U.S. patent application number 09/514891 was filed with the patent office on 2002-08-08 for sensitizing dye and silver halide photographic material.
Invention is credited to Kagawa, Nobuaki, Kashiwagi, Hiroshi, Kita, Noriyasu, Tanaka, Tatsuo.
Application Number | 20020106593 09/514891 |
Document ID | / |
Family ID | 26399710 |
Filed Date | 2002-08-08 |
United States Patent
Application |
20020106593 |
Kind Code |
A1 |
Kagawa, Nobuaki ; et
al. |
August 8, 2002 |
Sensitizing dye and silver halide photographic material
Abstract
Spectral sensitizing dyes represented by the following formulas
(1) to (4) are disclosed; silver halide photographic materials and
thermally developable photosensitive materials containing the dyes
are also disclosed. 1
Inventors: |
Kagawa, Nobuaki; (Tokyo,
JP) ; Kita, Noriyasu; (Tokyo, JP) ; Tanaka,
Tatsuo; (Tokyo, JP) ; Kashiwagi, Hiroshi;
(Tokyo, JP) |
Correspondence
Address: |
BIERMAN MUSERLIAN AND LUCAS
600 THIRD AVENUE
NEW YORK
NY
10016
|
Family ID: |
26399710 |
Appl. No.: |
09/514891 |
Filed: |
February 28, 2000 |
Current U.S.
Class: |
430/574 ;
430/588; 430/619; 544/101 |
Current CPC
Class: |
G03C 1/20 20130101; G03C
1/49881 20130101; C09B 23/0008 20130101; C09B 23/08 20130101; G03C
2200/39 20130101; C09B 23/0066 20130101; C09B 23/0075 20130101;
G03C 1/49854 20130101 |
Class at
Publication: |
430/574 ;
430/619; 430/588; 544/101 |
International
Class: |
G03C 001/20; G03C
001/498; G03C 001/29 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 5, 1999 |
JP |
058686 |
Jul 9, 1999 |
JP |
196659/1999 |
Claims
What is claimed is:
1. A spectral sensitizing dye represented by the following formulas
(1) to (4): 46wherein Y.sub.1, Y.sub.2 and Y.sub.11 each are
independently an oxygen atom, a sulfur atom, a selenium atom,
--C(Ra)(Rb)-- group or --CH.dbd.CH-- group, in which Ra and Rb each
are a hydrogen atom, a lower alkyl group or an atomic group
necessary to form an aliphatic spiro ring between Ra and Rb;
Z.sub.1 is an atomic group necessary to form a 5- or 6-membered
ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an
aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group
or a halogen atom; W.sub.1, W.sub.2, W.sub.3, W.sub.4, W.sub.11,
W.sub.12, W.sub.13 and W.sub.14 each are independently a hydrogen
atom, a substituent or a non-metallic atom group necessary to form
a condensed ring by bonding between W.sub.1 and W.sub.2 or W.sub.11
and W.sub.12; R.sub.1 and R.sub.11 are each an aliphatic group or a
non-metallic atom group necessary to form a condensed ring by
bonding between R.sub.1 and W.sub.3 or R.sub.11 and W.sub.14;
V.sub.1 to V.sub.9, and V.sub.11 to V.sub.13 each are independently
a hydrogen atom, a halogen atom, an amino group, an alkylthio
group, an arylthio group, a lower alkyl group, a lower alkoxy
group, an aryl group, an aryloxy group, a heterocyclic group or a
non-metallic atom group necessary to form a 5- to 7-membered ring
by bonding between V.sub.1 and V.sub.3, V.sub.2 and V.sub.4,
V.sub.3 and V.sub.5, V.sub.2 and V.sub.6, V.sub.5 and V.sub.7,
V.sub.6 and V.sub.8, V.sub.7 and V.sub.9, or V.sub.11 and V.sub.13,
provided that at least one of V.sub.1 to V.sub.9 and at least one
of V.sub.11 to V.sub.13 are a group other than a hydrogen atom;
X.sub.1 and X.sub.11 each are an ion necessary to compensate for an
intramolecular charge; l1 and l11 each an ion necessary to
compensate for an intramolecular charge; k1 and k2 each are 0 or 1;
p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided
that the sum of p1 and q1 and the sum of p11 and q11 are
respectively not more than 2; 47wherein Y.sub.21, Y.sub.22 and
Y.sub.31 each are independently an oxygen atom, a sulfur atom, a
selenium atom, --C(Ra)(Rb)-- group or --CH.dbd.CH-- group, in which
Ra and Rb each are a hydrogen atom, a lower alkyl group or an
atomic group necessary to form an aliphatic spiro ring between Ra
and Rb; R.sub.21, R.sub.22, R.sub.31 and R.sub.32 each are
independently an aliphatic group; Rc and Rd each are independently
an unsubstituted lower alkyl group, a cycloalkyl group, an aralkyl
group, an aryl group or a heterocyclic group; W.sub.21, W.sub.22,
W.sub.23, W.sub.24, W.sub.31, W.sub.32, W.sub.33 and W.sub.34 each
are independently a hydrogen atom, a substituent or a non-metallic
atom group necessary to form a condensed ring by bonding between
W.sub.21 and W.sub.22, W.sub.23 and W.sub.24, W.sub.31 and
W.sub.32, or W.sub.33 and W.sub.34; V.sub.21 to V.sub.29, and
V.sub.31 to V.sub.33 each are independently a hydrogen atom, a
halogen atom, an amino group, an alkylthio group, an arylthio
group, a lower alkyl group, a lower alkoxy group, an aryl group, an
aryloxy group, a heterocyclic group or a non-metallic atom group
necessary to form a 5- to 7-membered ring by bonding between
V.sub.21 and V.sub.23, V.sub.22 and V.sub.24, V.sub.23 and
V.sub.25, V.sub.24 and V.sub.26, V.sub.25 and V.sub.27, V.sub.26
and V.sub.28, V.sub.27 and V.sub.29, or V.sub.31 and V.sub.33;
X.sub.21 and X.sub.31 each are an ion necessary to compensate for
an intramolecular charge; l21 and l31 each an ion necessary to
compensate for an intramolecular charge; k21 and k22 each are 0 or
1; n21, n22, n31 and n32 each are 0, 1 or 2, provided that n21 and
n22, or n31 and n32 are not 0 at the same time.
