Cl,
or Br, or carbon in the aromatic ring may be substituted by
nitrogen, and R.sub.5 is an alkyl group having 1 to 5 carbon
atoms.
[0056] Preferable examples of the specific repeating units of the
hydrophobic block segment include the following units: ##STR5##
wherein Ph is 1,4-phenylene or 1,3-phenylene, and Np is
2,6-naphthylene, 1,4-naphthylene or 1,5-naphthylene.
[0057] The molecular weight distribution Mw (weight average
molecular weight)/Mn (number average molecular weight) of the block
polymer used in the present invention is preferably 2.0 or lower,
more preferably 1.6 or lower, still more preferably 1.3 or lower,
still further preferably 1.2 or lower.
[0058] The number average molecular weight (Mn) of the block
polymer or graft polymer used in the present invention is
preferably 200 or higher, preferably 3,000 or higher, but
preferably does not exceed 1,000,000. When the number average
molecular weight is 200 or higher, the dispersion stability of the
functional substance is improved. In the present invention, the
number average molecular weight and weight average molecular weight
of a polymer can be measured by volume exclusion chromatography
(another name: gel permeation chromatography/GPC).
[0059] The content of the block copolymer or graft polymer
contained in the liquid composition according to the present
invention is from 0.1% by mass to 90% by mass, preferably from 1%
by mass to 50% by mass. When the content is at least 0.1% by mass,
the functional substance is dispersed or dissolved in the liquid
composition in a sufficient state. When the content is not higher
than 90% by mass, the viscosity of the resulting liquid composition
becomes moderate. It is hence preferable to contain the block
polymer or graft polymer within the above-described range.
[0060] The liquid composition according to the present invention
contains a liquid medium. No particular limitation is imposed on
the liquid medium contained in the liquid composition according to
the present invention. The liquid medium means a liquid medium in
which components to be contained in the liquid composition can be
dissolved, suspended or dispersed. In the present invention,
water-insoluble organic solvents such as various kinds of linear,
branched and cyclic aliphatic hydrocarbons, aromatic hydrocarbons,
and heterocyclic aromatic hydrocarbons, water-soluble organic
solvents, and water may be used as the liquid medium. It goes
without saying that a mixed solvent thereof may be used.
[0061] A water-based liquid medium used in the liquid composition
according to the present invention is water or a hydrophilic liquid
medium composed of water and a water-soluble organic solvent.
[0062] Examples of the water-soluble organic solvent include
polyhydric alcohols such as ethylene glycol, diethylene glycol,
triethylene glycol, polyethylene glycol, propylene glycol,
polypropylene glycol and glycerol, polyhydric alcohol ethers such
as ethylene glycol monomethyl ether, ethylene glycol monoethyl
ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl
ether and diethylene glycol monobutyl ether, and
nitrogen-containing solvents such as N-methyl-2-pyrrolidone,
substituted pyrrolidone and triethanolamine. A monohydric alcohol
such as methanol, ethanol or isopropanol may also be used. A
water-soluble polymerizable compound may also be contained.
Examples thereof include hydroxyethylacrylic acid,
hydroxyethyl-methacrylic acid and styrenesulfonic acid. A
crosslinking agent may also be used at the same time. Two or more
of those described above may be used in combination as needed.
[0063] As an organic liquid medium used in the liquid composition
according to the present invention, may be used, for example,
toluene, hexane, heptane, nonane, an acetate, or a monohydric
alcohol such as methanol, ethanol or isopropyl alcohol.
Methacrylates, acrylates, styrene and the like may also be
mentioned. A crosslinking agent may also be used at the same time.
Two or more of those described above may be used in combination as
needed.
[0064] The content of the liquid medium used in the liquid
composition according to the present invention may be selected from
a range of from 0.9% by mass to 99% by mass, and it is preferably
from 10% by mass to 99% by mass. When the content is not lower than
0.1% by mass, the viscosity of the resulting liquid composition
becomes moderate. When the content is not higher than 99% by mass,
the function of the polymer can be sufficiently exhibited.
[0065] As the block polymer characteristically used in the present
invention, at least two amphiphilic polymers may also be used in
combination in the same liquid composition as needed.
