U.S. patent application number 12/562595 was filed with the patent office on 2010-01-14 for actinic ray curable composition, actinic ray curable ink, image formation method employing it, and ink-jet recording apparatus.
This patent application is currently assigned to Konica Minolta Medical & Graphic, Inc.. Invention is credited to Wataru ISHIKAWA.
Application Number | 20100007708 12/562595 |
Document ID | / |
Family ID | 34616584 |
Filed Date | 2010-01-14 |
United States Patent
Application |
20100007708 |
Kind Code |
A1 |
ISHIKAWA; Wataru |
January 14, 2010 |
ACTINIC RAY CURABLE COMPOSITION, ACTINIC RAY CURABLE INK, IMAGE
FORMATION METHOD EMPLOYING IT, AND INK-JET RECORDING APPARATUS
Abstract
The actinic ray curable composition has a radically,
photopolymerizable compound, and a non-reactive compound having a
viscosity at 25.degree. C. of from 0.1 to 20 mPas and a boiling
point of not less than 150.degree. C.
Inventors: |
ISHIKAWA; Wataru; (Tokyo,
JP) |
Correspondence
Address: |
LUCAS & MERCANTI, LLP
475 PARK AVENUE SOUTH, 15TH FLOOR
NEW YORK
NY
10016
US
|
Assignee: |
Konica Minolta Medical &
Graphic, Inc.
Tokyo
JP
|
Family ID: |
34616584 |
Appl. No.: |
12/562595 |
Filed: |
September 18, 2009 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10995400 |
Nov 23, 2004 |
7604343 |
|
|
12562595 |
|
|
|
|
Current U.S.
Class: |
347/93 ; 427/511;
524/853; 524/854; 524/879 |
Current CPC
Class: |
G03F 7/038 20130101;
C09D 11/101 20130101; C08G 65/18 20130101; B41J 2/2103 20130101;
C09D 171/00 20130101 |
Class at
Publication: |
347/93 ; 524/854;
524/853; 524/879; 427/511 |
International
Class: |
B41J 2/17 20060101
B41J002/17; C08L 33/08 20060101 C08L033/08; C08L 33/10 20060101
C08L033/10; C08F 2/46 20060101 C08F002/46 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 28, 2003 |
JP |
2003-398807 |
Claims
1. An actinic ray curable composition comprising: a radically
polymerizable compound as a photopolymerizable compound; and a
non-reactive compound having a viscosity at 25.degree. C. of from
0.1 to 20 mPas and a boiling point of not less than 150.degree.
C.
2. The actinic ray curable composition of claim 1, wherein the
non-reactive compound has a viscosity at 25.degree. C. of from 0.1
to 10 mPas and a boiling point of not less than 200.degree. C.
3. The actinic ray curable composition of claim 1, wherein the
actinic ray curable composition has a viscosity at 25.degree. C. of
from 7 to 40 mPas.
4. An actinic ray curable ink comprising pigment and the actinic
ray curable composition of claim 1.
5. A process of forming an image on a recording sheet employing an
ink-jet recording head, the process comprising the steps of:
ejecting the actinic ray curable ink of claim 4 from the ink-jet
recording head onto the recording sheet to form an image on the
recording sheet; and exposing the image to actinic rays after the
ink has been ejected onto the recording sheet.
6. The process of claim 5 wherein the image is exposed to the
octinic rays between 0.001 seconds and 2.0 seconds after the ink
has been ejected onto the recording sheet.
7. The process of claim 5, wherein the actinic ray curable ink is
ejected as ink droplets from each nozzle of the ink-jet recording
head, wherein the ink droplets have a volume of from 2 to 15
pl.
8. An ink-jet recording apparatus used in the process of claim 5,
wherein the actinic ray curable ink and the ink-jet recording head
was heated to a temperature of from 35 to 100.degree. C., and then
the heated ink was ejected.
9. An ink-jet recording apparatus used in the process of claim 5,
wherein the actinic ray curable ink was ejected to a recording
sheet heated to a temperature of from 35 to 60.degree. C.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Divisional of U.S. patent application
Ser. No. 10/995,400 filed Nov. 23, 2004, now U.S. Pat. No. ______,
which claimed the priority of JP 2003-398807 filed Nov. 28, 2003,
the priority of both applications are claimed and both applications
are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to an actinic ray curable
composition, and particularly to an actinic ray curable ink with a
low viscosity, which is capable of being cured with high speed, and
forms an ink layer which is high in hardness and in adhesion to a
recording sheet, an image formation method employing it, and an
ink-jet recording apparatus.
BACKGROUND OF THE INVENTION
[0003] A curable composition capable of being cured by actinic rays
such as ultraviolet rays or electron beams or heat has been applied
to various fields, for example, coating materials for plastics,
paper, or wood work; adhesives; printing inks, printed circuit
boards, or electrical insulations.
[0004] In recent years, particularly a curable composition for
printing inks, coating materials or adhesives is required to have
higher weather resistance and higher adhesion to a substrate. As
ink-jet ink employing such a curable composition, there is a
UV-curable ink.
[0005] The UV-curable ink has been noted recently in respect to
relatively low odor, rapid drying property, and capability of
recording on a recording medium having no ink absorption.
UV-curable ink jet inks are disclosed, for example, in Japanese
Patent O.P.I. Publication No. 6-20204 and Japanese Patent
Publication No 2000-504778. UV-curable inks are required which have
a low viscosity, and provide an ink layer with high fastness, high
flexibility, and high adhesion to a recording sheets. Curing speed
of these UV-curable ink jet inks is likely to change due to kinds
of recording sheets, or operating conditions.
[0006] An ink composition containing a radically polymerizable
compound is susceptible to oxygen. Therefore, when such ink
composition is used in a small amount as ink droplets, curing is
likely to be inhibited. Inks employing a cationically polymerizable
compound, disclosed in Japanese Patent O.P.I. Publication Nos.
2001-220526, 2002-188025, 2002-317139, and 2003-55449), are not
affected by oxygen, however, they have problem in that the
polymerization reaction is susceptible to moisture in the molecular
level (or humidity)
SUMMARY OF THE INVENTION
[0007] The present invention has been made in view of the above. An
object of the invention is to provide an actinic ray curable
composition with a low viscosity, which is capable of being cured
with high speed, and forms a coating layer with high hardness under
various operating conditions, an actinic ray curable ink employing
it, an image formation method employing it, and an ink-jet
recording apparatus employing it.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 shows a schematic view of one embodiment of the
structure of the main section of the ink-jet recording apparatus of
the invention.
[0009] FIG. 2 shows a schematic view of another embodiment of the
structure of the main section of the ink-jet recording apparatus of
the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The above object of the present invention can be achieved by
the following:
[0011] 1. An actinic ray curable composition comprising, as a
photopolymerizable compound, both an oxetane compound with an
oxetane ring and an epoxy compound, and a non-reactive compound
having a viscosity at 25.degree. C. of from 0.1 to 20 mPas and a
boiling point of not less than 150.degree. C.
[0012] 2. The actinic ray curable composition of item 1 above,
wherein the non-reactive compound has a viscosity at 25.degree. C.
of from 0.1 to 10 mPas and a boiling point of not less than
200.degree. C.
[0013] 3. The actinic ray curable composition of item 1 above,
wherein the content ratio by weight of the oxetane compound to the
epoxy compound is 7:3 to 3:7, and the content of the non-reactive
compound is from 1 to 50% by weight.
[0014] 4. The actinic ray curable composition of item 1 above,
wherein the oxetane compound is an oxetane compound with an oxetane
ring having a substituent at the 2-position.
[0015] 5. The actinic ray curable composition of item 1 above,
wherein the epoxy compound is an epoxidated fatty acid ester.
[0016] 6. The actinic ray curable composition of item 5 above,
wherein the epoxidated fatty acid ester is an epoxidated
glyceride.
[0017] 7. The actinic ray curable composition of item 1 above,
wherein the epoxy compound is an alicyclic epoxy compound.
[0018] 8. The actinic ray curable composition of item 7 above,
wherein the alicyclic epoxy compound is an alicyclic compound
represented by the following formula A:
##STR00001##
wherein R.sub.100 represents a substituent; m0 represents an
integer of from 0 to 2; r0 represents an integer of from 1 to 3;
and L.sub.0 represents a single bond or a (r0+1)-valent linkage
group having a carbon atom number of from 1 to 15, which may
contain an oxygen atom or a sulfur atom in the main chain.
[0019] 9. The actinic ray curable composition of item 7 above,
wherein the alicyclic epoxy compound is an alicyclic compound
represented by the following formula I or II:
##STR00002##
wherein R.sub.101 represents a substituent; m1 represents an
integer of from 0 to 2; r1 represents an integer of from 1 to 3;
and L.sub.1 represents a single bond or a (r1+1)-valent linkage
group having a carbon atom number of from 1 to 15, which may
contain an oxygen atom or a sulfur atom in the main chain,
##STR00003##
wherein R.sub.102 represents a substituent; m2 represents an
integer of from 0 to 2; r2 represents an integer of from 1 to 3;
and L.sub.2 represents a single bond or a (r2+1)-valent linkage
group having a carbon atom number of from 1 to 15, which may
contain an oxygen atom or a sulfur atom in the main chain.
[0020] 10. The actinic ray curable composition of item 7 above,
wherein the alicyclic epoxy compound is an alicyclic compound
represented by the following formula III or IV:
##STR00004##
wherein R.sub.200 represents an aliphatic group; m3 represents an
integer of from 0 to 2; X.sub.1 represents --(CH.sub.2).sub.n0-- or
--(O).sub.n0--, in which n0 represents an integer of 0 or 1; p1 and
q1 independently represent 0 or 1, provided that p1 and q1 are not
simultaneously 0; r3 represents an integer of from 1 to 3; and
L.sub.3 represents a single bond or a (r3+1)-valent linkage group
having a carbon atom number of from 1 to 15, which may contain an
oxygen atom or a sulfur atom in the main chain,
##STR00005##
wherein R.sub.201 represents an aliphatic group; m4 represents an
integer of from 0 to 2; X.sub.2 represents --(CH.sub.2).sub.n1-- or
--(O).sub.n1--, in which n1 represents an integer of 0 or 1; p2 and
q2 independently represent 0 or 1, provided that p2 and q2 are not
simultaneously 0; r4 represents an integer of from 1 to 3; and
L.sub.4 represents a single bond or a (r4+1)-valent linkage group
having a carbon atom number of from 1 to 15, which may contain an
oxygen atom or a sulfur atom in the main chain.
[0021] 11. The actinic ray curable composition of item 1 above,
wherein the actinic ray curable composition has a viscosity at
25.degree. C. of from 7 to 40 mPas.
[0022] 12. An actinic ray curable composition comprising a
radically polymerizable compound as a photopolymerizable compound,
and a non-reactive compound having a viscosity at 25.degree. C. of
from 0.1 to 20 mPas and a boiling point of not less than
150.degree. C.
[0023] 13. The actinic ray curable composition of item 12 above,
wherein the non-reactive compound has a viscosity at 25.degree. C.
of from 0.1 to 10 mPas and a boiling point of not less than
200.degree. C.
[0024] 14. The actinic ray curable composition of item 12 above,
wherein the actinic ray curable composition has a viscosity at
25.degree. C. of from 7 to 40 mPas.
[0025] 15. An actinic ray curable ink comprising pigment and the
actinic ray curable composition of any one of items 1 through 14
above.
[0026] 16. A process of forming an image on a recording sheet
employing an ink-jet recording head, the process comprising the
steps of ejecting the actinic ray curable ink of item 15 above from
the ink-jet recording head onto the recording sheet to form an
image on the recording sheet, and exposing the image to actinic
rays between 0.001 seconds and 2.0 seconds after the ink has been
ejected onto the recording sheet.
[0027] 17. A process of forming an image on a recording sheet
employing an ink-jet recording head, the process comprising the
steps of ejecting the actinic ray curable ink of item 15 above from
the ink-jet recording head onto the recording sheet to form an
image on the recording sheet, the ink being ejected as ink droplets
from each of nozzles of the ink-jet recording head, wherein the ink
droplets have a volume of from 2 to 15 pl.
[0028] 18. An ink-jet recording apparatus used in the process of
items 16 and 17 above, wherein the actinic ray curable ink and the
ink-jet recording head was heated to a temperature of from 35 to
100.degree. C., and then the heated ink was ejected.
[0029] 19. An ink-jet recording apparatus used in the process of
items 16 and 17 above, wherein the actinic ray curable ink was
ejected to a recording sheet heated to a temperature of from 35 to
60.degree. C.
[0030] 1-1. An actinic ray curable composition comprising a
radically polymerizable compound as a photopolymerizable compound,
and a non-reactive compound having a viscosity at 25.degree. C. of
from 0.1 to 20 mPas and a boiling point of not less than
150.degree. C.
[0031] 1-2. An actinic ray curable composition comprising, as a
photopolymerizable compound, both an oxetane compound with an
oxetane ring and an epoxy compound, and a non-reactive compound
having a viscosity at 25.degree. C. of from 0.1 to 20 mPas and a
boiling point of not less than 150.degree. C.
[0032] 1-3. The actinic ray curable composition of item 1-1 or 1-2
above, wherein the non-reactive compound has a viscosity at
25.degree. C. of from 0.1 to 10 mPas and a boiling point of not
less than 200.degree. C.