2. The spectral sensitizing dye of claim 1, wherein said dye is
represented by formula (1) or (2).
3. The spectral sensitizing dye of claim 2, wherein said dye is
represented by the following formula (1-1) or (2-1): 48wherein
Y.sub.1, Y.sub.2 and Y.sub.11 each are independently an oxygen
atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or
--CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen atom, a
lower alkyl group or an atomic group necessary to form an aliphatic
spiro ring when Ra and Rb are linked with each other; Z.sub.1 is an
atomic group necessary to form a 5- or 6-membered ring; R is a
hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group,
a lower alkoxy group, an aryl group, a hydroxy group or a halogen
atom; W.sub.1, W.sub.2, W.sub.3, W.sub.4, W.sub.11, W.sub.12,
W.sub.13 and W.sub.14 each are independently a hydrogen atom, a
substituent or a non-metallic atom group necessary to form a
condensed ring by bonding between W.sub.1 and W.sub.2 or W.sub.11
and W.sub.12; R.sub.1 and R.sub.11 are each an aliphatic group or a
non-metallic atom group necessary to form a condensed ring by
bonding between R.sub.1 and W.sub.3 or R.sub.11 and W.sub.14;
L.sub.1 to L.sub.9, and L.sub.11 to L.sub.15 each are independently
a methine group; X.sub.1 and X.sub.11 each are an ion necessary to
compensate for an intramolecular charge; l1 and l11 each an ion
necessary to compensate for an intramolecular charge; m1 to m3 each
are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2,
provided that the sum of p1 and q1 and the sum of p11 and q11 are
respectively not more than 2.
4. The spectral sensitizing dye of claim 1, wherein said dye is
represented by formula (3) or (4).
5. The spectral sensitizing dye of claim 4, wherein said dye is
represented by formula (3).
6. A silver halide photographic material comprising a support
having thereon at least a photosensitive layer containing a silver
halide emulsion layer, wherein said photosensitive layer contains a
compound represented by the following formulas (1) to (4):
49wherein Y.sub.1, Y.sub.2 and Y.sub.11 each are independently an
oxygen atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or
--CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen atom, a
lower alkyl group or an atomic group necessary to form an aliphatic
spiro ring between Ra and Rb; Z.sub.1 is an atomic group necessary
to form a 5- or 6-membered ring; R is a hydrogen atom, a lower
alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group,
an aryl group, a hydroxy group or a halogen atom; W.sub.1, W.sub.2,
W.sub.3, W.sub.4, W.sub.11, W.sub.12, W.sub.13 and W.sub.14 each
are independently a hydrogen atom, a substituent or a non-metallic
atom group necessary to form a condensed ring by bonding between
W.sub.1 and W.sub.2 or W.sub.11 and W.sub.12; R.sub.1 and R.sub.11
are each an aliphatic group or a non-metallic atom group necessary
to form a condensed ring by bonding between R.sub.1 and W.sub.3 or
R.sub.11 and W.sub.14; V.sub.1 to V.sub.9, and V.sub.11 to V.sub.13
each are independently a hydrogen atom, a halogen atom, an amino
group, an alkylthio group, an arylthio group, a lower alkyl group,
a lower alkoxy group, an aryl group, an aryloxy group, a
heterocyclic group or a non-metallic atom group necessary to form a
5- to 7-membered ring by bonding between V1 and V.sub.3, V.sub.2
and V.sub.4, V.sub.3 and V.sub.5, V.sub.2 and V6, V.sub.5 and
V.sub.7, V6 and V8, V.sub.7 and V.sub.9, or V.sub.11 and V.sub.13,
provided that at least one of V1 to V.sub.9 and at least one of
V.sub.11 to V.sub.13 are a group other than a hydrogen atom;
X.sub.1 and X.sub.11 each are an ion necessary to compensate for an
intramolecular charge; l1 and l11 each an ion necessary to
compensate for an intramolecular charge; k1 and k2 each are 0 or 1;
p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided
that the sum of p1 and q1 and the sum of p11 and q11 are
respectively not more than 2; 50wherein Y.sub.21, Y.sub.22 and
Y.sub.31 each are independently an oxygen atom, a sulfur atom, a
selenium atom, --C(Ra)(Rb)-- group or --CH.dbd.CH-- group, in which
Ra and Rb each are a hydrogen atom, a lower alkyl group or an
atomic group necessary to form an aliphatic spiro ring between Ra
and Rb; R.sub.21, R.sub.22, R.sub.31 and R.sub.32 each are
independently an aliphatic group; Rc and Rd each are independently
