U.S. patent application number 12/683097 was filed with the patent office on 2010-05-06 for ink-jet head and its manufacture method.
This patent application is currently assigned to CANON KABUSHIKI KAISHA. Invention is credited to Carsten Becker-Willinger, Etsuko Hino, Pamela Kalmes, Norio Ohkuma, Helmut Schmidt.
Application Number | 20100107412 12/683097 |
Document ID | / |
Family ID | 34074129 |
Filed Date | 2010-05-06 |
United States Patent
Application |
20100107412 |
Kind Code |
A1 |
Hino; Etsuko ; et
al. |
May 6, 2010 |
INK-JET HEAD AND ITS MANUFACTURE METHOD
Abstract
An ink jet head is formed of a nozzle material composed of a
condensation product comprising a hydrolysable silane compound
having a fluorine-containing group and a photo-polymerizable resin
composition.
Inventors: |
Hino; Etsuko; (Machida-shi,
JP) ; Ohkuma; Norio; (Machida-shi, JP) ;
Schmidt; Helmut; (Saarbrucken, DE) ;
Becker-Willinger; Carsten; (Saarbrucken, DE) ;
Kalmes; Pamela; (Quierschied, DE) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
1290 Avenue of the Americas
NEW YORK
NY
10104-3800
US
|
Assignee: |
CANON KABUSHIKI KAISHA
Tokyo
JP
|
Family ID: |
34074129 |
Appl. No.: |
12/683097 |
Filed: |
January 6, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10541767 |
Jul 8, 2005 |
7658469 |
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PCT/JP2003/009246 |
Jul 22, 2003 |
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12683097 |
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Current U.S.
Class: |
29/890.1 |
Current CPC
Class: |
B41J 2/1606 20130101;
B41J 2/1631 20130101; B41J 2/1603 20130101; Y10T 29/49401 20150115;
B41J 2/1433 20130101; B41J 2/1639 20130101; B41J 2/1645 20130101;
B41J 2/162 20130101 |
Class at
Publication: |
29/890.1 |
International
Class: |
B21D 53/76 20060101
B21D053/76 |
Claims
1-21. (canceled)
22. A method of manufacturing an ink jet head including a member
provided with an ejection opening for ejecting ink, the method
comprising: applying a material comprising a condensation product
comprising a hydrolysable silane compound having a
fluorine-containing group and a photo-polymerizable resin
composition for forming the member on a substrate; and forming the
ejection opening by exposing the material and removing an unexposed
portion of the material.
23. A method of manufacturing an ink jet head including a member
provided with an ejection opening for ejecting ink and an ink
passage communicating with the ejection opening, the method
comprising: providing a pattern of the ink passage on a substrate
provided with an ejection pressure generating element for ejecting
ink; providing a coating layer comprising a condensation product
comprising a hydrolysable silane compound having a
fluorine-containing group and a photo-polymerizable resin
composition for forming the member on the pattern; forming an
opening by exposing the coating layer and removing an unexposed
portion of the coating layer; and removing the pattern to form the
passage.
24. A method of manufacturing an ink jet head according to claim
22, wherein after the ejection opening formation, a curing reaction
is promoted with light or thermal energy.
25. A method of manufacturing an ink jet head according to claim
24, wherein the nozzle material is applied two or more times on the
substrate.
26. A method of manufacturing an ink jet head according to claim
22, wherein the photo-polymerizable resin composition is a
cationically photo-polymerizable resin composition.
27. A method of manufacturing an ink jet head according to claim
26, wherein the cationically photo-polymerizable resin composition
contains an epoxy compound.
28. A method of manufacturing an ink jet head according to claim
27, wherein the cationically photo-polymerizable resin composition
comprises an epoxy compound that is solid state at room
temperature.
29. A method of manufacturing an ink jet head according to claim
22, wherein the condensation product further comprises a
hydrolysable silane compound having no fluorine-containing
group.
30. A method of manufacturing an ink jet head according to claim
29, wherein the hydrolysable silane compound having no
fluorine-containing group is a hydrolysable silane compound having
a photo-polymerizable group.
31. A method of manufacturing an ink jet head according to claim
30, wherein the hydrolysable silane compound having a
photo-polymerizable group is a hydrolysable silane compound having
a cationic polymerization group.
32. A method of manufacturing an ink jet head according to claim
30, wherein the hydrolysable silane compound having a
photo-polymerizable group is a hydrolysable silane compound having
an epoxy group.
33. A method of manufacturing an ink jet head according to claim
29, wherein the hydrolysable silane compound having no
fluorine-containing group is selected from a silane having at least
one alkyl substituent, a silane having at least one aryl
substituent or a silane having no non-hydrolysable substituent.
34. A method of manufacturing an ink jet head according to claim
22, wherein the condensation product comprises a hydrolysable
silane compound having a fluorine-containing group, a hydrolysable
silane compound having a photo-polymerizable group, and a
hydrolysable silane compound selected from a silane having at least
one alkyl substituent, a silane having at least one aryl
substituent or a silane having no non-hydrolysable substituent.
35. A method of manufacturing an ink jet head according to claim
22, wherein the hydrolysable silane compound having a
fluorine-containing group is represented by general formula (1):
R.sub.fSi(R).sub.bX(.sub.3-b) (1) wherein R.sub.f is a
non-hydrolysable substituent having 1 to 30 fluorine atoms bonded
to a carbon atom, R is a non-hydrolysable substituent, X is a
hydrolysable substituent, and b is an integer from 0 to 2.
36. A method of manufacturing an ink jet head according to claim
35, wherein the non-hydrolysable substituent R.sub.f has at least 5
fluorine atoms bonded to a carbon atom.
37. A method of manufacturing an ink jet head according to claim
35, wherein the condensation product comprises at least two
hydrolysable silane compounds having a fluorine-containing group,
the silane compounds having a different number of fluorine atoms
contained therein.