[0033] 1-4. The actinic ray curable composition of item 1-2 or 1-3
above, wherein the content ratio by weight of the oxetane compound
to the epoxy compound is 7:3 to 3:7, and the content of the
non-reactive compound is from 1 to 50% by weight.
[0034] 1-5. The actinic ray curable composition of any one of items
1-2 through 1-4 above, wherein the oxetane compound is an oxetane
compound with an oxetane ring having a substituent at the
2-position.
[0035] 1-6. The actinic ray curable composition of any one of items
1-2 through 1-5 above, wherein the epoxy compound is an epoxidated
fatty acid ester or an epoxidated glyceride.
[0036] 1-7. The actinic ray curable composition of any one of items
1-2 through 1-6 above, wherein the epoxy compound is an alicyclic
epoxy compound.
[0037] 1-8. The actinic ray curable composition of item 1-7 above,
wherein the alicyclic epoxy compound is an alicyclic compound
represented by formula A above.
[0038] 1-9. The actinic ray curable composition of item 1-7 above,
wherein the alicyclic epoxy compound is an alicyclic compound
represented by formula I or II above.
[0039] 1-10. The actinic ray curable composition of item 1-7 above,
wherein the alicyclic epoxy compound is an alicyclic compound
represented by formula III or IV above.
[0040] 1-11. The actinic ray curable composition of any one of
items 1-1 through 1-10 above, wherein the actinic ray curable
composition has a viscosity at 25.degree. C. of from 7 to 40
mPas.
[0041] 1-12. An actinic ray curable ink comprising pigment and the
actinic ray curable composition of any one of items 1-1 through
1-11 above.
[0042] 1-13. A process of forming an image on a recording sheet
employing an ink-jet recording head, the process comprising the
steps of ejecting the actinic ray curable ink of item 1-12 above
from the ink-jet recording head onto the recording sheet to form an
image on the recording sheet, and exposing the image to actinic
rays between 0.001 seconds and 2.0 seconds after the ink has been
ejected onto the recording sheet. 1-14. A process of forming an
image on a recording sheet employing an ink-jet recording head, the
process comprising the steps of ejecting the actinic ray curable
ink of item 1-12 above from the ink-jet recording head onto the
recording sheet to form an image on the recording sheet, the ink
being ejected as ink droplets from each of nozzles of the ink-jet
recording head, wherein the ink droplets have a volume of from 2 to
15 pl.
[0043] 1-15. An ink-jet recording apparatus used in the process of
item 1-13 or 1-14 above, wherein the actinic ray curable ink and
the ink-jet recording head was heated to a temperature of from 35
to 100.degree. C., and then the heated ink was ejected.
[0044] 1-16. An ink-jet recording apparatus used in the process of
item 1-13 or 1-14 above, wherein the actinic ray curable ink was
ejected to a recording sheet heated to a temperature of from 35 to
60.degree. C.
[0045] The present invention will be detailed below.
[Actinic Ray]
[0046] In the ink-jet ink recording method in the invention,
ink-jet ink is ejected onto a recording medium (or material), and
the ejected ink is cured by actinic ray exposure. Kinds of the
actinic ray are not specifically limited. As actinic ray, visible
or ultraviolet light or electron beam can be used, and ultraviolet
light is preferably used. When ultraviolet light is used, exposure
amount is preferably from 100 to 10,000 mJ/cm.sup.2, and preferably
from 500 to 5,000 mJ/cm.sup.2. This range of exposure amount is
advantageous in providing sufficient curing of ink and preventing a
colorant from fading. Examples of an ultraviolet ray include a
metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical
lamp, a low pressure mercury lamp, and a high pressure mercury
lamp. An H lamp, D lamp and V lamp (all available from Fusion
System Co., Ltd.) are also used.
[0047] Unlike the high pressure mercury lamp (having an emission
wavelength of 365 nm as a main wavelength), the metal halide lamp
has a continuous emission spectra, a high emission efficiency at
the wavelength regions of from 200 to 450 nm, and rich longer
wavelength light. Accordingly, as the ultraviolet ray lamp, the
metal halide lamp is preferred in the invention.
[Non-Reactive Compound]
[0048] The non-reactive compound in the invention (hereinafter also
referred to simply as the non-reactive compound) is a compound
having a viscosity at 25.degree. C. of from 0.1 to 20 mPas and a
boiling point of not less than 150.degree. C., which does not react
with the photopolymerizable compound in the invention. The
non-reactive compound in the invention has a viscosity at
25.degree. C. of preferably from 0.1 to 10 mPas and a boiling point
of preferably from 150 to 200.degree. C.
[0049] As kinds of the non-reactive compound in the invention,
there are aromatic hydrocarbon compounds, halogenated hydrocarbons,
esters, ketones, and ethers. The content of the non-reactive
compound in the invention in the actinic ray curable composition is
preferably from 1 to 50% by weight, and more preferably from 2 to
20% by weight.
[0050] Examples of the non-reactive compound include methyl
acetoacetate (bp. 172.degree. C., viscosity: 1.6 mPas),
3-methyl-3-methoxybutyl acetate (bp. 188.degree. C., viscosity: 1.7
mPas), cyclohexanone (bp. 156.degree. C., viscosity: 2.0 mPas),
ethyl lactate (bp. 155.degree. C., viscosity: 2.4 mPas), methyl
2-methyllactate (bp. 137.degree. C., viscosity: 2.6 mPas),
propylene glycol mono-n-butyl ether (bp. 170.degree. C., viscosity:
2.9 mPas), diacetone alcohol (bp. 168.degree. C., viscosity: 3.0
mPas), butyl lactate (bp 188.degree. C., viscosity: 3.3 mPas),
diethylene glycol monomethyl ether (bp. 194.degree. C., viscosity:
3.5 mPas), and dipropylene glycol monomethyl ether (bp. 188.degree.
C., viscosity: 3.5 mPas).
[Radically Polymerizable Compound]
[0051] The radically polymerizable compound in the invention is a
compound having an ethylenically unsaturated bond capable of being
radically polymerized, and may be any as long as it has in the
molecule at least one ethylenically unsaturated bond which enables
radical polymerization. The radically polymerizable compound may be
in the form of monomer, oligomer or polymer. The radically
polymerizable compound may be used alone or as a mixture of two or
more kinds thereof, according to the object.
[0052] As the radically polymerizable compound in the invention,
there are unsaturated carboxylic acids such as acrylic acid, meth
acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and
maleic acid; and salts, esters, urethanes, amides, and anhydrides
each derived therefrom; acrylonitrile; styrene; various unsaturated
polyesters; various unsaturated polyethers; various unsaturated
polyamides; and various unsaturated polyurethanes.
[0053] Typical examples of the radically polymerizable compound
include an acrylic acid derivative such as 2-ethylhexyl acrylate,
2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate,
cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate,
bis(4-acryloxypolyethoxyphenyl)propane, neopentyl glycol
diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate,
diethylene glycol diacrylate, triethylene glycol diacrylate,
tetraethylene glycol diacrylate, polyethylene glycol diacrylate,
polypropylene glycol diacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate,
trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate,
oligo ester acrylate, N-methylol acryl amide, diacetone acryl
amide, or epoxy acrylate; a methacrylic acid derivative such as
methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl
methacrylate, lauryl methacrylate, allyl methacrylate, glycidyl
methacrylate, benzyl methacrylate, dimethylaminomethyl
methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol
dimethacrylate, triethylene glycol dimethacrylate, polyethylene
glycol dimethacrylate, polypropylene glycol dimethacrylate,
trimethylolethane trimethacrylate, trimethylolpropane
trimethacrylate, or
2,2-bis(4-methacryloxy-polyethoxyphenyl)propane; an allyl compound
such as alltl glycidyl ether, diallyl phthalate or triallyl
trimellitate; and radical polymerizable or crosslinkable monomers,
oligomers or polymers described in S. Yamashita et al.,
"Crosslinking agent Handbook", Taisei Co., Ltd. (1981), K. Kato et
al., "UV, EB Hardenable Handbook (Materials)", Kobunshi Kankokai
(1985), Radotek Kenkyukai, "UV, EB Hardening Technology,
Application and Market", pp. 79, CMC Co. Ltd. (1989), and E.
Takiyama, "Polyester Resin Handbook", Nikkan Kyogyo Shinbunsha
(1988). The content of the radical polymerizable compound in the
actinic ray curable composition is preferably from 1 to 97% by
weight, and more preferably from 30 to 95% by weight.
[0054] As radical polymerization initiators, there are a triazine
derivative disclosed in Japanese Patent Publication Nos. 591281 and
61-9621 and Japanese Patent O.P.I. Publication No. 60-60104; an
organic peroxide compound disclosed in Japanese Patent O.P.I.
Publication Nos. 59-1504 and 61-243807; a diazonium compound in
Japanese Patent Publication Nos. 43-23684, 44-6413, 47-1604 and
U.S. Pat. No. 3,567,453; an organic azide compound disclosed in
U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853;
orthoquinondiazide compounds disclosed in Japanese Patent
Publication Nos. 36-22062b, 37-13109, 38-18015 and 45-9610; various
onium compounds disclosed in Japanese Patent Publication No.
55-39162, Japanese Patent O.P.I. Publication No. 59-14023 and
"Macromolecules", Volume 10, p. 1307 (1977); azo compounds
disclosed in Japanese Patent Publication No. 59-142205; metal arene
complexes disclosed in Japanese Patent O.P.I. Publication No.
1-54440, European Patent Nos. 109,851 and 126,712, and "Journal of
Imaging Science", Volume 30, p. 174 (1986); (oxo) sulfonium
organoboron complexes disclosed in Japanese Patent O.P.I.
Publication Nos. 5-213861 and 5-255347; titanocenes disclosed in
Japanese Patent O.P.I. Publication Nos. 59-152396 and 61-151197;
transition metal complexes containing a transition metal such as
ruthenium disclosed in "Coordination Chemistry Review", Volume 84,
p. 85-277 (1988) and Japanese Patent O.P.I. Publication No.
2-182701; 2,4,5-triarylimidazol dimmer disclosed in Japanese Patent
O.P.I. Publication No. 3-209477; carbon tetrabromide; and organic
halide compounds disclosed in Japanese Patent O.P.I. Publication
No. 59-107344.
[Oxetane Compound/Oxetane Compound]
[0055] The actinic ray curable composition of the invention
preferably contains, as a photopolymerizable compound, an oxetane
compound with an oxetane ring. The compound with an oxetane ring is
preferably an oxetane compound with an oxetane ring having a
substituent at the 2-position.
[0056] The oxetane compound preferably used in the invention will
be explained below.
(Oxetane Compound With an Oxetane Ring Having a Substituent at the
2-Position)
[0057] In the invention, an oxetane compound with an oxetane ring
represented by formula 1 having a substituent at the 2-position is
preferably used.
##STR00006##
[0058] In formula 1, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
and R.sub.6 independently represent a hydrogen atom or a
substituent. At least one of R.sub.3 through R.sub.6 is preferably
a substituent.
[0059] In formula 1, examples of the substituent represented by
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 include a
fluorine atom, an alkyl group having from 1 to 6 carbon atoms (for
example, a methyl group, an ethyl group, a propyl group, a butyl
group, etc.), a fluoroalkyl group having from 1 to 6 carbon atoms,
an allyl group, an aryl group (for example, a phenyl group, a
naphthyl group, etc.), a furyl group and a thienyl group. These
substituents may have further have the substituent.
(Oxetane Compound With One Oxetane Ring in the Molecule)
[0060] Among the above oxetane compounds, an oxetane compound with
an oxetane ring represented by the following formula 2, 3, 4, or 5
is preferred.
##STR00007##
[0061] In formulae 2 through 5 above, R.sub.1 through R.sub.6
independently represent a hydrogen atom or a substituent, R.sub.7
and R.sub.8 independently represent a substituent, and Z represents
an oxygen atom, a sulfur atom, a divalent hydrocarbon group or a
divalent hydrocarbon group in which an oxygen atom or a sulfur atom
is intervened.
[0062] In formulae 2 through 5 above, the substituent represented
by R.sub.1 through R.sub.6 is the same as those denoted in R.sub.1
through R.sub.6 of formula 1.
[0063] In the formula 2 through 5, R.sub.7 and R.sub.8
independently represent an alkyl group having from 1 to 6 carbon
atoms (for example, a methyl group, an ethyl group, a propyl group,
a butyl group, etc.), an alkenyl group having from 1 to 6 carbon
atoms (a 1-propenyl group, a 2-propenyl group, a
2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-butenyl
group, a 2-butenyl group, a 3-butenyl group, etc.), an aryl group
(for example, a phenyl group, a naphthyl group, etc.), an aralkyl
group (for example, a benzyl group, a fluorobenzyl group, a
methoxybenzyl group), an acyl group having from 1 to 6 carbon atoms
(a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl
group, etc.), an alkoxycarbonyl group having from 1 to 6 carbon
carbons (for example, an ethoxycarbonyl group, a propoxycarbonyl
group, a butoxycarbonyl group, etc.), an alkylcarbamoyl group
having from 1 to 6 carbon atoms (for example, a propylcarbamoyl
group, a butylpentylcarbamoyl group, etc.), and an alkoxycarbamoyl
group (for example, an ethoxycarbamoyl group, etc.).