[0066] The functional substance contained in the liquid composition
is preferably included in the block polymer or graft polymer for
the purpose of inhibiting modification caused by attack from an
external environment (typically, for improving weatherability). The
block polymer or graft polymer is effective in that it can easily
include the functional substance therein by forming a
self-accumulating structure. In order to improve the dispersion
stability and inclusion property of the functional substance, the
molecular motion of the block polymer or graft polymer is
preferably more flexible because such a polymer is likely to
physically entangle with the surface of the functional substance
and have affinity for it. The polymer may also be preferably
flexible from the viewpoint of easy formation of a coating layer on
a recording medium as described in detail below. Therefore, the
glass transition temperature Tg of the main chain of the block
polymer is preferably 20.degree. C. or lower, more preferably
0.degree. C. or lower, still more preferably -20.degree. C. or
lower. In this regard, a polymer having a polyvinyl ether structure
is preferably used because it has properties of a low glass
transition point and is flexible. In this sense, the block polymer
having the polyvinyl ether structure may also be preferably
used.
[0067] The functional substance is preferably included in the
liquid composition according to the present invention. The included
state can be formed by, for example, adding a solution of a
coloring material in an organic solvent insoluble in water to a
micelle formed by the block polymer or graft polymer in water and
then distilling off the organic solvent. Besides, it may also be
formed by forming an inclusion state by conducting phase inversion
into a hydrophilic solvent from a state that both block polymer or
graft polymer and coloring material have been dissolved in an
organic solvent, and distilling off the remaining organic solvent.
The confirmation of the included state can be performed by various
kinds of electron microscopes and/or instrumental analyses such as
X-ray diffraction. In the case of inclusion in a micelle state, the
included state can be indirectly confirmed by separation of the
coloring material from the solvent independently of the polymer
under conditions of micelle collapse.
[0068] As described above, the block polymer or graft polymer
preferably forms a micelle state. Therefore, it is effective that
the block polymer or graft polymer used in the present invention is
amphiphilic. In this sense, the block polymer or graft polymer
preferably has a polymer segment having an ionic repeating unit
structure. In the present invention, the block polymer is
preferably used from the viewpoints of dispersion stability,
inclusion of the functional substance and various properties such
as viscosity.
[0069] The proportion of the functional substance included in the
block polymer or graft polymer of the functional substance
contained in the liquid composition is preferably 90% by mass or
higher, more preferably 95% by mass or higher, still more
preferably 98% by mass or higher based on the whole mass of the
functional substance. This quantitative proportion can also be
observed by various kinds of electron microscopes, instrumental
analyses such as X-ray diffraction, or coloring density analysis
when the functional substance is a coloring material, or by the
indirect method described above.
[0070] Besides the above components, various kinds of modifiers or
additives such as antioxidants, viscosity modifiers, ultraviolet
absorbents, surfactants and mildewproofing agents may be added to
the liquid composition according to the present invention.
[0071] In the present invention, plural kinds of liquid
compositions may also be used in combination to shape a
three-dimensional object. As described above, the multi-color
three-dimensional imaging is an example thereof. A
three-dimensionally structured material composed of plural kinds of
layers different in not only color species but also properties can
also be produced. For example, a three-dimensional object may be
formed by alternately stacking layers different in modulus or
strength to produce a three-dimensional object having both
properties that are not necessarily matched to each other, i.e.,
high modulus and excellent impact resistance. A multi-color
three-dimensional object may also be produced. When a
three-dimensional pattern is formed using such plural kinds of
liquid compositions, it is preferable that plural kinds of liquid
compositions containing the block polymer according to the present
invention be used, at least one of the liquid compositions be a
water-based liquid composition, and at least one of the other
liquid compositions be an oil-based liquid composition in that a
three-dimensional object improved in mixing of 2 liquids (2 colors)
can be produced. All the liquid compositions used do not always
contain the block polymer, only one of them may be a liquid
composition containing the block polymer.
[0072] In the present invention, the liquid composition described
above is modified to produce a three-dimensional object. Some
stimulus to be a trigger for modification is imparted to facilitate
the modification, thereby solidifying the liquid composition to
produce the three-dimensional object. The polymer-containing
composition according to the present invention can respond to
various stimuli to modify its state (properties). As example of
"stimuli" in the present invention, may be mentioned temperature
change; application of an electric field; exposure to light
(electromagnetic wave) such as ultraviolet light, visible light or
infrared light; pH change of the composition; addition of a
chemical substance; and concentration change of the composition.
These stimuli may preferably be used in combination.
[0073] A specific example of a three-dimensional pattern-forming
process for a three-dimensionally structured material according to
the present invention is illustrated in FIG. 1. FIG. 1 illustrates
a three-dimensional pattern-forming process by a liquid-jet method.