38. A method of manufacturing an ink jet head according to claim
31, wherein the hydrolysable silane compound having a cationic
polymerizable group is represented by general formula (2):
R.sub.cSi(R).sub.bX(.sub.3-b) (2) wherein R.sub.c is a
non-hydrolysable substituent having a cationic polymerizable group,
R is a non-hydrolysable substituent, X is a hydrolysable
substituent, and b is an integer from 0 to 2.
39. A method of manufacturing an ink jet head according to claim
33, wherein the hydrolysable silane compound selected from a silane
having at least one alkyl substituent, a silane having at least one
aryl substituent or a silane having no non-hydrolysable substituent
is represented by general formula (3): R.sub.aSiX(.sub.4-a) (3)
wherein R is a non-hydrolysable substituent selected from
substituted or unsubstituted alkyl groups and substituted or
unsubstituted aryl groups, X is a hydrolysable substituent, and a
is an integer from 0 to 3.
40. A method of manufacturing an ink jet head according to claim
22, wherein the hydrolysable silane compound having a
fluorine-containing group is represented by formula (4):
CF.sub.3(CF.sub.2).sub.n--Z--SiX.sub.3 (4) wherein X is a
hydrolysable substituent and preferably is methoxy or ethoxy, Z is
a divalent organic group, and n is an integer from 0 to 20.
Description
TECHNICAL FIELD
[0001] This invention is in an ink jet head and its manufacture
method.
BACKGROUND ART
[0002] Recently, the technical development to the improvement in a
performance of smaller droplet, higher drive frequency and more
number of nozzle is continued in order to make the record
characteristic more advanced in an ink jet record system. And image
recording is performed by ejecting liquid from an ejection opening
as small droplet which adheres to the recording medium typified by
paper.
[0003] Here, a surface treatment is becoming more important to
maintain ejecting performance by keeping ejecting opening surface
as same condition at any time. Moreover, it is common to wipe off
the ink which remained on the surface by e.g. rubber blade
periodically to maintain the condition of the ejecting opening
surface in an ink jet head. A liquid repellent material is demanded
for easy wiping, and wiping durability.
[0004] Moreover, when the liquid repellent layer is prepared on the
surface, the liquid repellent layer needs to adhere to its lower
layer, and the problem of peeling off of liquid repellent layer may
occur. Since the ink used for an ink jet head is not neutral in
many cases, it is also required that the liquid repellent material
should have durability against ink and have adhesion power to a
nozzle. In addition to preventing peeling, from a viewpoint of
simplification of manufacturing process and cost reduction, the
process is desired that the nozzle material and liquid repellent
layer is prepared all at once. That is, nozzle material itself is
desired to have liquid repellency.
[0005] Various methods have so far been indicated as the liquid
repellent processing on the surface of a nozzle in the ink jet
head. However, most of them were just the surface treatment of the
formed nozzle, and the nozzle material itself did not have the
liquid repellent nature.
[0006] The surface treatment method which used the fluoride
containing silane compound is indicated in Japanese Patent
Publication No 10-505870 and U.S. Pat. No. 6,283,578.
[0007] However, these surface treatments were aimed at liquid
repellent nature grant, and were not those in which the liquid
repellent material itself has patterning nature. Moreover, the
liquid repellent materials that had photosensitivity were indicated
by Japanese Patent Application Laid-Open No. 11-322896, Japanese
Patent Application Laid-Open No. 11-335440, and Japanese Patent
Application Laid-Open No. 2000-26575. These materials could not
form the solid structure like a nozzle.
[0008] When the fluorine-containing compound which is a typical
liquid repellent material is added to resin, it is well-known
phenomenon that fluorine-containing group is arranged in the
surface for its low surface energy, and presenting liquid
repellency.
[0009] However, since fluorine-containing compounds generally have
low dissolubility to other resin, it was difficult to mix with
photosensitive resin and to use together.
[0010] Although the block copolymer having fluorine-containing
group was indicated in Japanese Patent Application Laid-Open No.
2002-105152 as a coating composition, it could not be applied to
the high-precision patterning like nozzle forming. Japanese Patent
Application Laid-Open No. 2002-292878 referred to the orifice plate
having nozzle structure, which was made of fluorine-containing
resin. Since fluorine-containing resin did not have photosensitive
characteristic corresponding to patterning by photo-lithography,
the nozzle had to be formed by dry etching etc. Furthermore, the
inside of ink passage of a nozzle needs to be hydrophilic in order
to obtain the ejecting performance, hydrophilic processing needed
to be performed inside of the ink passage and the adhesion side
with basis material and so on.
[0011] Cationically polymerizable resin composition, which included
fluorine-containing compounds, was indicated by Japanese Patent
Application Laid-Open No. 8-290572. However, the purpose of this
invention was the rate reduction of water absorption of material,
not liquid repellency. Since the compound in this invention has
hydroxyl group for dissolubility with resin composition, the
composition did not show liquid repellency.
[0012] U.S. Pat. No. 5,644,014, EP B1 587667 and Japanese Patent
Publication No. 3306442 referred to the liquid repellent material
comprising hydrolysable silane compounds which had
fluorine-containing group. Although the above-mentioned material is
indicating the photo curability which was derived from photo
radical polymerization, it is not mentioned about pattern formation
using photo lithography technology nor the application to an ink
jet head.
DISCLOSURE OF THE INVENTION
[0013] This invention is made in view of above-mentioned many
points, carried out to provide liquid repellent material of an ink
jet head, which has high liquid repellency, high durability against
the wiping (to maintain high liquid repellency) and the ease of
wiping simultaneously, and which realizes high-quality image
recording.