[0064] In formulae 2 through 5, the divalent hydrocarbon group
represented by Z is an alkylene group (for example, an ethylene
group, a trimethylene group, a tetramethylene group, a propylene
group, an ethylethylene group, a pentamethylene group, a
hexamethylene group, a heptamethylene group, an octamethylene
group, a nonamethylene group, a decamethylene group, etc.), an
alkenylene group (for example, a vinylene group, a propenylene
group, etc.), an alkinylene group (an ethynylene group, or
3-pentynylene group, etc.). The divalent hydrocarbon group
represented by Z in which an oxygen atom or a sulfur atom is
intervened is the alkylene group, alkenylene group, or alkynylene
group described above each having an oxygen atom or a sulfur atom
intervened therein.
[0065] It is preferred in formulae 2 through 5 that R.sub.1 is a
lower alkyl group, and particularly an ethyl group, R.sub.7 and
R.sub.8 are independently a propyl group, a phenyl group or a
benzyl group, and Z is the divalent hydrocarbon group,
particularly, an alkylene group, an alkenylene group, or an
alkynylene group.
(Oxetane Compound With Two or More Oxetane Rings in the
Molecule)
[0066] In the invention, an oxetane compound with two or more of an
oxetane ring represented by the following formula 6 or 7 in the
molecule can be used.
##STR00008##
[0067] In formulae 6 and 7 above, m is 2, 3, or 4, and Z is the
same as those denoted in Z of formulae 2 through 5. R.sub.1 through
R.sub.6 independently represent a hydrogen atom, a fluorine atom,
an alkyl group having a carbon atom number of from 1 to 6 such as a
methyl group, an ethyl group, a propyl group or a butyl group, a
fluoroalkyl group having a carbon atom number of from 1 to 6, an
allyl group, an aryl group, or a furyl group. In formula 6, it is
preferred that at least one of R.sub.3 through R.sub.6 is a
substituent.
[0068] R.sub.9 represents a straight chain or branched chain
alkylene group having from 1 to 12 carbon atoms, a straight chain
or branched chain poly(alkylene oxy) group, or a divalent group
selected from the group consisting of the following formula 9, 10
and 11.
[0069] The straight chain or branched chain alkylene group having
from 1 to 12 carbon atoms is preferably a group represented by the
following formula 8.
##STR00009##
[0070] In formula 8, R.sub.10 represents a lower alkyl group such
as a methyl group, an ethyl group, or propyl group.
##STR00010##
[0071] In the formula 9, "n" represents an integer of from 0 to
2000, R.sub.12 represents an alkyl group having from 1 to 10 carbon
atoms (for example, a methyl group, an ethyl group, a propyl group,
a butyl group, a pentyl group, a hexyl group, a heptyl group, an
octyl group, a nonyl group, etc.), and R.sub.11 represents an alkyl
group having from 1 to 10 carbon atoms (for example, a methyl
group, an ethyl group, a propyl group, a butyl group, a pentyl
group, a hexyl group, a heptyl group, an octyl group, a nonyl
group, etc.), or a group represented by the following formula
12.
##STR00011##
[0072] In the formula 12, "j" represents an integer of from 0 to
100. R.sub.13 represents an alkyl group having from 1 to 10 carbon
atoms (for example, a methyl group, an ethyl group, a propyl group,
a butyl group, a pentyl group, a hexyl group, a heptyl group, an
octyl group, a nonyl group, etc.).
##STR00012##
[0073] In the formula 10, R.sub.14 represents an alkyl group having
from 1 to 10 carbon atoms (for example, a methyl group, an ethyl
group, a propyl group, a butyl group, a pentyl group, a hexyl
group, a heptyl group, an octyl group, a nonyl group, etc.), an
alkoxy group having from 1 to 10 carbon atoms (for example, a
methoxy group, an ethoxy group, a propoxy group, a butoxy group, a
pentoxy group, etc.), a halogen atom (for example, a fluorine atom,
a chlorine atom, a bromine atom, a iodine atom, etc.), a nitro
group, a cyano group, a mercapto group, an alkoxycarbonyl group
(for example, a methyloxycarbonyl group, an ethyloxycarbonyl group,
a butyloxycarbonyl group, etc.), or a carboxyl group.
##STR00013##
[0074] In the formula 10, R.sub.15 represents an oxygen atom, a
sulfur atom, --NH--, --SO--, --SO.sub.2, --(CH.sub.2)--,
--C(CH.sub.3).sub.2-- or --(CF.sub.3).sub.2--.
[0075] A preferred partial structure in the molecule of the oxetane
compound with an oxetane ring used in the invention will be
explained below.
[0076] In formula 6 or 7, R.sub.1 is preferably a lower alkyl group
such as a methyl group, an ethyl group, or a propyl group, and more
preferably an ethyl group. R.sub.9 is preferably a hexamethylene
group or one in which R.sub.14 in formula 10 above is a hydrogen
atom.
[0077] In formula 8 above, R.sub.10 is preferably an ethyl group,
and in formulae 9 and 12 above, R.sub.12 and R.sub.13 each are
preferably hydrogen atoms. In formula 6 above, it is preferred that
at least one of R.sub.3 through R.sub.6 is a substituent.
[0078] Further, as one of preferred embodiments of the oxetane
compound with an oxetane ring in the molecule, there is a compound
represented by the following formula 13.
##STR00014##
[0079] In the formula 13, r is an integer of from 25 to 200,
R.sub.16 represents an alkyl group having from 1 to 4 carbon atoms
or a trialkylsilyl group. R.sub.1 and R.sub.4 through R.sub.6 are
the same as those denoted in formula 1. it is preferred that at
least one of R.sub.3 through R.sub.6 is a substituent.
[0080] Exemplified compounds 1 through 15 will be listed below as
examples of the oxetane compound with an oxetane ring with a
substituent at the 2-position, but the invention is not limited
thereto. [0081] 1: Trans-3-tert-butyl-2-phenyloxetane [0082] 2:
3,3,4,4-Tetramethyl-2,2-diphenyloxetane [0083] 3: Di[3-ethyl
(2-methoxy-3-oxetanyl)]methyl ether [0084] 4:
1,4-Bis(2,3,4,4-tetramethyl-3-ethyl-oxetanyl)butane [0085] 5:
1,4-Bis(3-methyl-3-ethyloxetanyl)butane [0086] 6:
Di(3,4,4-trimethyl-3-ethyloxetanyl)butane [0087] 7:
3-(2-Ethylhexyloxymethyl)-2,2,3,4-tetramethyloxetane [0088] 8:
2-(2-Ethylhexyloxy)-2,3,3,4,4-pentamethyloxetane [0089] 9:
4,4'-Bis[(2,4-dimethyl-3-ethyl-3-oxetanyl)-methoxy]biphenyl [0090]
10: 1,7-Bis (2,3,3,4,4-pentamethyloxatanylheptane) [0091] 11:
Oxetanyl [0092] 12: 2-methoxy-3,3-dimethyloxatane [0093] 13:
2,2,3,3-Tetramethyloxatane [0094] 14:
2-(4-Methoxyphenyl)-3,3-dimethyloxetane [0095] 15:
Di(2-(4-methoxyphenyl)-3-3-methyloxetane-3-yl)-ether
[0096] The oxetane compound with an oxetane ring with a substituent
at the 2-position can be synthesized according to the procedures
disclosed in the following literatures. [0097] (1) Hu Xianming,
Richard M. Kellogg, Synthesis, 533-538, May (1955). [0098] (2) A.
O. Fitton, J. Hill, D. Ejane, R. Miller, Synth., 12, 1140 (1987).
[0099] (3) Toshiro Imai and Sinya Nishida, Can. J. Chem. Vol. 59,
2503-2509 (1981). [0100] (4) Nobujiro Shimizu, Shintaro Yamaoka,
and Yuho Tsuno, Bull. Chem. Soc. Jpn., 56, 3853-3854 (1983). [0101]
(5) Walter Fisher and Cyril A. Grob, Helv. Chim. Acta., 61, 2336
(1978). [0102] (6) Chem. Ber., 101, 1850 (1968). [0103] (7)
"Heterocyclic Compounds with Three- and Four-membered Rings", Part
Two, Chapter IX, Interscience Publishers, John Wiley & Sons,
New York (1964). [0104] (8) Bull. Chem. Soc. Jpn., 61, 1653 (1988).
[0105] (9) Pure Appl. Chem., A29 (10), 915 (1992). [0106] (10) Pure
Appl. Chem., A30 (2 & amp; 3), 189 (1993). [0107] (11) Japanese
Patent O.P.I. Publication No. 6-16804 [0108] (12) German Patent No.
1,021,858
[0109] The actinic ray curable ink contains the oxetane compound
with an oxetane ring with a substituent at the 2-position in an
amount of preferably from 1 to 97% by weight, and more preferably
from 30 to 95% by weight.
(Combined Use of the Oxetane Compound With an Oxetane Ring With a
Substituent at the 2-Position and Another Polymerizable
Compound)
[0110] The oxetane compound with an oxetane ring with a substituent
at the 2-position can be used alone or as a mixture of two or more
kinds thereof. Further, the oxetane compound with an oxetane ring
with a substituent at the 2-position can be used in combination
with another polymerizable compound. In combined use thereof it is
preferred that in a mixture the content ratio of the oxetane
compound with an oxetane ring with a substituent at the 2-position
to the polymerizable compound is from 10 to 98% by weight, and that
of the polymerizable compound is from 2 to 90% by weight.
(Oxetane Compound With an Oxetane Ring Having a Substituent Only at
the 3-Position)
[0111] In the invention, in addition to the above-described oxetane
compound with an oxetane ring having a substrate at the 2-position,
a known oxetane compound can be used in combination, and an oxetane
compound with an oxetane ring having a substituent only at the
3-position is preferably used in combination.
[0112] As the oxetane compound with an oxetane ring having a
substituent only at the 3-position, known ones disclosed in
Japanese Patent O.P.I. Publication Nos. 2001-220526 and 2001-310397
can be used.
[0113] As the oxetane compound with an oxetane ring having a
substituent only at the 3-position, there is a compound represented
by the following formula 14.
##STR00015##
[0114] In formula (101), R.sup.1 represents a hydrogen atom, an
alkyl group having from 1 to 6 carbon atoms such as a methyl group,
an ethyl group, a propyl group, a butyl group, etc.; a fluoroalkyl
group having from 1 to 6 carbon atoms; an allyl group; an aryl
group; a furyl group; or a thienyl group; and R.sup.2 represents an
alkyl group having from 1 to 6 carbon atoms such as a methyl group,
an ethyl group, a propyl group, a butyl group, etc.; an alkenyl
group having from 2 to 6 carbon atoms such as a 1-propenyl group, a
2-propenyl group, a 2-methyl-1-propenyl group, a
2-methyl-2-propenyl group, a 1-butenyl group, a 2-butenyl group, a
3-butenyl group, etc.), an aromatic ring-containing group such as a
phenyl group, a benzyl group, a fluorobenzyl group, a methoxybenzyl
group; a phenoxyethyl group, etc.; an alkylcarbonyl group having
from 2 to 6 carbon atoms such as an ethylcarbonyl group, a
propylcarbonyl group, a butylcarbonyl group, etc.; an
alkoxycarbonyl group having from 2 to 6 carbon carbons such as an
ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl
group, etc.; an N-alkylcarbamoyl group having from 2 to 6 carbon
atoms such as an ethylcarbamoyl group, a propylcarbamoyl group, a
butylcarbamoyl group, a pentylcarbamoyl, etc. The oxetane compound
used in the invention is preferably a compound having one oxetane
ring in that the composition containing such a compound is
excellent in tackiness, low in viscosity, and is easy to
handle.
[0115] As one example of an oxetane compound having two oxetane
rings, an oxetane compound represented by the following formula 15
is cited.
##STR00016##
[0116] In formula 15, R.sup.1 represents the same group as those
denoted in R.sub.1 in formula 14; and R.sup.3 represents a straight
chained or branched alkylene group such as an ethylene group, a
propylene group, a butylene group, etc.; a straight chained or
branched polyalkyleneoxy group such as a poly(ethyleneoxy) group, a
poly(propyleneoxy group, etc.; a straight chained or branched
unsaturated hydrocarbon group such a propenylene group, a
methylpropenylene group, a butenylene group, etc.; an alkylene
group containing a carbonyl group; an alkylene group containing a
carbonyloxy group; or an alkylene group containing a carbamoyl
group.
[0117] R.sup.3 also represents a polyvalent group selected from
groups represented by the following formulae 16, 17 and 18.
##STR00017##
[0118] In formula 16, R.sup.4 represents a hydrogen atom, an alkyl
group having from 1 to 4 carbon atoms such as a methyl group, an
ethyl group, a propyl group, a butyl group, etc.; an alkoxy group
having from 1 to 4 carbon atoms such as a methoxy group, an ethoxy
group, a propoxy group, a butoxy group, etc.; a halogen atom such
as a chlorine atom, a bromine atom, etc.; a nitro group; a cyano
group; a mercapto group; a lower alkylcarboxy group; a carboxyl
group; or a carbamoyl group.
##STR00018##
[0119] In formula 17, R.sup.5 represents an oxygen atom, a sulfur
atom, a methylene group, --NH--, --SO--, --SO.sub.2--,
--(CF.sub.3).sub.2--, or --C(CH.sub.3).sub.2--.