Reference numerals 1 and 2 indicate liquid-jet devices typically
illustrated. The liquid-jet device is basically the same device as
an ink-jet device of digital printing technology. A liquid is
ejected by a drive device 3 to form a pattern. The thermal-jet or
the piezo-jet is representative of the drive device 3. The
liquid-jet device may be a continuous liquid-jet device that does
not carry out on-demand driving. Reference numerals 4, 5 and 6 are
a liquid feed passage, a liquid ejection opening and a substrate on
which a three-dimensional object is formed, respectively.
[0074] As a specific three-dimensional pattern-forming process, the
liquid-jet devices 1, 2 are used as liquid-jet devices of the heat
retaining type. Two compositions are used as the liquid
compositions. One is a blue-pigment-including liquid composition
containing a block polymer of which the viscosity and the
elasticity at a temperature not higher than 60.degree. C. increase
3,000 times compared with those at a temperature higher than that,
and the other is a yellow pigment-including liquid composition
containing a block polymer of which the viscosity and the
elasticity at a temperature not higher than 60.degree. C. increase
4,000 times compared with those at a temperature higher than that.
The blue liquid composition is first ejected on a desired pattern
from a head of the liquid-jet device 1 retained to a temperature of
80.degree. C. and primarily solidified by increase in viscosity and
elasticity attending on temperature drop before and after impact on
the substrate after the ejection, thereby forming a
three-dimensional basic pattern, during which electromagnetic waves
7, typically ultraviolet rays, are continuously irradiated to
complete the crosslinking and solidification of the polymer. Before
long, the yellow liquid composition is ejected from a head of the
liquid-jet device 2 in the same manner as in the head of the
liquid-jet device 1 to form a pattern. In such a manner, a
three-dimensional object is easily formed because the
characteristic block polymer according to the present invention is
used. In addition, color mixing is markedly improved. In order to
effectively develop the feature of the present invention as
described above, a combination of plural stimuli such as thermal
stimulus and electromagnetic wave stimulus is preferably used.
Specifically, one of the stimuli is preferably electromagnetic wave
stimulus in that it can be imparted with no contact. In the present
invention, however, it is only necessary to use modification by at
least one stimulus, and it is not essential to conduct modification
by plural kinds of stimuli.
[0075] The present invention may also be applied to fabricating
processes for micromechanic devices, semiconductor devices, TFT,
and display devices such as an organic EL.
[0076] FIG. 2 is a functional diagram schematically illustrating a
liquid-jet recording apparatus. Reference numeral 50 indicates a
central processing unit (CPU) of the liquid-jet recording apparatus
20. A program for controlling the CPU 50 may be stored in a program
memory 66 or may also be stored in a memory means such as EEPROM
(not illustrated) as the so-called firmware. According to the
liquid-jet recording apparatus, recording data is received from a
recording data-preparing means (not illustrated, computer or the
like) to the program memory 66. The recording data may be
information itself of a three-dimensional object to be recorded,
compressed information thereof or encoded information. When the
compressed or encoded information is processed, expansion or
development can be conducted by the CPU 50 to obtain the
information of images or characters to be recorded. An X-encoder 62
(for example, relating to an X-direction or main scanning
direction) and a Y-encoder 64 (for example, relating to a
Y-direction or secondary scanning direction) can be provided to
notify a relative position of a head to a substrate as a recording
medium to the CPU 50.
[0077] The CPU 50 sends signals for recording a three-dimensional
image to an X-motor drive circuit 52, a Y-motor drive circuit 54
and a head drive circuit 60 on the basis of the information of the
program memory 66, X-encoder 62 and Y-encoder 64. The X-motor drive
circuit 52 and Y-motor drive circuit 54 drive an X-direction drive
motor 56 and a Y-direction drive motor 58, respectively, to move a
head 70 relatively to the substrate and to a recording position.
The head drive circuit 60 sends signals for conducting ejection of
various kinds of liquid compositions to the head 70 at the time the
head 70 has been moved to the recording position, thereby
conducting recording. The head 70 may be a head for ejecting a
single liquid composition or a head for ejecting plural kinds of
liquid compositions.
[0078] The present invention will hereinafter be described in
detail by the following examples. However, the present invention is
not limited to these examples.