[0014] The further purpose is to offer a manufacturing method of
ink jet head which realizes the improvement in accuracy of the
ejection outlet portion of a nozzle and a simple manufacturing
process, by giving liquid repellent nature to the above-mentioned
nozzle material itself, and making a liquid repellent processing
process unnecessary.
[0015] The present invention designed to attain the above-mentioned
objectives is an ink jet head, wherein the nozzle material
comprises condensation product of hydrolysable silane compound
having fluorine-containing group and photo-polymerizable resin
composition.
[0016] Another present invention designed to attain the
above-mentioned objectives is a method of manufacturing ink jet
head, which is forming the nozzle having liquid repellent nature on
the surface thereof by pattern-exposure and developing a nozzle
material on the substrate, wherein the nozzle material comprises
condensation product of a hydrolysable silane compound having
fluorine-containing group and photo-polymerizable resin
composition.
[0017] That is, the compatibility of liquid repellent material and
photo resist composition is improved by using the above-mentioned
composition. Thus, good patterning characteristic corresponding to
formation of a high precision structure like a nozzle, high liquid
repellency and high wiping durability are realized without liquid
repellent processing on the surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a perspective view of a substrate to be used for
manufacturing the ink jet head of this invention.
[0019] FIG. 2 is a 2-2 sectional view of FIG. 1, showing an initial
step of manufacturing the ink jet head of this invention.
[0020] FIG. 3 is a sectional view showing a step for manufacturing
the ink jet head of this invention.
[0021] FIG. 4 is a sectional view showing a step for manufacturing
the ink jet head of this invention.
[0022] FIG. 5 is a sectional view showing a step for manufacturing
the ink jet head of this invention.
[0023] FIG. 6 is a sectional view showing a step for manufacturing
the ink jet head of this invention.
[0024] FIG. 7 is a sectional view showing a step for manufacturing
the ink jet head of this invention.
[0025] FIG. 8 is a sectional view showing the ink jet head of this
invention manufactured by the steps of FIGS. 2 to 7.
BEST MODE FOR CARRYING OUT THE INVENTION
[0026] The present invention will be described in detail.
[0027] These inventors found out that the nozzle surface which has
high liquid repellency and high wiping durability even if liquid
repellent processing was not performed, as a result of using the
composition comprising condensation product containing hydrolysable
silane compound having fluorine-containing group and
photo-polymerizable resin composition as the nozzle material of the
ink jet head.
[0028] According to the composition of the nozzle material of this
invention, the cured material has the siloxane frame (Inorganic
frame) formed from the hydrolysable silane, and a frame (Organic
frame: ether bond when using the epoxy group) by curing the
cationically polymerizable group. Thereby, a cured material becomes
into the so-called organic and inorganic hybrid cured material, and
durability against wiping and its recording liquid is improved by
leaps and bounds. That is, it is thought that its strength as a
film improves and the wiping resistance improves compared with
liquid repellent layer formed only by the siloxane frame since
liquid repellent layer of this invention has an organic frame.
[0029] Furthermore, since it is organic and inorganic hybrid
material, the compatibility of fluorine-containing compound and
photo polymerizable resin composition, which was a problem
conventionally, is improved. And fluorine-containing compound which
has low surface free energy is able to mix with photo-polymerizable
resin composition as nozzle material.
[0030] Subsequently, the composition material of this invention
will be described concretely. The hydrolysable silane compound
having fluorine-containing group, which is one of the starting
materials of the condensation product, is indispensable to have one
or more non-hydrolysable fluorine-containing group and hydrolysable
substituent.
[0031] As the non-hydrolysable fluorine-containing group,
straight-chain or blanched-chain fluoro-carbon group can be
referred. In the case of blanched-chain fluoro-carbon group, the
terminal or the side chain is preferred to be trifluoromethyl or
pentafluoroethyl group. Owing to its surface free energy,
fluorine-containing group have tendency to arrange in the
surface.
[0032] On the other hand, fluorine-containing group of the
fluorosilane contains generally at least 1, preferably at least 3
and in particular at least 5 fluorine atoms, and generally not more
than 30, more preferably not more than 25 fluorine atoms which are
attached to one or more carbon atoms. It is preferred that said
carbon atoms are aliphatic including cycloaliphatic atoms. Further,
the carbon atoms to which fluorine atoms are attached are
preferably separated by at least two atoms from the silicon atom,
which are preferably carbon and/or oxygen atoms, e.g. a C.sub.1-4
alkylene or a C.sub.1-4 alkylenoxy, such as an ethylene or
ethylenoxy linkage.
[0033] Preferred hydrolysable silanes having a fluorine-containing
group are those of general formula (1):
R.sub.fSi(R).sub.bX.sub.(3-b) (1)
wherein R.sub.f is a non-hydrolysable substituent having 1 to 30
fluorine atoms bonded to carbon atoms, R is a non-hydrolysable
substituent, X is a hydrolysable substituent, and b is an integer
from 0 to 2, preferably 0 or 1 and in particular 0.
[0034] In general formula (1) the hydrolysable substituents X,
which may be identical or different from one another, are, for
example, hydrogen or halogen (F, Cl, Br or I), alkoxy (preferably
C.sub.1-6 alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy
and n-butoxy, sec-butoxy, isobutoxy, and tert-butoxy), aryloxy
(preferably C.sub.6-10 aryloxy, such as phenoxy), acyloxy
(preferably C.sub.1-6 acyloxy, such as acetoxy or propionyloxy),
alkylcarbonyl (preferably C.sub.2-7 alkycarbonyl, such as acetyl).
Preferred hydrolysable substituents are halogen, alkoxy groups, and
acyloxy groups. Particularly preferred hydrolysable substituents
are C.sub.1-4 alkoxy groups, especially methoxy and ethoxy.