##STR00019##
[0120] In formula 18, R.sub.6 represents an alkyl group having from
1 to 4 carbon atoms such as a methyl group, an ethyl group, a
propyl group, a butyl group, etc., or an aryl group; "n" represents
an integer of from 0 to 2000; and R.sup.7 represents an alkyl group
having from 1 to 4 carbon atoms such as a methyl group, an ethyl
group, a propyl group, a butyl group, etc, or an aryl group, or a
group represented by the following formula 19.
##STR00020##
[0121] In formula 19, R.sup.8 represents an alkyl group having from
1 to 4 carbon atoms such as a methyl group, an ethyl group, a
propyl group, a butyl group, etc., or an aryl group; and m
represents an integer of from 0 to 100.
[0122] Examples of a compound having two oxetane rings include the
following compounds.
Exemplified Compound 1
##STR00021##
[0123] Exemplified Compound 2
##STR00022##
[0125] Exemplified compound 1 is a compound in which in formula 15,
R.sup.1 is an ethyl group, and R.sup.3 is a carbonyl group.
Exemplified compound 2 is a compound in which in formula 15,
R.sup.1 is an ethyl group, and R.sup.3 is a group in which in
formula 18, R.sup.6 is a methyl group, R.sup.7 is a methyl group,
and n is 1.
[0126] As another example of an oxetane compound having two oxetane
rings, an oxetane compound represented by the following formula 20
is cited. In formula 20, R.sup.1 is the same as those denoted in
R.sup.1 of formula 14 above.
##STR00023##
[0127] As an example or an oxetane compound having three or four
oxetane rings, an oxetane compound represented by the following
formula 21 is cited.
##STR00024##
[0128] In formula 21, R.sup.1 is the same as those denoted in
R.sup.1 of formula 14; R.sup.9 represents a branched alkylene group
having 1 to 12 carbon atoms such as a group represented by formula
A, B or C below, a branched polyalkyleneoxy group such as a group
represented by formula D below, or a branched alkylene group
containing a silylether group such as a group represented by E
below; and j represents an integer of 3 or 4.
##STR00025##
[0129] In formula A, R.sup.10 represents a lower alkyl group such
as a methyl group, an ethyl group, or a propyl group. In formula D,
p represents an integer of from 1 to 10.
[0130] As an example of an oxetane compound having four oxetane
rings. Exemplified compound 3 below is cited.
Exemplified Compound 3
##STR00026##
[0132] As a compound having 1 to 4 oxetane rings other than the
compounds described above, a compound represented by formula 22
below is cited.
##STR00027##
[0133] In formula 22, R.sup.8 is the same as those denoted in
R.sup.8 of formula 19; R.sup.11 represents an alkyl group having 1
to 4 carbon atoms such as a methyl group, an ethyl group, a propyl
group or a butyl group, or a trialkylsilyl group; r represents an
integer of from 1 to 4, and R.sup.1 is the same as those denoted in
R.sup.1 of formula 14.
[0134] The preferred oxetane compounds used in the invention are
Exemplified compounds 4, 5, and 5 as shown below.
Exemplified Compound 4
##STR00028##
[0135] Exemplified Compound 5
##STR00029##
[0136] Exemplified Compound 6
##STR00030##
[0138] Synthetic method of the above-described oxetane compounds is
not specifically limited, and known methods can be used. There is,
for example, a method disclosed in D. B. Pattison, J. Am. Chem.
Soc., 3455, 79 (1957) in which an oxetane ring is synthesized from
diols.
[0139] Besides the above-described oxetane compounds, polymeric
oxetane compounds having 1 to 4 oxetane rings with a molecular
weight of 1000 to 5000 can be used. Examples thereof include the
following exemplified compounds 7, 8 and 9.
Exemplified Compound 7
##STR00031##
[0140] Exemplified Compound 8
##STR00032##
[0141] Exemplified Compound 9
##STR00033##
[0143] The content of the oxetane compound in the actinic ray
curable composition of the invention is preferably from 1 to 97% by
weight, and more preferably from 30 to 95% by weight.
(Epoxy Compound)
[0144] The epoxy compound herein referred to is a compound with an
oxirane ring (hereinafter referred to simply as the epoxy
compound). As the epoxy compound, there are known epoxy compounds,
for example, an aromatic epoxy compound (aromatic epoxide), an
alicyclic epoxy compound (alicyclic epoxide), and an aliphatic
epoxy compound (aliphatic epoxide). The epoxy compound has
preferably a low molecular weight, and more preferably a molecular
weight less than 1000.
[0145] The content of the alicyclic epoxy compound in the actinic
ray curable composition of the invention is preferably from 10 to
80% by weight.
[0146] The aromatic epoxide is preferably a di- or poly-glycidyl
ether manufactured by a reaction of polyhydric phenol having at
least one aromatic ring or of an alkylene oxide adduct thereof with
epichlorohydrin, and includes, for example, such as di- or
poly-glycidyl ether of bisphenol A or of an alkylene oxide adduct
thereof, di- or poly-glycidyl ether of hydrogenated bisphenol A or
of an alkylene oxide adduct thereof and novolac type epoxy resin.
Herein, alkylene oxide includes such as ethylene oxide and
propylene oxide.
[0147] The alicyclic epoxide is preferably a compound containing
cyclohexene oxide or cyclopentene oxide obtained by epoxydizing a
compound having at least one cycloalkane ring such as cyclohexene
or cyclopentene by use of a suitable oxidizing agent such as
hydrogen peroxide or a peracid. Examples thereof include compounds
described later.
[0148] The aliphatic epoxide is preferably a di- or polyglycidyl
ether of aliphatic polyhydric alcohol or of an alkylene oxide
adduct thereof; the typical examples include diglycidyl ether of
alkylene glycol, such as diglycidyl ether of ethylene glycol,
diglycidyl ether of propylene glycol and diglycidyl ether of
1,6-hexane dial; polyglycidyl ether of polyhydric alcohol such as
di- or triglycidyl ether of glycerin or of an alkylene oxide adduct
thereof; and diglycidyl ether of polyalkylene glycol such as
diglycidyl ether of polyethylene glycol or of an alkylene oxide
adduct thereof and diglycidyl ether of polypropylene glycol or of
an alkylene oxide adduct thereof. Herein, alkylene oxide includes
such as ethylene oxide and propylene oxide.
[0149] Besides the compounds above, a monoglycidyl ether of higher
alcohols, phenol or cresol, which is a monomer having one oxirane
ring in the molecule, can be used. Among these epoxides above, the
aromatic epoxide and alicyclic epoxide are preferable, and the
alicyclic epoxide is specifically preferable, taking a quick curing
property in consideration. In the invention, the epoxides described
above may be utilized alone or as a mixture of two or more kinds
thereof.
[0150] As the alicyclic epoxide, an alicyclic epoxide represented
by formula A, I, or II above is preferred, which will be explained
below.
[0151] In formula A, I or II above, R.sub.100, R.sub.101, and
R.sub.102 independently represent a substituent. Examples of the
substituent include a halogen atom (for example, a fluorine atom, a
chlorine atom, a bromine atom, a iodine atom, etc.), an alkyl group
having a carbon atom number of from 1 to 6 (for example, a methyl
group, an ethyl group, a propyl group, an isopropyl group, or a
butyl group); an alkoxy group having from 1 to 6 carbon atoms (for
example, a methoxy group, an ethoxy group, a propoxy group, an
isopropoxy group, an n-butoxy group, a tert-butoxy group), an acyl
group (for example, an acetyl group, a propionyl group or a
trifluoroacetyl group), an acyloxy group (for example, an acetoxy
group, a propionyloxy group or a trifluoroacetoxy group), and an
alkoxycarbonyl group (for example, a methoxycarbonyl group, an
ethoxycarbonyl group, or a tert-butoxycarbonyl group, etc.). The
substituent is preferably an alkyl group, an alkoxy group or an
alkoxycarbonyl group.
[0152] m.sub.0, m.sub.1, and m.sub.2 independently represent an
integer of from 0 to 2, and are preferably 0 or 1.
[0153] L.sub.0 represents a single bond or a (r.sub.0+1)-valent
linkage group having a carbon atom number of from 1 to 15, which
may contain an oxygen atom or a sulfur atom in the main chain.
L.sub.1 represents a single bond or a (r.sub.1+1)-valent linkage
group having a carbon atom number of from 1 to 15, which may
contain an oxygen atom or a sulfur atom in the main chain. L.sub.2
represents a single bond or a (r.sub.2+1)-valent linkage group
having a carbon atom number of from 1 to 15, which may contain an
oxygen atom or a sulfur atom in the main chain.
[0154] Examples of a divalent linkage group having a carbon atom
number of from 1 to 15, which may contain an oxygen atom or a
sulfur atom in the main chain include groups described below and a
combination of these groups and --O--, --S--, --CO--, or --CS--.
[0155] a methylene group [--CH.sub.2--], [0156] an ethylidene group
[>CHCH.sub.3], [0157] an isopropylidene group
[>C(CH.sub.3).sub.2], [0158] a 1,2-ethylene group
[--CH.sub.2CH.sub.2--], [0159] a 1,2-propylene group
[--CH(CH.sub.3)CH.sub.2--], [0160] a 1,3-propanediyl group
[--CH.sub.2CH.sub.2CH.sub.2--], [0161] a
2,2-dimethyl-1,3-propanediyl group
[--CH.sub.2C(CH.sub.3).sub.2CH.sub.2--], [0162] a
2,2-dimethoxy-1,3-propanediyl group
[--CH.sub.2C(OCH.sub.3).sub.2CH.sub.2--], [0163] a
2,2-dimethoxymethyl-1,3-propanediyl group [--CH.sub.2C
(CH.sub.2OCH.sub.3).sub.2CH.sub.2--], [0164] a
1-methyl-1,3-propanediyl group [--CH(CH.sub.3)CH.sub.2CH.sub.2--,
[0165] a 1,4-butanediyl group
[--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--], [0166] a 1,5-pentanediyl
group [--CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2--], [0167] an
oxydiethylene group [--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2--], [0168]
a thiociethylene group [--CH.sub.2CH.sub.2SCH.sub.2CH.sub.2--],
[0169] a 3-oxothiodiethylene group
[--CH.sub.2CH.sub.2SOCH.sub.2CH.sub.2--], [0170] a
3,3-dioxothiodiethylene group
[--CH.sub.2CH.sub.2SO.sub.2CH.sub.2CH.sub.2--], [0171] a
1,4-dimethyl-3-oxa-1,5-pentanediyl group
[--CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2--], [0172] a
3-oxopentanediyl group [--CH.sub.2CH.sub.2COCH.sub.2CH.sub.2--],
[0173] a 1,5-dioxo-3-oxapentanediyl group
[--COCH.sub.2OCH.sub.2CO--], [0174] a 4-oxa-1,7-heptanediyl group
[--CH.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2--], [0175] a
3,6-dioxa-1,8-octanediyl group
[--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--], [0176] a
1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group
[--CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2--],
[0177] a 5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group
[--CH.sub.2CH.sub.2OCH.sub.2C(CH.sub.3).sub.2CH.sub.2OCH.sub.2CH.sub.2--]-
, [0178] a 5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl group
[CH.sub.2CH.sub.2OCH.sub.2C(OCH.sub.3).sub.2CH.sub.2OCH.sub.2CH.sub.2--],
[0179] a 5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group
[--CH.sub.2CH.sub.2OCH.sub.2C(CH.sub.2OCH.sub.3).sub.2CH.sub.2OCH.sub.2CH-
.sub.2--], [0180] a 4,7-dioxo-3,8-dioxa-1,10-decanediyl group
[--CH.sub.2CH.sub.2O--COCH.sub.2CH.sub.2CO--OCH.sub.2CH.sub.2--],
[0181] a 3,8-dioxo 4,7-dioxa-1,10-decanediyl group
[--CH.sub.2CH.sub.2CO--OCH.sub.2CH.sub.2O--COCH.sub.2CH.sub.2--],
[0182] a 1,3-cyclopentanediyl group [-1,3-C.sub.5H.sub.8--], [0183]
a 1,2-cyclohexanediyl group [-1,2-C.sub.6H.sub.10--], [0184] a
1,3-cyclohexanediyl group [-1,3-C.sub.6H.sub.10--], [0185] a
1,4-cyclohexanediyl group [-1,4-C.sub.6H.sub.10--], [0186] a
2,5-tetrahydrofuranediyl group [2,5-C.sub.4H.sub.6O--], [0187] a
p-phenylene group [--P--C.sub.6H.sub.4--], [0188] a m-phenylene
group [-m-C.sub.6H.sub.4--], [0189] an .alpha.,.alpha.'-o-xylylene
group [-o--CH.sub.2--C.sub.6H.sub.4--CH.sub.2--], [0190] an
.alpha.,.alpha.'-m-xylylene group
[-m--CH.sub.2--C.sub.6H.sub.4--CH.sub.2--], [0191] an
.alpha.,.alpha.'-p-xylylene group
[-p--CH.sub.2--C.sub.6H.sub.4--CH.sub.2--], [0192] a
furane-2,5-diyl-bismethylene group
[2,5-CH.sub.2--C.sub.4H.sub.2O--CH.sub.2--], [0193] a
thiophene-2,5-diyl-bismethylene group
[2,5-CH.sub.2--C.sub.4H.sub.2S--CH.sub.2--], [0194] an
isopropylidene-p-phenylene group
[-p-C.sub.6H.sub.4--C(CH.sub.3).sub.2-p-C.sub.6H.sub.4--].