an unsubstituted lower alkyl group, a cycloalkyl group, an aralkyl
group, an aryl group or a heterocyclic group; W.sub.21, W.sub.22,
W.sub.23, W.sub.24, W.sub.31, W.sub.32, W.sub.33 and W.sub.34 each
are independently a hydrogen atom, a substituent or a non-metallic
atom group necessary to form a condensed ring by bonding between
W.sub.21 and W.sub.22, W.sub.23 and W.sub.24, W.sub.31 and
W.sub.32, or W.sub.33 and W.sub.34; V.sub.21 to V.sub.29, and
V.sub.31 to V.sub.33 each are independently a hydrogen atom, a
halogen atom, an amino group, an alkylthio group, an arylthio
group, a lower alkyl group, a lower alkoxy group, an aryl group, an
aryloxy group, a heterocyclic group or a non-metallic atom group
necessary to form a 5- to 7-membered ring by bonding between
V.sub.21 and V.sub.23, V.sub.22 and V.sub.24, V.sub.23 and
V.sub.25, V.sub.24 and V.sub.26, V.sub.25 and V.sub.27, V.sub.26
and V.sub.28, V.sub.27 and V.sub.29, or V.sub.31 and V.sub.33;
X.sub.21 and X.sub.31 each are an ion necessary to compensate for
an intramolecular charge; l21 and l31 each an ion necessary to
compensate for an intramolecular charge; k21 and k22 each are 0 or
1; n21, n22, n31 and n32 each are 0, 1 or 2, provided that n21 and
n22, or n31 and n32 are not 0 at the same time.
7. The photographic material of claim 6, wherein said compound is
represented by formula (1) or (2).
8. The photographic material of claim 7, wherein said compound is
represented by the following formula (1-1) or (2-1): 51wherein
Y.sub.1, Y.sub.2 and Y.sub.11 each are independently an oxygen
atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or
--CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen atom, a
lower alkyl group or an atomic group necessary to form an aliphatic
spiro ring when Ra and Rb are linked with each other; Z.sub.1 is an
atomic group necessary to form a 5- or 6-membered ring; R is a
hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group,
a lower alkoxy group, an aryl group, a hydroxy group or a halogen
atom; W.sub.1, W.sub.2, W.sub.3, W.sub.4, W.sub.11, W.sub.12,
W.sub.13 and W.sub.14 each are independently a hydrogen atom, a
substituent or a non-metallic atom group necessary to form a
condensed ring by bonding between W.sub.1 and W.sub.2 or W.sub.11
and W.sub.12; R.sub.1 and R.sub.11 are each an aliphatic group or a
non-metallic atom group necessary to form a condensed ring by
bonding between R.sub.1 and W.sub.3 or R.sub.11 and W.sub.14;
L.sub.1 to L.sub.9, and L.sub.11 to L.sub.15 each are independently
a methine group; X.sub.1 and X.sub.11 each are an ion necessary to
compensate for an intramolecular charge; l1 and l11 each an ion
necessary to compensate for an intramolecular charge; m1 to m3 each
are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2,
provided that the sum of p1 and q1 and the sum of p11 and q11 are
respectively not more than 2.
9. The photographic material of claim 6, wherein said compound is
represented by formula (3) or (4).
10. The photographic material of claim 9, wherein said compound is
represented by formula (3).
11. The photographic material of claim 10, wherein said
photosensitive layer further contains a compound represented by the
following formula (5): 52wherein Y.sub.4 and Y.sub.42 each are
independently an oxygen atom, a sulfur atom, a selenium atom,
--C(Ra)(Rb)-- group or --CH.dbd.CH-- group, in which Ra and Rb each
are a hydrogen atom, a lower alkyl group or an atomic group
necessary to form an aliphatic spiro ring together with Ra and Rb;
R.sub.41 and R.sub.42 each are independently an aliphatic group; Re
and Rf each are independently an unsubstituted lower alkyl group,
cycloalkyl group, aralkyl group, aryl group or heterocyclic group;
W.sub.41, W.sub.42, W.sub.43, and W.sub.44 each are independently a
hydrogen atom, a substituent or a non-metallic atom group necessary
to form a condensed ring by bonding between W.sub.41 and W.sub.42,
W.sub.43 and W.sub.44; L.sub.41 to L.sub.49 are each a methine
group; X.sub.41 is an ion necessary to compensate for an
intramolecular charge; l41 is an ion necessary to compensate for an
intramolecular charge; m42 and m43 each are 0 or 1; n41 and n42
each are 0, 1 or 2, provided that n41 and n42 are not 0 at the same
time.
12. The photographic material of claim 9, wherein said compound is
represented by formula (4).