[0035] The non-hydrolysable substituent R, which may be identical
to or different from one another, may be a non-hydrolysable
substituent R containing a functional group or may be a
non-hydrolysable substituent R without a functional group. In
general formula (I) the substituent R, if present, is preferably a
group without a functional group.
[0036] The non-hydrolysable substituent R without a functional
group is, for example, alkyl (e.g., C.sub.1-8 alkyl, preferably
C.sub.1-6 alkyl, such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, s-butyl and t-butyl, pentyl, hexyl, and octyl), cycloalkyl
(e.g. C.sub.3-8 cycloalkyl, such as cyclopropyl, cyclopentyl or
cyclohexyl), alkenyl (e.g. C.sub.2-6 alkenyl, such as vinyl,
1-propenyl, 2-propenyl and butenyl), alkynyl (e.g. C.sub.2-6
alkynyl, such as acetylenyl and propargyl), cycloalkenyl and
cycloalkynyl (e.g. C.sub.2-6 alkenyl and cycloalkynyl), aryl (e.g.
C.sub.6-10 aryl, such as phenyl and naphthyl), and corresponding
arylalkyl and alkylaryl (e.g. C.sub.7-15 arylalkyl and alkylaryl,
such as benzyl or tolyl). The substituent R may contain one or more
substituents, such as halogen, alkyl, aryl, and alkoxy. In formula
(1) R when present is preferably methyl or ethyl.
[0037] A particular preferred substituent R.sub.f is
CF.sub.3(CF.sub.2).sub.n--Z-- where n and Z are defined as defined
in general formula (4) below.
CF.sub.3 (CF.sub.2).sub.n--Z--SiX.sub.3 (4)
wherein X is as defined in general compound 1 and preferably is
methoxy or ethoxy, Z is a divalent organic group, and n is an
integer from 0 to 20, preferably 3 to 15, more preferably 5 to 10.
Preferably, Z contains not more than 10 carbon atoms and Z is more
preferably a divalent alkylene or alkyleneoxy group having not more
than 6 carbon atoms, such as methylene, ethylene, propylene,
butylene, methylenoxy, ethyleneoxy, propylenoxy, and butylenoxy.
Most preferred is ethylene. Specific examples are
CF.sub.3CH.sub.2CH.sub.2SiCl.sub.2(CH.sub.3),
CF.sub.3CH.sub.2CH.sub.2SiCl(CH.sub.3).sub.2,
CF.sub.3CH.sub.2CH.sub.2Si(CH.sub.3)(OCH.sub.3).sub.2,
CF.sub.3CH.sub.2CH.sub.2SiX.sub.3,
C.sub.2F.sub.5CH.sub.2CH.sub.2SiX.sub.3,
C.sub.4F.sub.9CH.sub.2CH.sub.2SiX.sub.3,
n-C.sub.6F.sub.13CH.sub.2CH.sub.2SiX.sub.3,
n-C.sub.8F.sub.17CH.sub.2CH.sub.2SiX.sub.3,
n-C.sub.10F.sub.21CH.sub.2CH.sub.2SiX.sub.3, (X.dbd.OCH.sub.3,
OC.sub.2H.sub.5 or Cl);
i-C.sub.3F.sub.7O--CH.sub.2CH.sub.2CH.sub.2--SiCl.sub.2 (CH.sub.3),
n-C.sub.6F.sub.13--CH.sub.2CH.sub.2--SiCl
(OCH.sub.2CH.sub.3).sub.2,
n-C.sub.6F.sub.13--CH.sub.2CH.sub.2--SiCl.sub.2 (CH.sub.3) and
n-C.sub.6F.sub.13--CH.sub.2CH.sub.2--SiCl (CH.sub.3).sub.2.
Particularly preferred are
C.sub.2F.sub.5--C.sub.2H.sub.4--SiX.sub.3,
C.sub.4F.sub.9--C.sub.2H.sub.4--SiX.sub.3,
C.sub.6F.sub.13--C.sub.2H.sub.4--SiX.sub.3,
C.sub.8F.sub.13--C.sub.2H.sub.4--SiX.sub.3,
C.sub.10F.sub.21--C.sub.2H.sub.4--SiX.sub.3 and
C.sub.12F.sub.25--C.sub.2H.sub.4--SiX.sub.3, where X is a methoxy
or ethoxy group.
[0038] Furthermore, the inventors have found that by using at least
two different hydrolysable silanes having a fluorine-containing
group of a different kind unexpectedly improved results are
obtained, especially with regard to liquid repellent properties,
wiping durability, and resistance to chemicals such as recording
liquid. The silanes used preferably differ in the number of
fluorine atoms contained therein or in the length (number of carbon
atoms in the chain) of the fluorine-containing substituent.
[0039] Although the reason for these improvements is not clear, the
fluoroalkyl groups of different length are believed to cause a
structural arrangement of higher density, since the fluoroalkyl
group should take an optimal arrangement in the uppermost surface.
For example, in the case where at least two of
C.sub.6F.sub.13--C.sub.2H.sub.4SiX.sub.3,
C.sub.8F.sub.17--C.sub.2H.sub.4SiX.sub.3, and
C.sub.10F.sub.21--C.sub.2H.sub.4--SiX.sub.3 (X as defined above)
are used together, the high fluorine concentration in the uppermost
surface is represented by fluoroalkyl groups of different length
which results in the named improvements compared to the addition of
a single fluorosilane.
[0040] Moreover, it is suitable to use together different silane
compound from above-mentioned silane compound having
fluorine-containing group, i.e., silane compound not having
fluorine-containing group, as starting materials of condensation
reaction. In that case, adjustment of fluorine content, reaction
control and control of the physical property become easy.
[0041] Although this invention uses together above-mentioned
condensation product and photo-polymerization composition, it is
also suitable for it from a viewpoint of durability to introduce a
polymerizable group into condensation product.