[0195] Examples of the 3 or more valent linkage group include
groups, which is obtained by eliminating a hydrogen atom from the
divalent linkage groups exemplified above, and a combination of
these groups and --O--, --S--, --CO--, or --CS--.
[0196] L.sub.o, L.sub.1 and L.sub.2 may have a substituent.
Examples of the substituent include a halogen atom (for example, a
chlorine atom, a bromine atom, or a fluorine atom), an alkyl group
having a carbon atom number of from 1 to 6 (for example, a methyl
group, an ethyl group, a propyl group, an isopropyl group, or a
butyl group), an alkoxy group having a carbon atom number of from 1
to 6 (for example, a methoxy group, an ethoxy group, an n-propoxy
group, an isopropoxy group, a n-butoxy group or a tert-butoxy
group), an acyl group (for example, an acetyl group, a propionyl
group, or a trifluoroacetyl group), an acyloxy group (for example,
an acetoxy group, a propionyloxy group, or a trifluoroacetoxy
group), and an alkoxycarbonyl group (for example, a methoxycarbonyl
group, an ethoxycarbonyl group, or a tert-butoxycarbonyl group).
Preferred substituents are an alkyl group, an alkoxy group and an
alkoxycarbonyl group.
[0197] L.sub.o, L.sub.1 and L.sub.2 represent preferably a divalent
linkage group having a carbon atom number of from 1 to 8, which may
contain an oxygen atom or a sulfur atom in the main chain, and more
preferably a divalent linkage group having a carbon atom number of
from 1 to 5, the main chain of which consists of a carbon atom
[0198] Typical examples of the alicyclic epoxide represented by
formula A, I or II will be listed later.
[0199] As the alicyclic epoxide, an alicyclic epoxide compound
represented by formula (III) or (IV) above is also preferred.
[0200] In formula (III) or (IV), R.sub.200 and R.sub.201
independently represent an aliphatic group. Examples of the
aliphatic group include an alkyl group having a carbon atom number
of from 1 to 6 (for example, a methyl group, an ethyl group, a
propyl group, an isopropyl group, or a butyl group); a cycloalkyl
group having a carbon number of from 3 to 6 (for example, a
cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a
cyclohexyl group); an alkenyl group having a carbon atom number of
from 1 to 6 (for example, a vinyl group, a 1-propenyl group, a
2-propenyl group, or a 2-butenyl group); and an alkinyl group
having a carbon atom number of from 1 to 6 (for example, an
acetylenyl group, a 1-propinyl group, a 2-propinyl group, or a
2-butinyl group). The aliphatic group is preferably an alkyl group
having a carbon atom number of from 1 to 3, and more preferably a
methyl group or an ethyl group.
[0201] "m.sub.3" and "m.sub.4" independently represent an integer
of from 0 to 2, and preferably not less than 1.
[0202] X.sub.1 represents --(CH.sub.2).sub.n0-- or --(O).sub.n0--,
and X.sub.2 represents --(CH.sub.2).sub.n1-- or --(O).sub.n1--, in
which n0 and n1 independently represent an integer of 0 or 1,
provided that when n0 and n1 are 0, respectively, neither X.sub.1
nor X.sub.2 exists. P1 and q1 independently represent 0 or 1,
provided that they are not simultaneously 0. P2 and q2
independently represent 0 or 1, provided that they are not
simultaneously 0.
[0203] It is preferred that (m.sub.3+n.sub.0) is not less than 1,
or (m.sub.4+n.sub.1) is not less than 1.
[0204] L.sub.3 represents a single bond, or a (r3+1)-valent linkage
group having a branched structure, provided that the linkage group
may contain an oxygen atom or a sulfur atom in the main chain; and
L.sub.4 represents a single bond, or a (r4+1)-valent linkage group
having a branched structure, provided that the linkage group may
contain an oxygen atom or a sulfur atom in the main chain.
[0205] As a divalent linkage group with a carbon number of from 1
to 15 which may contain an oxygen atom or a sulfur atom in the main
chain, are cited the following groups and their combination with
--O--, --S--, --CO-- and/or --CS--. [0206] an ethylidene group
[>CHCH.sub.3], [0207] an isopropylidene group
[>C(CH.sub.3).sub.2], [0208] a 2,2-dimethyl-1,3-propanediyl
group [--CH.sub.2C(CH.sub.3).sub.2CH.sub.2--], [0209] a
2,2-dimethoxy-1,3-propanediyl group
[--CH.sub.2C(OCH.sub.3).sub.2CH.sub.2--], [0210] a
2,2-dimethoxymethyl-1,3-propanediyl group
[--CH.sub.2C(CH.sub.2OCH.sub.3).sub.2CH.sub.2--], [0211] a
1,3-dimethyl-2-oxa-1,4-butanediyl group
[--CH(CH.sub.3)CH.sub.2OCH(C.sub.3)CH.sub.2--], [0212] a
1,4-dimethyl-3-oxa-1,5-pentanediyl group
[--CH(CH.sub.3)CH.sub.2CH.sub.2OCH(CH.sub.3)CH.sub.2--], [0213] a
1,3,5-trimethyl-2,4-dioxa-1,6-hexanediyl group
[--CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2--],
[0214] a 4,4-dimethyl-2,5-dioxa-1,7-heptanediyl group
[--CH.sub.2CH.sub.2OCH.sub.2C(OCH.sub.3).sub.2CH.sub.2OCH.sub.2CH.sub.2---
], [0215] a 4,4-dimethoxy-2,5-dioxa-1,7-heptanediyl group
[--CH.sub.2CH.sub.2OCH.sub.2C(OCH.sub.3).sub.2CH.sub.2OCH.sub.2CH.sub.2---
], [0216] a 4,4-dimethoxymethyl-2,5-dioxa-1,7-heptanediyl group
[--CH.sub.2CH.sub.2OCH.sub.2C(CH.sub.2OCH.sub.3).sub.2CH.sub.2OCH.sub.2CH-
.sub.2--], [0217] a 1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group
[--CH(CH.sub.3)CH.sub.2CH.sub.2OCH(CH.sub.3)CH.sub.2CH.sub.2OCH(CH.sub.3)-
CH.sub.2--], [0218] a 5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group
[--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2C(CH.sub.3).sub.2CH.sub.2CH.sub.2OCH.-
sub.2CH.sub.2--], [0219] a 5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl
group
[--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2C(OCH.sub.3).sub.2CH.sub.2CH.sub.2OCH-
.sub.2CH.sub.2--], [0220] a
5,5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group
[--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2C(CH.sub.2OCH.sub.3).sub.2CH.su-
b.2CH.sub.2OCH.sub.2CH.sub.2--], [0221] an
isopropylidene-p-phenylene group
[-p-C.sub.6H.sub.4--C(CH.sub.3).sub.2-p-C.sub.6H.sub.4--[
[0222] As a tri- or more-valent linkage group are cited a group in
which an arbitrary hydrogen atom is withdrawn from the divalent
linkage group described above and its combination with --O--,
--S--, --CO-- and/or --CS--.
[0223] L.sub.3 and L.sub.4 preferably have a substituent. Examples
of the substituent include a halogen atom (for example, a chlorine
atom, a bromine atom, or a fluorine atom), an alkyl group having a
carbon atom number of from 1 to 6 (for example, a methyl group, an
ethyl group, a propyl group, an isopropyl group, or a butyl group),
an alkoxy group having a carbon atom number of from 1 to 6 (for
example, a methoxy group, an ethoxy group, an n-propoxy group, an
isopropoxy group, a n-butoxy group or a tert-butoxy group), an acyl
group (for example, an acetyl group, a propionyl group, or a
trifluoroacetyl group), an acyloxy group (for example, an acetoxy
group, a propionyloxy group, or a trifluoroacetoxy group), and an
alkoxycarbonyl group (for example, a methoxycarbonyl group, an
ethoxycarbonyl group, or a tert-butoxycarbonyl group). Preferred
substituents are a halogen atom, an alkyl group, and an alkoxy
group.
[0224] Typical examples of the compound represented by formula A,
I, II, III, or IV will be listed below.
##STR00034## ##STR00035##
[0225] In the above, Mw is molecular weight.
##STR00036##
[0226] The content of the alicyclic epoxy compound in the invention
is preferably from 10 to 80% by weight. In the invention, the
alicyclic epoxy compound may be used alone or as a mixture of two
or more kinds thereof.
[0227] A synthetic method of the epoxy compound in the invention is
not specifically limited. The epoxy compound can be synthesized
according to the methods described in for example, "Jiken Kagaku
Koza 20, Yukigosei II", 213-(1992), Fourth Edition, published by
Maruzen K K Shuppan; Ed. by Alfred Hasfner, "The chemistry of
heterocyclic compounds-Small Ring Heterocycles part 3 Oxiranes",
John and Wiley and Sons, An Interscience Publication, New York
(1985); Yoshimura, "Secchaku", Vol. 29, 12, pp. 32 (1985);
Yoshimura, "Secchaku", Vol. 30, 5, pp. 42 (1986); Yoshimura,
"Secchaku", Vol. 30, 7, pp. 42 (1986); and Japanese Patent O.P.I.
Publication No. 11-100378.
[Epoxidated Fatty Acid Ester or Epoxidated Glyceride]
[0228] In the invention, epoxidated fatty acid ester or epoxidated
glyceride is contained in an amount of preferably up to 20% by
weight, based on the actinic ray curable composition.
[0229] Incorporation of the epoxidated fatty acid ester or
epoxidated glyceride is preferred in safety such as AMES,
sensitization, less skin irritation or odor, and can solve problems
such as occurrence of creases due to shrinkage or deterioration of
curability or ejection stability which is caused depending on
environmental conditions (such as temperature and humidity).
[0230] In the invention, at least one of epoxidated fatty acid
ester or epoxidated glyceride is preferably used as the oxirane
ring-containing compound, in view of AMES or sensitization.
[0231] The epoxidated fatty acid ester or epoxidated glyceride
usable in the invention is obtained by incorporating an epoxy group
into fatty acid ester or glyceride, and can be used without any
limitations.
[0232] As the epoxidated fatty acid ester, there is one
manufactured by epoxidation of fatty acid ester, and examples
thereof include epoxy methyl stearate, epoxy butyl stearate, and
epoxy octyl stearate. Similarly, as the epoxidated glyceride, there
is one manufactured by epoxidation of soybean oil, linseed oil or
castor oil, and examples thereof include epoxy soybean oil, epoxy
linseed oil and epoxy castor oil.
[0233] The actinic ray curable composition the invention can
contain a photopolymerization initiator, for example, a known
photolytically acid generating agent.
[0234] As the photolytically acid generating agent, for example,
compounds used in a chemical amplification type photo resist or in
a light cation polymerizable composition are used (Organic
electronics material seminar "Organic material for imaging" from
Bunshin publishing house (1993), refer to page 187-192). Examples
suitable for the present invention will be listed below.
[0235] Firstly, an onium compound, for example, a
B(C.sub.6F.sub.5).sub.4.sup.-, PF.sub.6.sup.-, AsF.sub.6.sup.-,
SbF.sub.6.sup.-, CF.sub.3SO.sub.3.sup.- salt of an aromatic onium
ion such as an aromatic diazonium, ammonium, iodonium, sulfonium,
or phosphonium, can be listed.
[0236] Examples of the onium compounds used in the invention will
be shown below.
##STR00037## ##STR00038##
[0237] Secondly, sulfone compounds, which generate sulfonic acid,
can be listed. Examples thereof will be shown below.
##STR00039##
[0238] Thirdly, halide compounds, which generate hydrogen halide,
can also be used. Examples thereof will be shown below.
##STR00040##
[0239] Fourthly, iron arene complexes as described below can be
listed.
##STR00041##
[0240] In the invention, a photolytically radical generating agent
can be used in combination. Examples thereof include known
photolytically radical generating agents such as aryl alkyl ketone,
oxime ketone, S-phenyl thiobenzoate, titanocene, aromatic ketones,
thioxanthone, benzil, quinone derivatives and coumarin derivatives.
Those agents are is described in detail in "Application and Market
of UVEB Hardening Technology", edited by Radotech Kenkyuu
Kai/supervised by Y. Tabata, published by CMC Syuppan. Among them,
acylphosphine oxide and acylphosphonate are particularly effective
for internal hardening of an ink image layer having a thickness of
from 5 to 12 .mu.m per one color ink according to an ink-jet
process, since they are high in the sensitivity and reduce the
light absorption on account of their photodecomposition. In
concrete, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide are
preferable. Like the monomer described above, 1-hydroxycyclohexyl
phenyl ketone,
2-methyl-1[4-methylthio]phenyl]-2-morpholinopropane-1-one,
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphin oxide, and
2-hydroxy-2-methyl-1-phenylpropane-1-one (DAROCURE.RTM. 1173) are
preferably used. The addition amount of the photolytically radical
generating agent is preferably from 1 to 6% by weight, and more
preferably from 2 to 5% by weight, based on the ink
composition.