13. The photographic material of claim 12, wherein said
photosensitive layer further contains a compound represented by
formula (6): 53wherein Y.sub.51 is independently an oxygen atom, a
sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or --CH.dbd.CH--
group, in which Ra and Rb each are a hydrogen atom, a lower alkyl
group or an atomic group necessary to form an aliphatic spiro ring
together with Ra and Rb; R.sub.51 and R.sub.52 each are
independently an aliphatic group; Re and Rf each are independently
an unsubstituted lower alkyl group, cycloalkyl group, aralkyl
group, aryl group or heterocyclic group; W.sub.51, W.sub.52,
W.sub.53 and W.sub.54 each are independently a hydrogen atom, a
substituent or a non-metallic atom group necessary to form a
condensed ring by bonding between W.sub.51 and W.sub.52, or
W.sub.53 and W.sub.54; L.sub.51 to L.sub.55 are each a methine
group; X.sub.51 is an ion necessary to compensate for an
intramolecular charge; l51 is an ion necessary to compensate for an
intramolecular charge; n51 and n52 each are 0, 1 or 2, provided
that n51 and n52 are not 0 at the same time.
14. The photographic material of claim 6, wherein said
photosensitive layer further contains an organic silver salt and a
reducing agent.
15. The photographic material of claim 14, wherein said compound is
represented by formula (1) or (2).
16. The photographic material of claim 15, wherein said compound is
represented by the following formula (1-1) or (2-1): 54wherein
Y.sub.1, Y.sub.2 and Y.sub.11 each are independently an oxygen
atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or
--CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen atom, a
lower alkyl group or an atomic group necessary to form an aliphatic
spiro ring when Ra and Rb are linked with each other; Z.sub.1 is an
atomic group necessary to form a 5- or 6-membered ring; R is a
hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group,
a lower alkoxy group, an aryl group, a hydroxy group or a halogen
atom; W.sub.1, W.sub.2, W.sub.3, W.sub.4, W.sub.11, W.sub.12,
W.sub.13 and W.sub.14 each are independently a hydrogen atom, a
substituent or a non-metallic atom group necessary to form a
condensed ring by bonding between W.sub.1 and W.sub.2 or W.sub.11
and W.sub.12; R.sub.1 and R.sub.11 are each an aliphatic group or a
non-metallic atom group necessary to form a condensed ring by
bonding between R.sub.1 and W.sub.3 or R.sub.11 and W.sub.14;
L.sub.1 to L.sub.9, and L.sub.11 to L.sub.15 each are independently
a methine group; X.sub.1 and X.sub.11 each are an ion necessary to
compensate for an intramolecular charge; l1 and l11 each an ion
necessary to compensate for an intramolecular charge; m1 to m3 each
are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2,
provided that the sum of p1 and q1 and the sum of p11 and q11 are
respectively not more than 2.
17. The photographic material of claim 14, wherein said compound is
represented by formula (3) or (4).
18. The photographic material of claim 17, wherein said compound is
represented by formula (3).
19. The photographic material of claim 18, wherein said
photosensitive layer further contains a compound represented by the
following formula (5): 55wherein Y.sub.4 and Y.sub.42 each are
independently an oxygen atom, a sulfur atom, a selenium atom,
--C(Ra)(Rb)-- group or --CH.dbd.CH-- group, in which Ra and Rb each
are a hydrogen atom, a lower alkyl group or an atomic group
necessary to form an aliphatic spiro ring together with Ra and Rb;
R.sub.41 and R.sub.42 each are independently an aliphatic group; Re
and Rf each are independently an unsubstituted lower alkyl group,
cycloalkyl group, aralkyl group, aryl group or heterocyclic group;
W.sub.41, W.sub.42, W.sub.43, and W.sub.44 each are independently a
hydrogen atom, a substituent or a non-metallic atom group necessary
to form a condensed ring by bonding between W.sub.41 and W.sub.42,
W.sub.43 and W.sub.44; L.sub.41 to L.sub.49 are each a methine
group; X.sub.41 is an ion necessary to compensate for an
intramolecular charge; l41 is an ion necessary to compensate for an
intramolecular charge; m42 and m43 each are 0 or 1; n41 and n42
each are 0, 1 or 2, provided that n41 and n42 are not 0 at the same
time.
20. The photographic material of claim 17, wherein said compound is
represented by formula (4).
21. The photographic material of claim 20, wherein said
photosensitive layer further contains a compound represented by
formula (6): 56wherein Y.sub.51 is independently an oxygen atom, a
sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or --CH.dbd.CH--
group, in which Ra and Rb each are a hydrogen atom, a lower alkyl
group or an atomic group necessary to form an aliphatic spiro ring
together with Ra and Rb; R.sub.51 and R.sub.52 each are
independently an aliphatic group; Re and Rf each are independently
an unsubstituted lower alkyl group, cycloalkyl group, aralkyl
group, aryl group or heterocyclic group; W.sub.51, W.sub.52,
W.sub.53 and W.sub.54 each are independently a hydrogen atom, a
substituent or a non-metallic atom group necessary to form a
condensed ring by bonding between W.sub.51 and W.sub.52, or
W.sub.53 and W.sub.54; L.sub.51 to L.sub.55 are each a methine
group; X.sub.51 is an ion necessary to compensate for an
intramolecular charge; l51 is an ion necessary to compensate for an
intramolecular charge; n51 and n52 each are 0, 1 or 2, provided
that n51 and n52 are not 0 at the same time.