[0042] As polymerizable substituent of hydrolysable silane
compound, radical polymerizable group and cationically
polymerizable group can be used. From a viewpoint of alkali ink
resistance, cationically polymerizable group is desirable here.
[0043] A preferred hydrolysable silane having a cationically
polymerizable group is a compound of general formula (2):
R.sub.cSi(R).sub.bX.sub.(3-b) (2)
wherein R.sub.c is a non-hydrolysable substituent having a
cationically polymerizable group, R is a non-hydrolysable
substituent, X is a hydrolysable substituent, and b is an integer
from 0 to 2.
[0044] As a cationically polymerizable organic group, a cyclic
ether group represented epoxy group and oxetane group, a vinyl
ether group etc. can be used. In the viewpoint of availability and
reaction control, an epoxy group is preferable.
[0045] Specific examples of said substituent Rc are glycidyl or
glycidyloxy C.sub.1-20alkyl, such as .gamma.-glycidylpropyl,
.beta.-glycidoxyethyl, .delta.-glycidoxybutyl,
.epsilon.-glycidoxypentyl, .omega.-glycidoxyhexyl, and
2-(3,4-epoxycyclohexyl)ethyl. The most preferred substituents
R.sub.c are glycidoxypropyl and epoxycyclohexylethyl.
[0046] Specific examples of corresponding silanes are
g-glycidoxypropyltrimethoxysilane (GPTS), g.quadrature.
glycidoxypropyltriethoxysilane (GPTES),
epoxycyclohexylethyltrimethoxysilane, and
epoxycyclohexylethyltriethoxysilane. However, the invention is not
limited to the above-mentioned compounds.
[0047] Furthermore, in addition to the hydrolysable silane
compounds having fluorine-containing group or photo-polymerizable
group, a hydrolysable silane having at least one alkyl substituent,
a silane having at least one aryl substituent, or a silane having
no non-hydrolysable substituent can be used together for
controlling the physical properties of the liquid repellent
layer.
[0048] Preferred further hydrolysable silanes, which may be used in
the present invention are those of general formula (3):
R.sub.aSiX.sub.(4-a) (3)
wherein R is a non-hydrolysable substituent selected from
substituted or unsubstituted alkyl and substituted or unsubstituted
aryl, X is a hydrolysable substituent, and a is an integer from 0
to 3.
[0049] Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
methyltrimethoxysilane, methyltriethoxysilane,
methyltripropoxysilane, ethyltrimethoxysilane, ethyl
triethoxysilane, ethyltripropoxysilane, propyltrimethoxysilane,
propyltriethoxysilane, propyltripropoxysilane,
phenyltrimethoxysilane, phenyltriethoxysilane,
phenyltripropoxysilane, diphenyldimethoxysilane,
diphenyldiethoxysilane, dimethyldimethoxysilane,
dimethyldiethoxysilane, etc. are specifically mentioned. This
invention is not limited to the above-mentioned compound.
[0050] The proportion of the silanes used for preparing the
condensation product is selected according to the application
desired and is within the knowledge of a person skilled in the art
of manufacture of inorganic polycondensates. It has been found that
the hydrolysable silanes having a fluorine-containing group are
appropriately used in amounts in the range from 0.5 to 20% by mole,
preferably 1 to 10% by mole, based on the total amount of
hydrolysable compounds used. Within these ranges a high liquid
repellency as well as a very uniform surface are obtained. The
latter is especially important for photo-curing and/or recording
applications involving irradiation since the surface obtained often
tends to have concave and/or convex forms which affect light
scattering. Thus, the above-mentioned ranges provide highly
repellent, even surfaces which are especially suited for
photo-curing and/or recording applications.
[0051] The proportion between the hydrolysable silane having the
cationically polymerizable group and the further hydrolysable
silane is preferably in the range of 10:1 to 1:10.
[0052] Generally, the condensation product of the above-mentioned
hydrolysable silanes is prepared by hydrolysis and condensation of
said starting compounds in accordance with the sol-gel method,
which is known to those skilled in the art. The sol-gel method
generally comprises the hydrolysis of said hydrolysable silanes,
optionally aided by acid or basic catalysis. The hydrolysed species
will condense at least partially. The hydrolysis and condensation
reactions cause the formation of condensation products having e.g.
hydroxy groups and/or oxo bridges. The hydrolysis/condensation
product may be controlled by appropriately adjusting parameters,
such as e.g. the water content for hydrolysis, temperature, period
of time, pH value, solvent type, and solvent amount, in order to
obtain the condensation degree and viscosity desired.
[0053] Moreover, it is also possible to use a metal alkoxide in
order to catalyse the hydrolysis and to control the degree of
condensation. For said metal alkoxide, the other hydrolysable
compounds defined above may be used, especially an aluminum
alkoxide, a titanium alkoxide, a zirconium alkoxide, and
corresponding complex compounds (e.g. with acetyl acetone as the
complex ligand) are appropriate.
[0054] The composite coating composition further comprises at least
one cationically polymerizable organic resin, which is preferably
cationically photo-polymerizable. Since an organic frame is formed
by cationic polymerization (typically ether bond formation),
re-hydrolysis of a siloxane frame is subdued, and the resistance to
recording liquid (typically alkaline ink) is improved. Meanwhile in
this invention, the inorganic frame of siloxane shows high
mechanical durability against wiping. As a result of coexistence of
the organic frame and inorganic frame, it is surprisingly improved
both of recording liquid resistance and wiping durability.
[0055] The cationically polymerizable resin is preferably a
cationically polymerisable epoxy resin known to those skilled in
the art. The cationically polymerisable resin can also be any other
resin having electron rich nucleophilic groups such as oxetane,
vinylether, vinylaryl or having heteronuclear groups such as
aldehydes, ketones, thioketones, diazoalkanes. Of special interest
are also resins having cationically polymerisable ring groups such
as cyclic ethers, cyclic thioethers, cyclic imines, cyclic esters
(lactone), 1,3-Dioxacycloalkane (ketale), spiroorthoesters or
spiroorthocarbonates.