[0241] The actinic ray curable ink of the invention contains any
known dye or pigment, and preferably pigment, in addition to the
actinic ray curable composition as described above.
[0242] Pigments preferably utilized in the invention will be listed
below, but the invention is not limited thereto.
[0243] C.I. Pigment Yellow-1, 3, 12, 13, 14, 17, 81, 83, 87, 95,
109, 42,
[0244] C.I. Pigment Orange-16, 36, 38,
[0245] C.I. Pigment Red-5, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1,
57:1, 63:1, 144, 146, 185, 101,
[0246] C.I. Pigment Violet-19, 23,
[0247] C.I. Pigment Blue-15:1, 15:3, 15:4, 4, 18, 60, 27, 29,
[0248] C.I. Pigment Green-7, 36,
[0249] C.I. Pigment White-6, 18, 21,
[0250] C.I. Pigment Black-7,
[0251] Further, in the invention, white ink is preferably utilized
to increase a covering power of colors with transparent base
materials such as a plastic film. It is preferable to utilize white
ink, specifically in light package printing and label printing,
however, due to increase of ejection amount, the using amount is
naturally limited in respect to the above-mentioned ejection
stability, and generation of curl and wrinkles of a recording
material.
[0252] To disperse the above-described pigment, for example, a ball
mill, a sand mill, an attritor mill, a roll mill, an agitator, a
Henshel mixer, a colloidal mixer, a ultrasonic homogenizer, a pearl
mill, a wet jet mill, a paint shaker, etc. can be utilized.
Further, a dispersant can be added at dispersion of a pigment. As a
dispersant, a polymer dispersant is preferably utilized and
Soisperse Series manufactured by Avecia Co. is included. Further,
as a dispersion aid, a synergist corresponding to each kind of a
pigment can also be utilized. The dispersant and dispersion aid are
preferably added in a range of from 1 to 50 weight parts based on
100 parts of a pigment. As a dispersion medium, a solvent or a
polymerizable compound is utilized, however, the actinic ray
curable ink used in the invention is preferably an ink containing
no solvent, since curing was carried out immediately after the ink
was deposited on recording material. When a solvent is left in a
cured image, there caused problems of deterioration of resistance
against solvents and VOC of residual solvent. Therefore, as a
dispersion medium, polymerizable compounds are used but a solvent
not. Particularly monomers having the lowest viscosity among them
are preferably used in view of dispersion suitability.
[0253] In dispersion of a pigment, selection of a pigment, a
dispersant and a dispersion medium, dispersion conditions and
filtering conditions are suitably set so as to make a mean particle
diameter of a pigment of preferably from 0.08 to 0.5 .mu.m and the
maximum particle diameter of from 0.3 to 10 .mu.m and preferably
from 0.3 to 3 .mu.m. By this particle diameter control, it is
possible to depress clogging of a head nozzle and maintain keeping
stability of ink, as well as transparency and curing sensitivity of
ink.
[0254] In ink according to the invention, colorant concentration is
preferably from 1 to 10 weight % based on the total ink.
[0255] Various kinds of additives other than those explained above
can be added to the actinic ray curable ink of the invention. For
example, a surfactant, a leveling additive, a matting agent,
polyester type resin, polyurethane type resin, vinyl type resin,
acryl type resin, rubber type resin and wax series can be added to
the ink when necessary. Further, in order to increase storage
stability, various basic compounds can be used. Examples of the
basic compounds include a basic alkali metal compound, a basic
alkali earth metal compound and an organic basic compound such as
amine. The actinic ray curable ink of the invention may be a
radical and cationic polymerization hybrid curable ink further
containing a radical polymerization composition comprising a
radical polymerization monomer and a radical initiator.
[Ink Properties and Recording Sheets]
[0256] It is preferred that the ink of the invention has an ink
viscosity at 25.degree. C. of from 7 to 50 mPas, since it provides
good ejection stability regardless of ambient atmosphere conditions
(such as temperature and humidity) and good curability.
[0257] As a recording material used in the invention, besides
ordinary non-coated paper or coated paper, various non-absorptive
plastics or their films, which are used in a so-called light
packaging, can be utilized. Examples of the plastic films include
for example, a polyethylene terephthalate (PET) film, an oriented
polystyrene (OPS) film, an oriented polypropylene (OPP) film, an
oriented nylon (Ony) film, a polyvinyl chloride (PVC) film, a
polyethylene (PE) film and a triacetyl cellulose (TAC) film. As
plastic films other than these, polycarbonate, acryl resin, ABS,
polyacetal, PVA and a rubber series can be utilized. A metal series
and a glass series are also applicable.
[0258] Plastic films greatly differ in surface energy depending on
the kinds, and heretofore, there has been a problem in that the ink
dot diameter after ink deposition on recording material varies
depending on the kinds of the recording materials. The constitution
of the invention can form an image with high precision on recording
materials having a surface energy of from 35 to 60 mN/m, the
recording materials ranging from those having a low surface energy
such as an OPP or OPS film to those having a relatively high
surface energy such as a PET film.
[0259] In the invention, a long length roll (web) of a recording
material is advantageously utilized in respect to a cost of a
recording material such as a packaging cost and a manufacturing
cost, an efficiency of print preparation and applicability to
variety of print sizes.
[Image Formation Method]
[0260] An image forming method of the invention will be
explained.
[0261] In the image forming method in the invention, it is
preferred that the ink described above be ejected onto a recording
material according to an ink jet recording method, and then cured
by irradiation of actinic ray such as UV ray.
(Thickness of Ink Layer Formed After Ink is Ejected Onto Recording
Material)
[0262] In the invention, the thickness of an ink layer, after ink
has been elected onto recording material and cured by actinic ray
irradiation, is preferably from 2 to 20 .mu.m. In actinic ray
curable ink jet recording in the field of screen printing, the
total thickness of the ink is at present over 20 .mu.m. Ink
ejecting to give an excessive layer thickness is not preferred in
the field of flexible package printing where a thin plastic film is
used as a recording material, because problems are caused in that
stiffness and texture of printed matter vary, in addition to
problems of the aforementioned curl and wrinkles of recording
material.
[0263] Herein, the thickness of ink layer refers to a maximum
thickness of the ink layer deposited on recording material. This
applies to a single color ink layer, and an overlapped layer of two
different color (secondary color) inks, three different color inks
or four different color inks (including white ink as a base ink),
which are formed on recording material according to an ink jet
recording process.
(Conditions of Ink Ejection)
[0264] As conditions of ink ejection, ink ejection is preferably
performed while a recording head and ink being heated at from 35 to
100.degree. C. in respect to ejection stability. Since actinic ray
curable ink shows a large viscosity variation width depending on
temperature variation and which in turn significantly influences a
liquid droplet size and a liquid drop let ejection speed resulting
in deterioration of image quality, it is required to keep an ink
temperature constant while raising the ink temperature. A control
width of ink temperature is a set temperature.+-.5.degree. C.,
preferably a set temperature.+-.2.degree. C. and furthermore
preferably a set temperature.+-.1.degree. C.
[0265] The droplet volume of the ink ejected from each ink nozzle
is preferably 2 to 15 pl. The droplet volume of the ink has to be
in the range described above to form images with high resolution,
however, this droplet volume tends to lower the aforementioned
ejection stability. In the invention, even when a small droplet
volume such as 2 to 15 pl is ejected, ejection stability is
improved, and images with high resolution can be formed.
(Actinic Ray Irradiation Condition After Ink Has Been Ejected Onto
Recording Material)
[0266] In an image recording method of the invention, it is
preferred that actinic ray is irradiated 0.001 to 2.0 seconds after
ink has been ejected on recording material, and it is more
preferred that actinic ray is irradiated 0.001 to 1.0 second after
ink has been ejected on recording material. It is specifically
important that the irradiation timing be as early as possible in
order to form an image with high resolution.
[0267] As an actinic ray irradiation method, a basic method is
disclosed in JP-A No. 60-132767, in which light sources are
provided at the both sides of a head unit where a head and a light
are scanned in a shuttle mode. Irradiation is performed in a
certain time interval after ink has been ejected onto recording
material. Further, curing is completed by another light source
which is not driven. As a light irradiation method, a method
utilizing optical fiber, and a method in which collimated light
source is reflected by a mirror provided on the side surface of a
head unit and UV light (ultraviolet light) is irradiated on a
recording portion are disclosed in U.S. Pat. No. 6,145,979. In an
image forming method of the invention, any of these irradiation
methods can be utilized.
[0268] Further, a method is also a preferable embodiment, in which
actinic ray irradiation is divided into two steps; firstly, a first
actinic ray irradiation is carried between the period from 0.001 to
2.0 seconds after ink was deposited on recording material by the
above-described method and further a second actinic ray irradiation
is carried after printing has been completed. Shrinkage of
recording materials caused at the time of ink curing can be
depressed by dividing actinic ray irradiation into two steps.
[0269] Heretofore, in a UV ink jet method, it has been usual to
utilize a light source of high illuminance having a power exceeding
1 kWhr in order to minimize widening of dots and bleeding-out
caused after ink deposition on recording material. However,
particularly in such as a shrink label, utilizing the light sources
makes shrinkage of a recording material too large to be used
practically at present.
[0270] In the invention, an actinic ray having a maximum
illuminance in a wavelength range from 280 to 320 nm is preferably
used, and even when a light source a power exceeding 1 kWhr is
used, images with high resolution can be formed, and shrinkage of a
recording material is in the permissible range.
[0271] In the invention, the power of light sources irradiating an
actinic ray is preferably less than 1 kWhr. Examples of the light
sources having a power of less than 1 kWhr include a fluorescent
lamp, a cold cathode tube and an LED, but are not limited
thereto.
[0272] An ink jet recording apparatus (hereinafter also referred to
as a recording apparatus) in the invention will be explained.
[0273] Next, the recording apparatus in the invention will be
explained suitably in reference to a drawing. Herein, the recording
apparatus of the drawing is only an embodiment of a recording
apparatus of the invention, and a recording apparatus of the
invention is not limited to the drawing.
[0274] FIG. 1 shows a schematic view of one embodiment of the
structure of the main section of the ink-jet recording apparatus of
the invention.
[0275] Recording apparatus 1 is equipped with head carriage 2,
recording head 3, irradiation means 4 and platen portion 5. In
recording apparatus 1, platen portion 5 is arranged under recording
material P. Platen portion 5 has a UV ray absorbing function, and
absorbs extra UV ray having passed through recording sheet P. As a
result, images with high resolution can be reproduced quite
stably.
[0276] Recording sheet P is guided by guide member 6 to be moved to
the back side from the front side in FIG. 1 by operation of a
transport means (not illustrated). Scan of recording heads 3 held
in the head carriage 2 is made by reciprocating head carriage 2 in
the R direction in FIG. 1 according to a head scanning means (not
illustrated).
[0277] Head carriage 2 is provided over recording sheet P, and
stores recording heads 3 described below with the ink ejection
outlets arranged downward, the number of recording heads 3 being
the same as that of different color inks used in an ink image
formed on the recording sheet. Head carriage 2 is provided in the
main body of recording apparatus 1 so as to reciprocate in the R
direction shown in FIG. 1 by a drive of a head scanning means.
[0278] Herein, FIG. 1 illustrates that head carriage 2 is supposed
to store recording heads 3 each containing a white ink composition
W, a yellow ink composition Y, a magenta ink composition M, a cyan
ink composition C, a black ink composition K, a light yellow ink
composition Ly, a light magenta ink composition Lm, a light cyan
ink composition Lc, a light black ink composition Lk and a white
ink composition W, however, the number of recording heads 3 stored
in head carriage 2 in practical operation is suitably
determined.
[0279] Recording heads 3 eject an actinic ray curable ink (for
example, UV curable ink) to be supplied by means of an ink
supplying means (not illustrated) from the ink ejection outlets
onto recording sheet P by action of plural ejecting means (not
illustrated) equipped in the recording apparatus. Ink to have been
ejected from recording heads 3 is cured by UV irradiation.
[0280] The recording heads 3 eject ink as ink droplets onto a
pre-determined region (a region capable of receiving the ink) of
recording sheet P while the scan of the head is made in which the
head moves from one edge to another of the recording sheet in the R
direction in FIG. 1 by drive of the head scanning means, whereby
the ink is deposited on that region of the recording sheet.
[0281] The above scan is suitably made several times to elect ink
onto one region of recording sheet. After that, while the recording
sheet P is transported from the front side to the back side of the
page in FIG. 1 by a transport means and the scan of the recording
heads 3 is again made by the head scan means, ink is ejected from
the recording heads onto a region adjacent to the one region of the
recording sheet transported to the back side of the page.
[0282] The above operation is repeated, whereby the ink is ejected
from recording heads 3 employing the head scan means and the
transport means to form an image comprised of aggregates of ink
droplets on recording sheet P.
[0283] Irradiation means 4 is equipped with a UV lamp which emits
ultraviolet ray with a specific wavelength region at a stable
exposure energy and a filter which transmits ultraviolet ray with a
specific wavelength. Herein, Examples of the UV lamp include a
mercury lamp, a metal halide lamp, an excimer laser, a UV laser, a
cold cathode tube, a black light, and an LED, and a metal halide
lamp tube, a cold cathode tube, a mercury lamp tube and a black
light, having a band-shape, are preferable. Specifically a cold
cathode tube and a black light which emit a 365 nm ultraviolet ray
are preferable, which can prevent bleeding-out, efficiently control
a dot diameter, and reduce wrinkles on curing. Utilizing a black
light as a radiation source of irradiation means 4 reduces a
manufacturing cost of irradiation means 4 for ink curing.