EXAMPLE 1
<Block Polymer 1 Used>
Synthesis of triblock polymer composed of isobutyl vinyl ether
(IBVE; block A), 2-(2-ethoxyethyl)oxyethyl vinyl ether (EOEOVE;
block B) and ethyl 4-(2-vinyloxy)ethoxy-benzoate (VEOEtPhCOOEt;
block C)
[0079] After the interior of a glass container equipped with a
three-way stop-cock was purged with nitrogen, the container was
heated to 250.degree. C. under a nitrogen gas atmosphere to remove
adsorbed water. After the system was returned to room temperature,
12 mmol of IBVE, 16 mmol of ethyl acetate, 0.05 mmol of
1-isobutoxyethyl acetate and 11 ml of toluene were added to cool
the reaction system. At the time the temperature within the system
had reached 0.degree. C., 0.2 mmol of ethylaluminum sesquichloride
(equimolar mixture of diethylaluminum chloride and ethylaluminum
dichloride) was added to initiate polymerization. The molecular
weight was periodically monitored by means of gel permeation
chromatography (GPC) to confirm completion of the polymerization of
a block A.
[0080] Then, 18 mmol of a monomer of a block B was added to
continue the polymerization. After completion of the polymerization
of the block B was confirmed by monitoring by means of GPC, a
toluene solution of 10 mmol of a component of a block C was added
to continue the polymerization. After 20 hours, the polymerization
reaction was terminated. The termination of the polymerization
reaction was conducted by adding a 0.3% by mass aqueous solution of
ammonia/methanol into the system. The reaction mixture solution was
diluted with dichloromethane and washed 3 times with 0.6 M
hydrochloric acid and then 3 times with distilled water. The
resultant organic phase was concentrated and dried to solids by an
evaporator, and the residue was vacuum-dried. The resultant product
was dialyzed repeatedly in a methanol solvent using a
semi-permeable membrane composed of cellulose to remove monomeric
compounds, thereby obtaining the intended triblock polymer. The
identification of the compound was conducted by means of NMR and
GPC. Mn was 50,600, and Mw/Mn was 1.34. The polymerization ratio of
A to B to C was 200:300:30.
[0081] The block polymer thus obtained was hydrolyzed in a mixed
solution of dimethylformamide and aqueous sodium hydroxide, whereby
the block C component was hydrolyzed to obtain a triblock polymer
in the form of a sodium salt. The identification of the compound
was conducted by means of NMR and GPC.
[0082] This polymer was neutralized with 0.1N hydrochloric acid in
an aqueous dispersion to obtain a triblock polymer, in which the
block C component turned into a free carboxylic acid. The
identification of the compound was conducted by means of NMR and
GPC.
<Block Polymer 2 Used>
[0083] Block Polymer 2 was obtained by copolymerizing 2 mol % of
2-vinyloxyethyl methacrylate with the monomer of the segment B of
Block Polymer 1.
<Liquid Composition>
[0084] One hundred parts by mass of Block Polymer 1 in the form of
a carboxylate obtained above and 20 parts by mass of Oil Blue N
(trade name, C.I. Solvent Blue 14, product of Aldrich Co.) were
both dissolved in 250 parts by mass of THF and 80 parts by mass of
ethylene glycol, the resultant solution was inverted into a water
phase with 1,000 parts by mass of distilled water, and water was
distilled off under pressure to reduce the amount of the liquid,
thereby obtaining Liquid Composition (1). Even when the ink
composition thus obtained was left to stand for 10 days at room
temperature, neither separation nor precipitation occurred.
[0085] Liquid Composition (2) was prepared in the same manner as in
the preparation of Liquid Composition (1) except that the coloring
material was changed to C.I. Pigment Blue 15:3. Even when the ink
composition thus obtained was left to stand for 10 days at room
temperature, neither separation nor precipitation occurred.
[0086] Liquid Composition (3) was prepared in the same manner as in
the preparation of Liquid Composition (1) except that the coloring
material was changed to a yellow oil-soluble dye (VALIFAST YELLOW
3108, trade name, product of Orient Chemical Industries Ltd.). Even
when the ink composition thus obtained was left to stand for 10
days at room temperature, neither separation nor precipitation
occurred.
[0087] Liquid Composition (4) was prepared in the same manner as in
the preparation of Liquid Composition (1) except that Block Polymer
2 in the form of a carboxylate obtained above was used, a yellow
oil-soluble dye (VALIFAST YELLOW 3108, trade name, product of
Orient Chemical Industries Ltd.) was used as the coloring material,
and 3 parts by mass of a photo-polymerization initiator (IRGACURE
184, trade name, product of Ciba-Geigy Limited) was added.