[0056] The term "cationically polymerizable resin" herein refers to
an organic compound having at least 2 cationically polymerizable
groups including monomers, dimers, oligomers or polymers or
mixtures thereof.
[0057] Accordingly, the cationically polymerizable organic resin
preferably comprises epoxy compounds, such as monomers, dimers,
oligomers, and polymers. The epoxy compound used for the coating
composition is preferably solid-state at room temperature (approx.
20.degree. C.), more preferably it has a melting point of
40.degree. C. or higher.
[0058] Examples of said epoxy compound for the coating composition
are epoxy resins having at least one of the structural units (1)
and (2):
##STR00001##
[0059] Further examples are epoxy resins of the bisphenol type
(e.g. Bisphenol-A-diglycidylether (Araldit GY 266 (Ciba)),
Bisphenol-F-diglycidylether) and epoxy resins of the novolak type,
such as phenol novolak (e.g.
Poly[(phenyl-2,3-epoxypropylether)-.omega.-formaldehyde]) and
cresol novolak as well as cycloaliphatic epoxy resins such as e.g.
4-Vinylcyclohexene-diepoxide,
3,4-Epoxycyclohexane-carboxylic-acid-(3,4-epoxycyclohexylmethylesther)
(UVR 6110, UVR 6128 (Union Carbide)). Additional examples are
Triphenylolmethanetriglycidylether,
N,N-Bis-(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)-aniline and
Bis-{4-[bis-(2,3-epoxypropyl)-amino]-phenyl}methane.
[0060] Concerning the epoxy resin compound, epoxy equivalent is
preferably less than 2000, more preferably less than 1000. If epoxy
equivalent exceeds 2000, the degree of cross-linking decreases in
the curing reaction, and some problems may occur, decline of Tg,
adhesion power to a substrate and ink-resistance etc.
[0061] The coating composition according to the present invention
further contains a cationic initiator. The specific type of the
cationic initiator used may e.g. depend on the type of cationically
polymerizable groups present, the mode of initiation (thermal or
photolytic), the temperature, the type of radiation (in the case of
photolytic initiation) etc.
[0062] Suitable initiators include all common initiator systems,
including cationic photo-initiators, cationic thermal initiators,
and combinations thereof.
[0063] Cationic photo-initiators are preferred. Representative of
cationic initiators that can be used include onium salts, such as
sulfonium, iodonium, carbonium, oxonium, silecenium, dioxolenium,
aryldiazonium, selenonium, ferrocenium and immonium salts, borate
salts and corresponding salts of Lewis acids AlCl.sub.3,
TiCl.sub.4, SnCl.sub.4, compounds containing an imide structure or
a triazine structure, azo compounds, perchloric acid, and
peroxides. As cationic photoinitiators, aromatic sulfonium salts or
aromatic iodonium salts are advantageous in view of sensitivity and
stability.
[0064] A mixing ratio by weight of condensation product and
cationically polymerizable organic resin is preferably 0.001-1:1,
more preferably it is 0.005-0.5:1.
[0065] When the mixing ratio of condensation product is lower, the
liquid repellency of the surface is not sufficient. And when
higher, photo-patterning characteristic and/or adhesion power to a
substrate may decrease.
[0066] Generally, in liquid repellent layer of an ink jet head, it
is desirable that it has a flat surface with little unevenness. The
liquid repellent layer, which has unevenness, shows high liquid
repellency (high advancing contact angle or high static contact
angle) against recording liquid droplet. However when rubbing
liquid repellent layer in wiping operation etc with recording
liquid, recording liquid remains in a concave portion and the
liquid repellency of liquid repellent layer may be spoiled as a
result. This phenomenon is remarkable in the embodiment that
recording liquid contains pigment, i.e., a color material particle,
since the color material particle enters and adheres to the concave
portion. Therefore, as for the surface roughness Ra, which
indicates the unevenness of liquid repellent layer, it is desirable
to be less than 5.0 nm, and it is still more desirable especially
that Ra is less than 1.0 nm.
[0067] In this invention, addition of the condensation product
containing hydrolysable silane compound having fluorine-containing
group leads to lower surface free energy, and flat surface can be
obtained.
[0068] To above-mentioned nozzle forming material, it is also
possible to use various additive agents together for the purpose of
increasing the degree of cross-linking, improvement in
photo-sensitivity, prevention of swelling, improvement of coating
characteristics, improvement of adhesion power to substrate, giving
flexibility, to attain mechanical strength, the higher resistance
against chemicals and so on. For example, above-mentioned photo
cationic initiator can be used with a reducing agent such as copper
(II) trifluoromethanesulfonate, ascorbic acid etc, to attain higher
degree of cross-linking. Moreover, in order to prevent swelling and
size modification of the nozzle part in ink, it is also useful to
add fluorine compound in Japanese Patent Application Laid-Open No.
8-290572. Furthermore, for the purpose of improvement of adhesion
power to substrate, addition of coupling agent (ex. Silane
compounds) is also effective.
[0069] Next, the manufacturing method of an ink-jet head using an
above-mentioned nozzle material will be explained.
[0070] This invention is suitable for the manufacturing method,
which forms a nozzle by pattern-exposure and developing. For
example, it is applied to the method which form precise nozzle
structure with photo lithography technology using photosensitive
material, indicated in Japanese Patent Application Laid-Open Nos.
4-10940 to 4-10942, Japanese Patent Application Laid-Open No.
6-286149, and the Japanese Patent No. 3143307 etc.