[0284] Irradiation means 4 has the possible largest size which can
be installed in the recording apparatus 1 (an ink jet printer) or
the irradiation region of the irradiation means 4 is larger than
the largest region of recording sheet, onto which ink is ejected by
one time scan of recording heads 3 driven by the head scanning
means.
[0285] The irradiation means 4 is arranged nearly in parallel with
recording sheet 4 at the both sides of head carriage 2, and
fixed.
[0286] In order to adjust illuminance at the ink ejection outlets,
the whole of recording heads 3 is light-shielded, however, in
addition, it is preferable to make distance h2 between the ink
ejection outlet 31 of recording heads 3 and recording sheet P
longer than distance h1 between irradiation means 4 and recording
sheet P (h1<h2) or to make distance d between recording heads 3
and irradiation means 4 long (to make d large). Further, it is more
preferable to provide bellows structure 7 between recording heads 3
and irradiation means 4.
[0287] Herein, the wavelength of ultraviolet rays, which are
irradiated through irradiation means 4 can be suitably changed by
exchange of a UV lamp or a filter, which is installed in
irradiation means 4.
[0288] The ink-jet ink of the invention has excellent ejection
stability, and is useful especially when used in a line head type
ink-jet recording apparatus.
[0289] FIG. 2 shows a schematic view of another embodiment of the
structure of the main section of the ink-jet recording
apparatus.
[0290] The ink-jet recording apparatus in FIG. 2 is called a line
head type ink-jet recording apparatus. Recording heads 3 are
provided in a head carriage 2 to cover the entire width of
recording sheet P. The recording heads 3 each stores a different
color ink, a white ink composition W, a yellow ink composition Y, a
magenta ink composition M, a cyan ink composition C, a black ink
composition K, and a white ink composition W.
[0291] Irradiation means 4 is provided just downstream of head
carriage 2 to cover the entire width of recording sheet P and the
entire printed surface. In FIG. 2, a metal halide lamp can be used
as a light source in the irradiation means 4.
[0292] In the line head type recording apparatus, head carriage 2
and irradiation means 4 are fixed, and recording sheet P only is
transported in the direction as shown in FIG. 2. Ink is ejected
onto the recording sheet to be transported and then exposed through
the irradiation means to form a cured image on the recording
sheet.
EXAMPLES
[0293] The present invention will be explained in detail employing
the following examples. However, the invention is not limited
thereto.
Example 1
[0294] In this example, a coating layer from the actinic ray
curable composition was evaluated.
[Preparation of Actinic Ray Curable Composition]
[0295] A photopolymerizable compound, a photopolymerization
initiator, a non-reactive compound and other additives as shown in
Table 1 were mixed to obtain an actinic ray curable
composition.
[Curing of Actinic Ray Curable Composition]
[0296] The resulting actinic ray curable composition was coated on
a synthetic paper sheet (synthetic paper YUPO FGS, produced by YUPO
CORPORATION) to form a layer with a thickness of 3 .mu.m, and
exposed to a 800 mJ/cm2 UV rays employing a metal halide lamp to
obtain a cured coating layer.
TABLE-US-00001 TABLE 1 Actinic Ray Curable Composition containing a
radically polymerizable compound Non- Photopolymerization reactive
Radically initiator Compound Actinic Polymerizable (Addition
(Addition Ray Compound amount, amount, Curable (Addition amount,
Parts by Parts by Composition Parts by weight) weight) weight)
Remarks 1 TEDA CPEHA PEMA IRGACURE 184 None Comp. (40) (20) (30)
(10) 2 TEDA CPEHA PEMA IRGACURE 184 Hisolve BDB Inv. (35) (20) (25)
(10) (10) 3 TEDA CPEHA PEMA IRGACURE 184 Anisole Inv. (35) (20)
(25) (10) (10) 4 TEDA CPEHA PEMA IRGACURE 184 Excelpearl Inv. (35)
(20) (25) (10) HO (10) Comp.: Comparative, Inv.: Inventive TEDA:
Tetraethylene diacrylate, CPEHA: .epsilon.-Caprolactam modified
pentaerythritol hexacrylate PEMA: Phenoxyethyl methacrylate
TABLE-US-00002 TABLE 2 Actinic Ray Curable Composition containing a
cationically polymerizable compound *2 Photopolymerization Basic
Non-reactive *1 *3 *4 Initiator compound Compound Remarks 5 OXT221
*6 UVI6992 TBA None Comp. (65) (29.5) (5) (0.5) 6 OXT221 *6 UVI6992
TBA HISOLVE BDB Inv. (60) (24.5) (5) (0.5) (10) 7 OXT221 *6 UVI6992
TBA Anisole Inv. (60) (31.5) (5) (0.5) (10) 8 OXT221 *6 UVI6992 TBA
EXCELPEARL HO Inv. (60) (24.5) (5) (0.5) (10) 9 OXT221 *6 UVI6992
TBA EXCELPEARL IPM Inv. (60) (31.5) (5) (0.5) (10) 10 OXT221 *6
UVI6992 TBA HISOLVE DB Inv. (20) (14.5) (5) (0.5) (10) 11 OXT221 *6
UVI6992 TBA HISOLVE BTM Inv. (60) (24.5) (5) (0.5) (10) 12 OXT221
*6 UVI6992 TBA HIMOL TM Inv. (60) (24.5) (5) (0.5) (10) 13 OXT221
*6 UVI6992 TBA HISOL SAS296 Inv. (60) (24.5) (5) (0.5) (10) 14
OXT221 *6 UVI6992 TBA HISOLVE BDB Inv. (34.5) (50) (5) (0.5) (10)
15 OXT221 *6 UVI6992 TBA HISOLVE BDB Inv. (29.5) (60) (5) (0.5)
(15) 16 OXT221 *6 UVI6992 TBA Anisole Inv. (34.5) (50) (5) (0.5)
(10) 17 OXT221 *7 *8 *9 None Comp. (65) (29.5) (5) (0.5) 18 OXT221
*7 *8 *9 HISOLVE BDB Inv. (60) (24.5) (5) (0.5) (10) 19 OXT221 *7
*8 *9 Anisole Inv. (60) (24.5) (5) (0.5) (10) 20 OXT221 *7 *8 *9
EXCELPEAR HO Inv. (60) (24.5) (5) (0.5) (10) 21 OXT221 EP-1 UVI6992
TBA None Comp. (65) (29.5) (5) (0.5) 22 OXT221 EP-1 UVI6992 TBA
HISOLVE BDB Inv. (60) (24.5) (5) (0.5) (10) 23 OXT221 EP-1 UVI6992
TBA Anisole Inv. (60) (24.5) (5) (0.5) (10) 24 OXT221 EP-1 UVI6992
TBA EXCELPEAR HO Inv. (60) (24.5) (5) (0.5) (10) 25 OXT221 EP-8
UVI6992 TBA HISOLVE BDB Inv. (60) (24.5) (5) (0.5) (10) 26 OXT221
EP-15 UVI6992 TBA HISOLVE BDB Inv. (60) (24.5) (5) (0.5) (10) 27
OXT222 EP-15 UVI6992 TBA Anisole Inv. (55) (19.5) (5) (0.5) (20) 28
*5 EP-8 UVI6992 *9 None Comp. (65) (29.5) (5) (0.5) 29 *5 EP-8
UVI6992 *9 HISOLVE BDB Inv. (60) (24.5) (5) (0.5) (10) 30 *5 EP-8
UVI6992 *9 Anisole Inv. (60) (24.5) (5) (0.5) (10) 31 *5 EP-8
UVI6992 *9 EXCELPEAR HO Inv. (60) (24.5) (5) (0.5) (10) Inv.:
Inventive, Comp.: Comparative Numeral values in the parentheses
represent an addition amount (parts by weight). *1: Actinic Ray
Curable Composition No., *2: Photopolymerizable Compound, *3:
Oxetane compound, *4: Epoxy Compound, *5:
2-Methoxy-3,3-dimethyloxetane, *6: Celloxide 2021P, *7: Vf7010,
Vikoflex 7010, produced by ATOFINA CO., LTD., *8: I-250, IRGACURE
250, *9: N-Ethyldiethanolamine TBA: Tributylamine
Compounds Used for Preparation of the Actinic Ray Curable
Composition and Their Physicochemical Properties
Measurement of Viscosity
[0297] Viscosity was measured at a shear rate of 1000 (l/s) at
25.degree. C., employing a viscoelasticity meter MCR 300 produced
by Physica Co., Ltd.
TABLE-US-00003 TABLE 3 Temperature at which Viscosity was Boiling
Viscosity measured point Product (Trade name) (mPa s) (.degree. C.)
(.degree. C.) EXELPEARLHO (produced 14 25 228 by KAO CO., LTD.)
EXCELPEARLIPM 6.6 25 304 (produced by KAO CO., LTD.) HISOLVE DB
(produced 6.6 25 230 by TOHO CHEMICAL INDUSTRY CO., LTD.) HISOLVE
BDB (produced 2.4 25 256 by TOHO CHEMICAL INDUSTRY CO., LTD.)
HISOLVE BTM (produced 2.9 25 261 by TOHO CHEMICAL INDUSTRY CO.,
LTD.) HIMOL TM (produced by 8.3 25 249 TOHO CHEMICAL INDUSTRY CO.,
LTD.) Anisole 1.2 25 154 HISOL SAS296 (produced 8.3 25 300 by
NIPPON PETROLEUM CHEMICAL CO., LTD.)
Compounds used in the above
(Photopolymerizable Compound)
[0298] CELLOXIDE 2021P: Alicyclic epoxide, produced by DAICELL
KAGAKU KOGYO CO., LTD. [0299] Vf7010: Vikoflex7010 epoxidated
soybean oil, produced by ATOFINA CO., LTD. [0300] OXT-221: Oxetane
Compound, produced by TOA GOSEI CO., LTD.
(Photolytically Acid Generating Agent)
[0300] [0301] I-250: IRGACURE 250, produced by CIBA SPECIALTY
CHEMICALS INC. [0302] UVI6992: 50% propylene carbonate solution,
produced by DOW CHEMICAL CO., LTD.
(Photolytically Radical Generating Agent)
[0302] [0303] I-184: IRGACURE 184, produced by CIBA SPECIALTY
CHEMICALS INC.
(Surfactant)
[0303] [0304] MEGAFACS F178k: Perfluoroalkyl group-containing acryl
oligomer, produced by DAINIPPON INK KAGAKU KOGYO CO., LTD. [0305]
MEGAFACS F1405: Perfluoroalkyl group-containing ethylene oxide
adduct, produced by DAINIPPON INK KAGAKU KOGYO CO., LTD.
(Miscibility Promoting Agent)
[0305] [0306] HARITAC R100: Rosin modified maleic acid resin,
produced by HARIMA KAGAKU CO., LTD. [0307] HARITAC 145P: Rosin
modified maleic acid resin, produced by HARIMA KAGAKU CO., LTD.
(Dispersant)
[0307] [0308] PB822: Product of AJINOMOTO FINE TECHNO CO., LTD.
(Others)
[0308] [0309] N-Ethyldiethanolamine (Basic compound) [0310]
Tributylamine (Basic compound)
[Evaluation]
(Evaluation of Cured Layer)
[0311] The resulting cured layer was evaluated according to the
following methods.
1) Pencil Scratching Test
[0312] Hardness of the resulting layer was measured according to
JIS K 5400.
2) Cross-Cut Adhesion Test
[0313] Adhesive tape SCOTCH #250 (produced by SUMITOMO 3M CO.,
LTD.) was adhered onto the cured layer of a cured sample obtained
according to the cross-cut adhesion test of JIS K 5400, and a 2 kg
roller was reciprocated one time to press the adhered tape. After
that, the tape was quickly peeled from the cured layer, and the
percentage of the remaining layer was determined.
3) Flexibility Test
[0314] The resulting actinic ray curable composition was coated on
a synthetic paper sheet YUPO FGS (produced by YUPO Corporation) to
obtain a layer with a thickness of 30 .mu.m, and exposed to 800
mJ/cm.sup.2 UV rays within 1 second after coated, employing a metal
halide lamp to form a cured layer. The resulting cured layer was
evaluated according to the flexibility test of JIS K 5600.
[0315] The results are shown in Table 4.
TABLE-US-00004 TABLE 4 Pencil Percentage of Sample Scratching Test
remaining layer Flexibility No. Pencil Hardness (%) .phi.: mm
Remarks 1 2H 40 **1 Comp. 2 2H 60 3 mm.phi. Inv. 3 2H 55 3 mm.phi.
Inv. 4 1H 50 4 mm.phi. Inv. 5 2H 50 10 mm.phi. Comp. 6 2H 80 **2
Inv. 7 2H 75 1 mm.phi. Inv. 8 2H 70 3 mm.phi. Inv. 9 1H 75 2
mm.phi. Inv. 10 1H 70 2 mm.phi. Inv. 11 1H 75 1 mm.phi. Inv. 12 1H
70 2 mm.phi. Inv. 13 1H 70 2 mm.phi. Inv. 14 2H 80 1 mm.phi. Inv.