22. The photographic material of claim 14, wherein the photographic
material further has a non-photosensitive layer, said
non-photosensitive layer containing a binder, a phthalazine
compound, a benzenepolycarboxylic acid or an acid anhydride
compound.
23. An image forming method comprising exposing a photosensitive
material to laser, the photosensitive material comprising a support
having thereon at least a photosensitive layer containing a
compound represented by the following formulas (1) to (4):
57wherein Y.sub.1, Y.sub.2 and Y.sub.11 each are independently an
oxygen atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or
--CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen atom, a
lower alkyl group or an atomic group necessary to form an aliphatic
spiro ring between Ra and Rb; Z.sub.1 is an atomic group necessary
to form a 5- or 6-membered ring; R is a hydrogen atom, a lower
alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group,
an aryl group, a hydroxy group or a halogen atom; W.sub.1, W.sub.2,
W.sub.3, W.sub.4, W.sub.11, W.sub.12, W.sub.13 and W.sub.14 each
are independently a hydrogen atom, a substituent or a non-metallic
atom group necessary to form a condensed ring by bonding between
W.sub.1 and W.sub.2 or W.sub.11 and W.sub.12; R.sub.1 and R.sub.11
are each an aliphatic group or a non-metallic atom group necessary
to form a condensed ring by bonding between R.sub.1 and W.sub.3 or
R.sub.11 and W.sub.14; V.sub.1 to V.sub.9, and V.sub.11 to V.sub.13
each are independently a hydrogen atom, a halogen atom, an amino
group, an alkylthio group, an arylthio group, a lower alkyl group,
a lower alkoxy group, an aryl group, an aryloxy group, a
heterocyclic group or a non-metallic atom group necessary to form a
5- to 7-membered ring by bonding between V.sub.1 and V.sub.3,
V.sub.2 and V.sub.4, V.sub.3 and V.sub.5, V.sub.2 and V.sub.6,
V.sub.5 and V.sub.7, V.sub.6 and V.sub.8, V.sub.7 and V.sub.9, or
V.sub.11 and V.sub.13, provided that at least one of V.sub.1 to
V.sub.9 and at least one of V.sub.11 to V.sub.13 are a group other
than a hydrogen atom; X.sub.1 and X.sub.11 each are an ion
necessary to compensate for an intramolecular charge; l1 and l11
each an ion necessary to compensate for an intramolecular charge;
k1 and k2 each are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11
each are 1 or 2, provided that the sum of p1 and q1 and the sum of
p11 and q11 are respectively not more than 2; 58wherein Y.sub.21,
Y.sub.22 and Y.sub.31 each are independently an oxygen atom, a
sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or --CH.dbd.CH--
group, in which Ra and Rb each are a hydrogen atom, a lower alkyl
group or an atomic group necessary to form an aliphatic spiro ring
between Ra and Rb; R.sub.21, R.sub.22, R.sub.31 and R.sub.32 each
are independently an aliphatic group; Rc and Rd each are
independently an unsubstituted lower alkyl group, a cycloalkyl
group, an aralkyl group, an aryl group or a heterocyclic group;
W.sub.21, W.sub.22, W.sub.23, W.sub.24, W.sub.31, W.sub.32,
W.sub.33 and W.sub.34 each are independently a hydrogen atom, a
substituent or a non-metallic atom group necessary to form a
condensed ring by bonding between W.sub.21 and W.sub.22, W.sub.23
and W.sub.24, W.sub.31 and W.sub.32, or W.sub.33 and W.sub.34;
V.sub.21 to V.sub.29, and V.sub.31 to V.sub.33 each are
independently a hydrogen atom, a halogen atom, an amino group, an
alkylthio group, an arylthio group, a lower alkyl group, a lower
alkoxy group, an aryl group, an aryloxy group, a heterocyclic group
or a non-metallic atom group necessary to form a 5- to 7-membered
ring by bonding between V.sub.21 and V.sub.23, V.sub.22 and
V.sub.24, V.sub.23 and V.sub.25, V.sub.24 and V.sub.26, V.sub.25
and V.sub.27, V.sub.26 and V.sub.28, V.sub.27 and V.sub.29, or
V.sub.31 and V.sub.33; X.sub.21 and X.sub.31 each are an ion
necessary to compensate for an intramolecular charge; l21 and l31
each an ion necessary to compensate for an intramolecular charge;
k21 and k22 each are 0 or 1; n21, n22, n31 and n32 each are 0, 1 or
2, provided that n21 and n22, or n31 and n32 are not 0 at the same
time.
24. The image forming method of claim 23, wherein said compound is
represented by formula (1) or (2).