[0071] For example, the following methods are mentioned. Namely,
the method of manufacturing ink jet head comprising:
[0072] coating a nozzle material resin on a substrate,
[0073] forming nozzle plate having ink ejection opening by
pattern-exposure and developing of the nozzle material, and
[0074] adhere the nozzle plate on the substrate having ink ejection
pressure generating element.
[0075] Another method of manufacturing ink jet head comprising:
[0076] forming a ink passage pattern with dissoluble resin material
on a substrate having an ink ejection pressure generating
element,
[0077] forming a coating resin later by applying a polymerizable
coating resin of this invention as an ink passage wall on the
dissoluble resin material layer,
[0078] forming an ink ejection opening by removing coating resin
layer above ink ejection pressure generating element,
[0079] dissolving the dissoluble resin material pattern,
wherein the coating resin layer contains condensation product of
hydrolysable silane compound and polymerizable resin
composition.
[0080] Subsequently, it is explained the example of the ink jet
head of this invention.
[0081] FIG. 1 is a perspective view of the substrate 1 having the
ink ejection pressure-generating element 2. FIG. 2 is a 2-2
sectional view of FIG. 1. FIG. 3 is a figure of the substrate
formed ink passage pattern 3 with dissoluble resin material. It is
suitably used a positive type resist, especially a
photo-decomposable positive type resist with a comparatively high
molecular weight, in order to prevent a collapse of the ink passage
pattern during processing of nozzle formation. Subsequently, FIG. 4
shows that the coating resin layer 4 of this invention has arranged
on the ink passage pattern. The coating resin layer is
polymerizable with light or thermal energy, especially cationic
photo-polymerizable. The coating resin layer can be suitably formed
by spin coating, direct coating, etc. Subsequently, an ejection
opening 6 is formed by a pattern exposure through mask 5, as shown
in FIG. 5 and, developed as shown in FIG. 6.
[0082] Subsequently, an ink supply opening 7 is suitably formed to
substrate (FIG. 7), and an ink passage pattern is made to dissolve
(FIG. 8). Finally, if needed, heat-treats is applied, thus the
nozzle material is cured completely, and an ink jet head is
completed.
[0083] The coating resin layer of this invention can be applied to
a substrate two or more times, in order to obtain desired thickness
of coating. In this case, it is indispensable to use
above-mentioned coating resin composition as the most upper layer.
Regarding lower layer, it is also possible to use above-mentioned
coating resin composition and photo-polymerizable resin composition
not containing hydrolysable condensation product.
[0084] In the nozzle manufacturing process of this invention, a
liquid repellent surface is obtained using hydrolysable
condensation product containing fluorine atom, without performing a
liquid repellent process. Since this liquid repellent nature is
obtained at the time of an application and dryness, the liquid
repellent nature inside of ejection outlet and ink passage, which
formed of subsequent exposure and the development process, can be
restrained and does not cause any problem concerning its
performance as ink jet head.
[0085] This invention has the feature that shows liquid repellency
only for the nozzle surface through applying nozzle material on a
substrate. Therefore, the mechanical methods, such as molding,
laser processing and dry etching etc., can be useful also. In that
case, hydrophilic processing is not needed, but it is used
suitably.
[0086] The nozzle material in this invention has reactive group
such as polymerizable and hydrolysable group. Since those reactive
groups remain even after pattern-exposure and developing, curing
reaction can be promoted with additional light exposure or heat
treatment. That additional curing process has positive effect on
performance of the material such as adhesive property, ink
resistance, wiping durability and so on.
EMBODIMENTS
Synthetic Example 1
[0087] Hydrolysable condensation product was prepared according to
the following procedures.
[0088] Glycidylpropyltriethoxysilane 28 g (0.1 mol),
methyltriethoxysilane 18 g (0.1 mol), trideca fluoro-1,
1,2,2-tetrahydroctyltriethoxysilane 6.6 g (0.013 mol, equivalent
for 6 mol % in total amount of the hydrolysable silane compound),
water 17.3 g, and ethanol 37 g was stirred at room temperature,
subsequently refluxed for 24 hours, thus hydrolysable condensation
product was obtained.
[0089] Furthermore, the condensation product was diluted with
2-butanol and ethanol to 20 wt % as nonvolatile content, and the
hydrolysable condensation product was obtained.
Embodiment 1
[0090] An ink jet head was produced according to the procedure
shown in the above-mentioned method in FIGS. 1 to 8.
[0091] At first, the silicone substrate 1 having the electric heat
conversion element as ink ejection pressure generating element 2
was prepared, and the dissoluble resin layer was formed by applying
polymethyl isopropenyl ketone (ODUR-1010, Tokyo Oka Kogyo Kabushiki
Kaisha) by spin coating on the silicone substrate. Subsequently,
after prebaking at 120.degree. C. for 6 minutes, pattern exposure
of ink passage was performed by mask aligner UX3000 (USHIO
Electrical Machinery).
[0092] Exposure time was for 3 minutes, and development was carried
out with methyl isobutyl ketone/xylene=2/1, and rinsed with
xylene.
[0093] Said polymethyl isopropeny ketone is the so-called positive
type resist, which decomposes and becomes soluble to the organic
solvent by UV irradiation. The pattern formed with the dissoluble
resin material was the portion which was not exposed in the case of
pattern exposure, and became the ink supply passage 3 (FIG. 3). In
addition, the thickness of the dissoluble resin material layer
after development was 20 micrometers. Subsequently, A cationic
photo-polymerizable coating resin shown in Table 1 was dissolved in
methyl isobutyl ketone/xylene mixture solvent by 55 wt % as solid
content, and applied on the substrate 1 with ink passage pattern 3
of dissoluble resin material layer by spin coating, and prebaking
was performed at 90.degree. C. for four minutes. The thickness of
the coating resin layer 4 on ink passage pattern was 55 micrometers
after repeating this application and prebaking 3 times (FIG.