15 2H 85 **2 Inv. 16 2H 80 1 mm.phi. Inv. 17 1H 40 8 mm.phi. Comp.
18 1H 60 **2 Inv. 19 1H 60 2 mm.phi. Inv. 20 1H 55 2 mm.phi. Inv.
21 2H 60 10 mm.phi. Comp. 22 2H 85 **2 Inv. 23 2H 85 **2 Inv. 24 2H
75 1 mm.phi. Inv. 25 2H 80 **2 Inv. 26 2H 80 **2 Inv. 27 1H 85 **2
Inv. 28 3H 70 10 mm.phi. Comp. 29 3H 95 **2 Inv. 30 3H 90 **2 Inv.
31 2H 90 1 mm.phi. Inv. Comp.: Comparative, Inv.: Inventive **1:
Cracks were observed at 10 mm.phi.. **2: No cracks were observed at
1 mm.phi..
[0316] As is apparent from Table 4, inventive samples provide a
cured layer with improved adhesion and flexibility, and without
lowering of hardness.
Example 2
[0317] Herein, ink prepared from an actinic ray curable composition
was evaluated.
[Ink Set]
[0318] The photopolymerizable compound shown in Table 5 and 5 parts
by weight of dispersant PB822 (produced by AJINOMOTO CO., LTD.)
were incorporated into a stainless steel beaker on a 65.degree. C.
hot plate and stirred for one hour to obtain a solution. Each of
the pigments as shown in Table 6 was added to the resulting
solution, and incorporated in a plastic vessel together with 200 g
of zirconia beads with a diameter of 1 mm. The plastic vessel was
tightly sealed and dispersed in a paint shaker for 2 hours to
obtain a dispersion liquid. After the zirconia beads were removed,
the dispersion liquid was added with additives as shown in Table 5
such as the photopolymerization initiator, the basic compound and
the surfactant, and filtered with a 0.8 .mu.m membrane filter.
Thus, ink composition set sample was obtained, which included seven
different color inks.
[0319] Viscosity of the ink prepared above was 20 to 30 mPaS.
TABLE-US-00005 TABLE 5 Actinic Ray Curable Composition containing a
cationically polymerizable compound Non- *2 Photopolymerization
Basic reactive *1 *3 *4 Initiator compound Compound *5 *6
Dispersant Colorant Remarks 1 OXT221 *8 UVI6992 *11 None *13 *16
PB822 Pigment Comp. (60) (25.3) (5) (1) (0.1) (5) (1) (3) 2 OXT221
*8 UVI6992 *11 HISOLVE *13 *16 PB822 Pigment Inv. (50) (25.3) (5)
(1) BDB (10) (0.1) (5) (1) (3) 3 OXT221 *8 UVI6992 *11 Anisole *13
*16 PB822 Pigment Inv. (50) (25.3) (5) (1) (10) (0.1) (5) (1) (3) 4
OXT221 *8 UVI6992 *11 EXCELPEARL *13 *16 PB822 Pigment Inv. (50)
(25.3) (5) (1) HO (10) (0.1) (5) (1) (3) 5 OXT221 *8 UVI6992 *11
HISOLVE *13 *16 PB822 Pigment Inv. (45) (25.3) (5) (1) BDB (15)
(0.1) (5) (1) (3) 6 OXT221 *8 UVI6992 *11 HISOLVE *13 *16 PB822
Pigment Inv. (20) (55.3) (5) (1) BDB (15) (0.1) (5) (1) (3) 7
OXT221 *9 *10 *12 None *13 *16 PB822 Pigment Comp. (60) (25.3) (5)
(1) (0.1) (5) (1) (3) 8 OXT221 *9 *10 *12 HISOLVE *13 *16 PB822
Pigment Inv. (50) (25.3) (5) (1) BDB (10) (0.1) (5) (1) (3) 9
OXT221 *9 *10 *12 Anisole *13 *16 PB822 Pigment Inv. (50) (25.3)
(5) (1) (10) (0.1) (5) (1) (3) 10 OXT221 EP-1 UVI6992 *11 None *14
*17 PB822 Pigment Comp. (60) (25.3) (5) (1) (0.1) (5) (1) (3) 11
OXT221 EP-1 UVI6992 *11 HISOLVE PB822 Pigment Inv. (50) (25.3) (5)
(1) BDB (10) (1) (3) 12 OXT221 EP-1 UVI6992 *11 Anisole *14 *17
PB822 Pigment Inv. (50) (25.3) (5) (1) (10) (0.1) (5) (1) (3) 13
OXT221 EP-1 UVI6992 *11 EXCELPEARL *14 *17 PB822 Pigment Inv. (30)
(15.3) (5) (1) HO (10) (0.1) (5) (1) (3) 14 OXT222 EP-2 UVI6992 *11
Anisole *15 *18 PB822 Pigment Inv. (55) (25.3) (5) (1) (5) (0.1)
(5) (1) (3) 15 OXT221 EP-8 UVI6992 *11 HISOLVE *14 *17 PB822
Pigment Inv. (50) (25.3) (5) (1) BDB (10) (0.1) (5) (1) (3) 16
OXT221 EP-15 UVI6992 *11 HISOLVE *14 *17 PB822 Pigment Inv. (50)
(25.3) (5) (1) BDB (10) (0.1) (5) (1) (3) 17 *7 EP-8 UVI6992 *12
None *14 *16 PB822 Pigment Comp. (60) (25.3) (5) (1) (0.1) (5) (1)
(3) 18 *7 EP-8 UVI6992 *12 Anisole *14 *16 PB822 Pigment Inv. (55)
(25.3) (5) (1) (5) (0.1) (5) (1) (3) 19 *7 EP-8 UVI6992 *12 HISOLVE
*14 *16 PB822 Pigment Inv. (50) (25.3) (5) (1) BDB (10) (0.1) (5)
(1) (3) 20 *7 EP-8 UVI6992 *12 HISOLVE *14 *16 PB822 Pigment Inv.
(45) (25.3) (5) (1) BDB (15) (0.1) (5) (1) (3) Inv.: Inventive,
Comp.: Comparative Numeral values in the parentheses represent an
addition amount (parts by weight). In Table 5, *-marked numerals
represent the following: *1: Actinic Ray Curable Composition No.,
*2: Photopolymerizable Compound, *3: Oxetane compound, *4: Epoxy
Compound, *5: Nonionic fluorine-containing surfactant, *6:
Rosin-modified maleic acid resin, *7:
2-Methoxy-3,3-dimethyloxetane, *8: Celloxide 2021P, *9: Vf7010,
Vikoflex 7010, produced by ATOFINA CO., LTD., *10: I-250, IRGACURE
250, *11: Tributylamine, *12: N-Ethyldiethanolamine, *13: MEGAFAC
F1405, *14: MEGAFAC F178k, *15: MEGAFAC F179k, *16: HARITAC 145P,
*17: HARITAC R100, *18: HARITAC R101,
[0320] Pigments used in the ink set samples are shown in Table 6.
Inks, Lk, Lc, Lm and Ly represent light color inks, and employed
1/5 of the amount used in inks K, C, M, and Y, respectively.
[0321] Further, the following ink set samples were prepared. [0322]
Ink set sample No. 21: To the sample No. 17 were added 10% by
weight of acetone (bp. 56.degree. C.). [0323] Ink set sample No.
22: To the sample No. 17 were added 10% by weight of silicone oil
SH 550 (produced by TORAY DOW CORNING CO., LTD., viscosity: 130
mPaS).
TABLE-US-00006 [0323] TABLE 6 Ink K C M Y W Lk Lc Lm Ly Pigment CI
CI CI CI Titanium CI CI CI CI used Pigment Pigment Pigment Pigment
Oxide: Pigment Pigment Pigment Pigment Black 7 Blue Red Yellow
Anatase Black 7 Blue Red Yellow 15:3 57:1 13 type, 15:3 57:1 13
Particle diameter: 0.2 .mu.m
[Ink-Jet Image Formation Method]
[0324] The ink set sample prepared above was mounted on an ink jet
recording apparatus as shown in FIG. 1 equipped with a piezo-type
ink jet nozzle, and image recording was performed continuously on
each of 600 mm wide and 1000 m long recording sheets described
later.
[0325] An ink supply system is comprised of an ink tank, a supply
pipe, a pre-chamber ink tank directly before a head, a piping
attached with a filter, and a piezo-head, and the portion from the
pre-chamber tank to the head was heated at 50.degree. C. The
piezo-head was appropriately heated to meet viscosity of each ink
and driven so as to eject ink droplets of from 2 to 15 pl at a
resolution of 720 dpi.times.720 dpi. Thus, each ink was
continuously ejected onto the recording sheet.
[0326] The recording sheet was heated to 50.degree. C. by a heater.
Within less than 0.5 seconds after ink was ejected and arrived at
the recording sheet, exposure was carried out, employing the light
sources on both sides of the carriage to form a cured ink image. As
the light source, light source A, a high pressure mercury lamp
Vzero 085, produced by INTEGRATION TECHNOLOGY CO., or light source
B, a metal halide lamp MAL400NL, produced by NIPPON DENCHI CO.,
LTD., 120 W/cm, output power: 3 kWhr), was employed.
The total thickness of the resulting ink image layer was measured
to be in a range of from 2.3 to 13 .mu.m. Herein, dpi represents a
dot number per 2.54 cm.
[0327] The above ink image formation was carried out at 32.degree.
C. and 80% RH.
[0328] Luminance of each light source was measured through
employing UVPF-A1 produced by IWASAKI DENKI CO., LTD., and
integrated illuminance was determined.
[0329] In Table 7, abbreviation of each of the recording sheets is
as follows: [0330] YUPO FGS: Synthetic paper produced by YUPO
CORPORATION [0331] PVC: Polyvinyl chloride
(Ejection Property)
[0332] Ink was continuously ejected for 30 minutes, and thereafter,
failure of the ink was visually observed according to the following
criteria. [0333] A: No ink failure was observed, resulting in good
level. [0334] B: A little ink failure was observed but not
problematic. [0335] C: Some ink failure was observed and was the
level having an influence on image quality. [0336] D: Much ink
failure was observed and impermissible level.
<Evaluation of Ink Jet Ink Image>
[0337] The following evaluations were carried out with respect to
each image recorded according to the above-described image forming
method.
(Character Quality)
[0338] 6-point MS Minchyc font characters were recorded at an aimed
density, and the resulting characters were evaluated for roughness
through a magnifying glass according to the following criteria.
[0339] A: No roughness was observed. [0340] B: Slight roughness was
observed. [0341] C: Roughness was observed, however, the resulting
characters were legible, which was the lowest usable level. [0342]
D: Significant roughness was observed, and the resulting characters
were scratchy, which could not be put into practical use.
(Color Contamination (Bleeding-Out or Crease))
[0343] One dot of each of inks Y, M, C and K was recorded at 720
dpi to be adjacent to each other, and the resulting two adjacent
dots were evaluated for color contamination (bleeding-out or
crease) through a magnifying glass according to the following
criteria. [0344] A: The shapes of the two adjacent dots kept a true
circle, and no bleeding-out was observed. [0345] B: The shapes of
the two adjacent dots kept a nearly true circle, and little
bleeding-out was observed. [0346] C: The two adjacent dots showed a
little bleeding-out, and the dot shapes were slightly deformed,
however, which was the lowest usable level. [0347] D: The two
adjacent dots showed bleeding-out and were contaminated with each,
which could not be put into practical use.
[0348] The results are shown in Table 7.
TABLE-US-00007 TABLE 7 30.degree. C., 25.degree. C., Ejec- 80% RH
20% RH tion Sample PVC YUPOFGS PVC YUPOFGS Pro- Re- No. *a) *b) *a)
*b) *a) *b) *a) *b) perty marks 1 D D D D D C D C C Comp. 2 B B B B
B B B B A Inv. 3 B B B B B B B B B Inv. 4 C C C C B B B B B Inv. 5
B B B B B A B A A Inv. 6 A A A A A A A A A Inv. 7 D D D D D D D D B
Comp. 8 B B B B B B B B A Inv. 9 C C C C B B B B A Inv. 10 C D C D
C C C C C Comp. 11 A B A B B A B A A Inv. 12 B B B B B B B B B Inv.
13 B C B C B B B B B Inv. 14 B C B C B B B B B Inv. 15 B B B B B B
B B A Inv. 16 A B A B B A B A B Inv. 17 C C C C C C C C D Comp. 18
B B B B B B B B B Inv. 19 B B B B B B B B B Inv. 20 A A A A A A A A
A Inv. 21 C D C D C D C D D Comp. 22 C B C B C B C B D Comp. Comp.:
Comparative, Inv.: Inventive *a) Character Quality, *b) Color
Contamination (bleeding-out or crease)
[0349] As is apparent from Table 7 above, the inventive ink sets
exhibit excellent ejection property, and improved image quality.
Further, the inventive ink sets provide excellent results,
regardless of ambient condition under which an ink image was
recorded.
Effects of the Invention
[0350] The present invention can provide an actinic ray curable
composition with a low viscosity, which is capable of being cured
with high speed, and forms a coating layer with high hardness under
various operating conditions, an actinic ray curable ink employing
it, an image formation method employing it, and an ink-jet
recording apparatus employing it.
* * * * *