[0088] G' and G'' of Liquid Compositions (1) to (4) at 80.degree.
C. and 0.degree. C. are shown in the following Table 1. The
measurement was conducted by means of Rheometer DAR100 (trade name,
manufactured by Rheologica Instruments) by applying sinusoidal
oscillation of 1 Hz. TABLE-US-00001 TABLE 1 80.degree. C. 0.degree.
C. G' (Pa) G'' (Pa) G' (Pa) G'' (Pa) Liquid Composition (1) 0.012
0.009 8,142 1,320 Liquid Composition (2) 0.008 0.010 12,290 4,578
Liquid Composition (3) 0.010 0.009 9,788 5,544 Liquid Composition
(4) 0.010 0.010 10,234 2,320
[0089] Each of Liquid Compositions (1) to (4) was adjusted to pH 2
with diluted hydrochloric acid at 80.degree. C. As a result,
colored micelle particles were precipitated. A supernatant obtained
by removing the particles by centrifugation was colorless. With
respect to the density ratio in terms of the intensity ratio at
.lamda.max between the ink composition and the decolored water
phase, the absorbancy of the supernatant was lower than the
detection limit. From this fact, it was found that the coloring
material was completely included in the block polymer micelle.
<Production of Three-Dimensional Object>
[0090] A heater was installed in a head part of an ink-jet printer
(BJC-800J, trade name, manufactured by Canon Inc.) to control the
head part within a range of 80.degree. C..+-.4.degree. C. using a
thermocouple. A cover was removed from the printer to arrange a
silane-coupling-agent-coated stainless substrate having a thickness
of 0.3 mm, which was a recording medium, with a distance of 20 mm
from the head. The substrate was held at 0.degree. C. Liquid
Composition (4) was charged into an ink tank to conduct recording
2,500 times in the whole region of 1 mm.times.5 mm while being
irradiated with ultraviolet light of about 2 mW/cm.sup.2 with a
central wavelength of 365 nm at a time duty of 4% and 0.1 Hz,
thereby producing a three-dimensional object A. The
three-dimensional object A thus obtained had an average width of
1.22 mm, an average length of 5.45 mm and an average height of 9.55
mm.
[0091] Liquid Composition (1) was used to produce a
three-dimensional object B in the same manner as described above.
The three-dimensional object thus obtained had an average width of
1.26 mm, an average length of 5.99 mm and an average height of 7.55
mm. G' and G'' of this three-dimensional object were measured in
accordance with the method described above and were found to be
18,442 Pa and 8,541 Pa, respectively.
[0092] Liquid Compositions (2) and (3) were respectively used to
produce three-dimensional-objects C and D in the same manner as in
Liquid Composition (1), so that similar three-dimensional objects
could be produced.
[0093] Just after the production of the three-dimensional object B,
Liquid Composition (4) was applied on the object with the same
pattern to produce a three-dimensional object. The
three-dimensional object thus obtained had an average width of 1.23
mm, an average length of 5.67 mm and an average height of 18.44 mm.
Color mixing between blue and yellow colors was scarcely observed.
The color mixing thickness at the portion where the most severe
color mixing was observed was at most 0.05 mm.
COMPARATIVE EXAMPLE 1
[0094] Water, acrylic acid and 2-hydroxyethyl acrylate were mixed
in a mass ratio of 68:12:20 (in terms of parts by mass). To this
mixture were added 1 part by mass of a photo-polymerization
initiator (IRGACURE 184, trade name, product of Ciba-Geigy Limited)
and 3 parts by mass of C.I. Direct Yellow 12, thereby preparing
Liquid Composition .alpha.. Liquid Composition .beta. was also
prepared in the same manner as described above except that the
coloring material was changed to C.I. Direct Red 1. A two-color
three-dimensional object was produced in the same manner as in
EXAMPLE 1 except that Liquid Compositions .alpha. and .beta. were
used. However, severe color mixing between yellow and red colors
was observed, and the whole thereof turned orange.
[0095] According to the process and apparatus of the present
invention for producing a three-dimensionally structured material,
the three-dimensionally structured material can be easily produced
by modifying a liquid composition comprising a block polymer and a
liquid medium, so that they can be utilized in a process for
forming a steric three-dimensional pattern in fabrication of
devices making good use of micromechanics or active devices used in
semiconductors and display elements.
[0096] This application claims priority from Japanese Patent
Application No. 2004-018877 filed on Jan. 27, 2004, which is hereby
incorporated by reference herein.
* * * * *