4).
TABLE-US-00001 TABLE 1 Composition 1 hydrolysable hydrolysable
condensation 25 parts condensation product of synthetic example
product 1 (20 wt %) Epoxy resin EHPE-3150 (Daicel Chemical) 100
parts Additive 1,4-HFAB (Central Glass) 20 parts photo cationic
SP172, Asahi Denka Industry 5 parts initiator Reducing agent copper
(II) 0.5 parts trifluoromethanesulfonate Silane A187 (Nippon
Unicar) 5 parts coupling agent
1,4-HFAB:(1,4-bis(2-hydroxyhexafluoroisopropyl)benzene)
[0094] Subsequently, pattern exposure of the ink ejection opening
was applied using mask aligner "MPA600 super" made by CANON (FIG.
5).
[0095] Next, the ejection opening pattern 6 was formed through
heating at 90 degrees C. for 4 minutes, developing by methyl
isobutyl ketone (MIBK)/xylene=2/3 and performing a rinse with
isopropyl alcohol. The coating resin layer was cured by the photo
cationic polymerization except the ejection opening pattern, and
the ejection opening pattern which had sharp edge was obtained
(FIG. 6). Subsequently, mask for forming ink supply opening in the
back side of the substrate was arranged suitably, and ink supply
opening 7 was formed by anisotropic etching of silicone substrate
(FIG. 7). The surface of the substrate having the nozzle was
protected by a rubber film during anisotropic etching of silicone.
The rubber protective film was removed after completing anisotropic
etching, and further the dissoluble resin material layer forming
ink passage pattern was decomposed by irradiating UV using said
UX3000 on the whole surface again. Subsequently, the ink passage
pattern 3 dissolved by immersing into methyl lactate for 1 hour
while giving an ultrasonic wave to said substrate. Subsequently, in
order to cure the coating resin layer 4 completely, heat treatment
was performed at 200 degrees C. for 1 hour (FIG. 8). Finally, an
ink jet head was completed by adhering the ink supply member on the
ink supply opening.
Embodiment 2
[0096] An ink jet head was produced like embodiment 1 except for
applying composition 2 shown in Table 2 instead of the composition
1 as underlayer, which application and prebaking were repeated
twice, and as the most upper layer above-mentioned composition 1
was applied.
TABLE-US-00002 TABLE 2 Composition 2 Epoxy resin EHPE-3150, Daicel
Chemical 100 parts Additive 1,4-HFAB, Central Glass 20 parts photo
SP172, Asahi Denka Industry 5 parts cationic initiator Reducing
copper (II) 0.5 parts agent trifluoromethanesulfonate Silane A187,
Nippon Unicar 5 parts coupling agent 1,4-HFAB:(1,4-bis
(2-hydroxyhexafluoroisopropyl)benzene)
Embodiment 3
[0097] An ink jet head was made like embodiment 1, except for using
the composition 3 shown in Table 3 instead of the composition
1.
TABLE-US-00003 TABLE 3 Composition 3 hydrolysable hydrolysable
condensation 5 parts condensation product of synthetic example
product 1 (20 wt %) Epoxy resin EHPE-3150, Daicel Chemical 100
parts Additive 1,4-HFAB, Central Glass 20 parts photo cationic
SP172, Asahi Denka Industry 5 parts initiator Silane A187, Nippon
Unicar 5 parts coupling agent
1,4-HFAB:(1,4-bis(2-hydroxyhexafluoroisopropyl)benzene)
Embodiment 4
[0098] Using the composition 3 shown in Table 3, an ink jet head
was produced completely like embodiment 1, except for an
application and an prebaking were performed only once, and
thickness of the coating resin layer was 20 micrometers of on an
ink passage pattern.
<Evaluation of Printing Quality>
[0099] The obtained ink jet recording head of Embodiments 1 to was
filled up with ink BCI-3Bk (Canon) and printing was carried out.
And the highly quality image was obtained.
<Evaluation of Wiping Durability>
[0100] When printing again after performing wiping operation 30000
times with the HNBR rubber blade while spraying ink for the nozzle
surface of this ink jet head, the same high-quality image as before
wiping could be obtained. Thus wiping durability was proved to be
excellent.
<Preservation Property>
[0101] Furthermore, after this ink jet head was filled up with the
above-mentioned ink, preserved at 60 degrees C. for two months. The
printing quality was the same as before preservation.
<Evaluation of Liquid Repellency>
[0102] Moreover, both values of advancing and receding contact
angle against ink BCI-3Bk for an ink jet head was high. And liquid
repellency was excellent (Table 4).
<Surface Roughness>
[0103] The surface roughness of this ink jet head was measured in
contact mode using scanning probe model microscope JSPM-4210. The
surface roughness is Index Ra was 0.2 to 0.3 nm (it scans on
10-micrometer square), and the surface of this nozzle material was
confirmed to be very flat and smooth (Table 4).
<Elementary Analysis of Surface>
[0104] Furthermore, surface analysis by ESCA (Electron Spectroscopy
for Chemical Analysis) was performed with the measurement angle of
6 degrees by Quantum 2000 (Ulvac-phi).
[0105] When the ratio of four elements of C, O, Si, and F is
measured, it was observed that F atom was arranged on the surface
at higher content than the calculated value 6 atom % (Table 4).
TABLE-US-00004 TABLE 4 (Evaluation result) Embodiment Embodiment
Embodiment Embodiment 1 2 3 4 Printing quality good good good good
(First stage) Printing quality good good good good (after wiping)
Printing quality good good good good (After a preservation)
Advancing 83 83 87 87 contact angle Receding 57 55 63 62 contact
angle Surface 0.3 0.4 0.3 0.2 roughness Ra/nm Surface 32 32 38 38
fluoride atom ratio/atom %
* * * * *