25. The image forming method of claim 24, wherein said compound is
represented by the following formula (1-1) or (2-1): 59wherein
Y.sub.1, Y.sub.2 and Y.sub.11 each are independently an oxygen
atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or
--CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen atom, a
lower alkyl group or an atomic group necessary to form an aliphatic
spiro ring when Ra and Rb are linked with each other; Z.sub.1 is an
atomic group necessary to form a 5- or 6-membered ring; R is a
hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group,
a lower alkoxy group, an aryl group, a hydroxy group or a halogen
atom; W.sub.1, W.sub.2, W.sub.3, W.sub.4, W.sub.11, W.sub.12,
W.sub.13 and W.sub.14 each are independently a hydrogen atom, a
substituent or a non-metallic atom group necessary to form a
condensed ring by bonding between W.sub.1 and W.sub.2 or W.sub.11
and W.sub.12; R.sub.1 and R.sub.11 are each an aliphatic group or a
non-metallic atom group necessary to form a condensed ring by
bonding between R.sub.1 and W.sub.3 or R.sub.11 and W.sub.14;
L.sub.1 to L.sub.9, and L.sub.11 to L.sub.15 each are independently
a methine group; X.sub.1 and X.sub.11 each are an ion necessary to
compensate for an intramolecular charge; l1 and l11 each an ion
necessary to compensate for an intramolecular charge; m1 to m3 each
are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2,
provided that the sum of p1 and q1 and the sum of p11 and q11 are
respectively not more than 2.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to an infrared-sensitizing dye
and infrared-sensitive photographic materials by the use thereof
and in particular to a photographic material and a thermally
developable photothermographic material by the use of an
infrared-sensitive silver halide emulsion exhibiting a high
sensitivity, a low fog and reduced variation in sensitivity
following storage.
BACKGROUND OF THE INVENTION
[0002] There are known silver halide photographic light sensitive
materials employing silver halide grains and photo-recording
materials employing photopolymerization or cleavage reaction.
However, the longest photosensitivity edge of the silver halide
grains is in the vicinity of 500 nm and the photosensitivity region
of photopolymers is in a ultraviolet region so that spectral
sensitization by use of dyes is indispensable to provide
sensitivity at the loner wavelength side. Particularly with recent
progress in light sources, importance of photosensitive materials
sensitive to the laser wavelength region increases in the field of
recording materials for industrial use. Further in the field of
picture-taking photosensitive materials are noted infrared
photosensitive materials used for recording environment information
and superior in portrayability.
[0003] There are known a number of compounds as a sensitizing dye
or spectral sensitizing dye, including cyanine dyes and merocyanine
dyes described in T. H. James "The Theory of the Photographic
Process" Fourth ed. (1977, Macmillan Co. N.Y.) pages 194-234; F. M.
Hammer "The Cyanine Dyes and Related Compounds" (1964, John Wiley
& Sons, N.Y.); D. M. Sturmer "The Chemistry of Heterocyclic
Compounds" vol. 30, page 441 (1977, John Wiley & Sons, N.Y.);
JP-A 3-138638, 3-163440, 5-72660, 5-72661, 5-88292, 8-194282,
9-166844, 9-281631, 9-282672, 9-292673 and 10-73900 (hereinafter,
the term, JP-A means a unexamined and published Japanese Patent
Application); U.S. Pat. Nos. 2,320,439, 2,398,999, 2,734,900,
3,582,344, 4,536,473, 4,740,455, 4,835,096, and 5,393,654; British
Patent 774,779, 625,245, and 895,930; European Patent 420,012 and
821,811.
[0004] These sensitizing dyes and spectral sensitizing dyes are
required not only to expand spectral sensitivity region but also to
satisfy the following conditions:
[0005] 1) optimum spectral sensitization region,
[0006] 2) high spectral sensitization efficiency (sensitivity),
[0007] 3) no unfavorable interaction with other additives such as a
stabilizer, antifoggant, coating aid, high boiling solvent and
binder,
[0008] 4) no adverse effect on the characteristic curve such as
fogging or contrast variation,
[0009] 5) no variation in photographic performance such as
reduction in a S/N ratio or sensitivity when the dye containing
photosensitive material is aged (particularly when aged at a high
temperature or high humidity),
[0010] 6) no diffusion of an added sensitizing dye to a different
photosensitivity layer, causing color mixing, and
[0011] 7) removal or discoloration of the dye after development,
fixing and washing, causing no color stain.
[0012] However, commonly known spectrally sensitizing dyes have not
satisfied these conditions to sufficiently satisfactory levels.
Specifically, photosensitive materials to be recorded by using a
laser light source are desired to have a high absorption fitted to
the bright line wavelengths. However, a dye having an absorption in
the region of red to infrared contains a long conjugated chain and
is so susceptible to environments that although exhibiting a high
molar extinction coefficient in a solution, phenomena easily occur
such that the dye discolors during the preparation process or
causes a number of conformational changes, forming a broad
absorption spectrum exhibiting a low absorption maximum. Further,
the energy gap between the lowest unoccupied level and the highest
occupied level is so narrow that the lowest unoccupied level and
the highest occupied level are close to the conduction band level
of silver halide grains, producing problems that fogging easily
occur or sensitivity is reduced.
[0013] Accordingly, there are desired an infrared-sensitive
recording material exhibiting high sensitivity in the region of red
to infrared and further an infrared sensitive recording material
exhibiting high sensitivity and low fog and reduced variation in
performance even when being aged.
[0014] Infrared sensitizing dyes generally exhibit a lower
adsorption to silver halide grains than dyes sensitizing to the
visible region, producing problems such as low sensitivity or
marked desensitization during pre-exposure storage during standing
in the form of a solution in the process of preparing a coating
solution. There have been made various attempts of overcoming these
problems by varying the structure of the dye. However, disclosed
dyes have not yet reached levels solving the problems.
SUMMARY OF THE INVENTION
[0015] Accordingly, an object of the present invention is to
provide an image forming composition exhibiting a high sensitivity
to infrared laser light exposure and an image forming method by the
use thereof, and in particular an infrared sensitive silver halide
emulsion exhibiting a high sensitivity and low fog and superior in
storage stability, a silver halide photographic light sensitive
material and thermally developable photosensitive material
containing the emulsion and an image forming method by the use of
the materials.
[0016] An object of the invention is to provide a thermally
developable photosensitive material exhibiting a high sensitivity
and reduced desensitization during pre-exposure storage and
preparation method thereof.
[0017] An object of the invention is to provide a thermally
developable photosensitive material exhibiting little variation in
photographic performance even when a standing time of a
photosensitive solution is extended during the preparation thereof,
in particular, a preparation method of the photosensitive solution
and a coating method thereof.
[0018] An object of the invention is to provide an image recording
method and image forming method by use of a thermally developable
photosensitive material accomplishing the objects described
above.
[0019] The above objects of the invention can be accomplished by
the following constitution:
[0020] 1. A spectral sensitizing dye represented by the following
formulas (1) to (4): 2
[0021] wherein Y.sub.1, Y.sub.2 and Y.sub.11 each are independently
an oxygen atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group
or --CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen
atom, a lower alkyl group or an atomic group necessary to form an
aliphatic spiro ring between Ra and Rb; Z.sub.1 is an atomic group
necessary to form a 5- or 6-membered ring; R is a hydrogen atom, a
lower alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy
group, an aryl group, a hydroxy group or a halogen atom; W.sub.1,
W.sub.2, W.sub.3, W.sub.4, W.sub.11, W.sub.12, W.sub.13 and
W.sub.14 each are independently a hydrogen atom, a substituent or a
non-metallic atom group necessary to form a condensed ring by
bonding between W.sub.1 and W.sub.2 or W.sub.11 and W.sub.12;
R.sub.1 and R.sub.11 are each an aliphatic group or a non-metallic
atom group necessary to form a condensed ring by bonding between
R.sub.1 and W.sub.3 or R.sub.11 and W.sub.14; V.sub.1 to V.sub.9,
and V.sub.11 to V.sub.13 each are independently a hydrogen atom, a
halogen atom, an amino group, an alkylthio group, an arylthio
group, a lower alkyl group, a lower alkoxy group, an aryl group, an
aryloxy group, a heterocyclic group or a non-metallic atom group
necessary to form a 5- to 7-membered ring by bonding between
V.sub.1 and V.sub.3, V.sub.2 and V.sub.4, V.sub.3 and V.sub.5,
V.sub.2 and V.sub.6, V.sub.5 and V.sub.7, V.sub.6 and V.sub.8,
V.sub.7 and V.sub.9, or V.sub.11 and V.sub.13, provided that at
least one of V.sub.1 to V.sub.9 and at least one of V.sub.11 to
V.sub.13 are a group other than a hydrogen atom; X.sub.1 and
X.sub.11 each are an ion necessary to compensate for an
intramolecular charge; l1 and l11 each an ion necessary to
compensate for an intramolecular charge; k1 and k2 each are 0 or 1;
p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided
that the sum of p1 and q1 and the sum of p11 and q11 are
respectively not more than 2; 3
[0022] wherein Y.sub.21, Y.sub.22 and Y.sub.31 each are
independently an oxygen atom, a sulfur atom, a selenium atom,
--C(Ra)(Rb)-- group or --CH.dbd.CH-- group, in which Ra and Rb each
are a hydrogen atom, a lower alkyl group or an atomic group
necessary to form an aliphatic spiro ring between Ra and Rb;
R.sub.21, R.sub.22, R.sub.31 and R.sub.32 each are independently an
aliphatic group; Rc and Rd each are independently an unsubstituted
lower alkyl group, a cycloalkyl group, an aralkyl group, an aryl
group or a heterocyclic group; W.sub.21, W.sub.22, W.sub.23,
W.sub.24, W.sub.31, W.sub.32, W.sub.33 and W.sub.34 each are
independently a hydrogen atom, a substituent or a non-metallic atom
group necessary to form a condensed ring by bonding between
W.sub.21 and W.sub.22, W.sub.23 and W.sub.24, W.sub.31 and
W.sub.32, or W.sub.33 and W.sub.34; V.sub.21 to V.sub.29, and
V.sub.31 to V.sub.33 each are independently a hydrogen atom, a
halogen atom, an amino group, an alkylthio group, an arylthio
group, a lower alkyl group, a lower alkoxy group, an aryl group, an
aryloxy group, a heterocyclic group or a non-metallic atom group
necessary to form a 5- to 7-membered ring by bonding between
V.sub.21 and V.sub.23, V.sub.22 and V.sub.24, V.sub.23 and
V.sub.25, V.sub.24 and V.sub.26, V.sub.25 and V.sub.27, V.sub.26
and V.sub.28, V.sub.27 and V.sub.29, or V.sub.31 and V.sub.33;
X.sub.21 and X.sub.31 each are an ion necessary to compensate for
an intramolecular charge; l21 and l31 each an ion necessary to
compensate for an intramolecular charge; k21 and k22 each are 0 or
1; n21, n22, n31 and n32 each are 0, 1 or 2, provided that n21 and
n22, or n31 and n32 are not 0 at the same time;
[0023] 2. The spectral sensitizing dye described 1 above, wherein
the dye is represented by formula (1) or (2);
[0024] 3. The spectral sensitizing dye described in 2 above,
wherein the dye is represented by the following formula (1-1) or
(2-1): 4
[0025] wherein Y.sub.1, Y.sub.2 and Y.sub.11 each are independently
an oxygen atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group
or --CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen
atom, a lower alkyl group or an atomic group necessary to form an
aliphatic spiro ring when Ra and Rb are linked with each other;
Z.sub.1 is an atomic group necessary to form a 5- or 6-membered
ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an
aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group
or a halogen atom; W.sub.1, W.sub.2, W.sub.3, W.sub.4, W.sub.11,
W.sub.12, W.sub.13 and W.sub.14 each are independently a hydrogen
atom, a substituent or a non-metallic atom group necessary to form
a condensed ring by bonding between W.sub.1 and W.sub.2 or W.sub.11
and W.sub.12; R.sub.1 and R.sub.11 are each an aliphatic group or a
non-metallic atom group necessary to form a condensed ring by
bonding between R.sub.1 and W.sub.3 or R.sub.11 and W.sub.14;
L.sub.1 to L.sub.9, and L.sub.11 to L.sub.15 each are independently
a methine group; X.sub.1 and X.sub.11 each are an ion necessary to
compensate for an intramolecular charge; l1 and l11 each an ion
necessary to compensate for an intramolecular charge; m1 to m3 each
are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2,
provided that the sum of p1 and q1 and the sum of p1 and q11 are
respectively not more than 2;
[0026] 4. The spectral sensitizing dye described in 1 above,
wherein the dye is represented by formula (3) or (4);
[0027] 5. The spectral sensitizing dye described 4 above, wherein
the dye is represented by formula (3);
[0028] 6. A silver halide photographic material comprising a
support having thereon at least a photosensitive layer containing a
silver halide emulsion layer, wherein said photosensitive layer
contains a compound represented by the formulas (1) to (4)
described above;
[0029] 7. The photographic material described in 6 above, wherein
the compound is represented by formula (1) or (2);
[0030] 8. The photographic material described in 7 above, wherein
the compound is represented by the formula (1-1) or (2-1) described
above;
[0031] 9. The photographic material described in 6 above wherein
the compound is represented by the formula (3) or (4) described
above;
[0032] 10. The photographic material described in 9 above, wherein
the compound is represented by the formula (3) described above;
[0033] 11. The photographic material described in 10 above, wherein
the photosensitive layer further contains a compound represented by
the following formula (5): 5
[0034] wherein Y.sub.4 and Y.sub.42 each are independently an
oxygen atom, a sulfur atom, a selenium atom, --C(Ra)(Rb)-- group or
--CH.dbd.CH-- group, in which Ra and Rb each are a hydrogen atom, a
lower alkyl group or an atomic group necessary to form an aliphatic
spiro ring together with Ra and Rb; R.sub.41 and R.sub.42 each are
independently an aliphatic group; Re and Rf each are independently
an unsubstituted lower alkyl group, cycloalkyl group, aralkyl
group, aryl group or heterocyclic group; W.sub.41, W.sub.42,
W.sub.43, and W.sub.44 each are independently a hydrogen atom, a
substituent or a non-metallic atom group necessary to form a
condensed ring by bonding between W.sub.41 and W.sub.42, W.sub.43
and W.sub.44; L.sub.41 to L.sub.49 are each a methine group;
X.sub.41 is an ion necessary to compensate for an intramolecular
charge; l41 is an ion necessary to compensate for an intramolecular
charge; m42 and m43 each are 0 or 1; n41 and n42 each are 0, 1 or
2, provided that n41 and n42 are not 0 at the same time;
[0035] 12. The photographic material described in 9 above, wherein
said compound is represented by the formula (4) described
above;
[0036] 13. The photographic material described in 12 above, wherein
the photosensitive layer further contains a compound represented by
formula (6): 6
[0037] wherein Y.sub.51 is independently an oxygen atom, a sulfur
atom, a selenium atom, --C(Ra)(Rb)-- group or --CH.dbd.CH-- group,
in which Ra and Rb each are a hydrogen atom, a lower alkyl group or
an atomic group necessary to form an aliphatic Spiro ring together
with Ra and Rb; R.sub.51 and R.sub.52 each are independently an
aliphatic group; Re and Rf each are independently an unsubstituted
lower alkyl group, cycloalkyl group, aralkyl group, aryl group or
heterocyclic group; W.sub.51, W.sub.52, W.sub.53 and W.sub.54 each
are independently a hydrogen atom, a substituent or a non-metallic
atom group necessary to form a condensed ring by bonding between
W.sub.51 and W.sub.52, or W.sub.53 and W.sub.54; L.sub.51 to
L.sub.55 are each a methine group; X.sub.51 is an ion necessary to
compensate for an intramolecular charge; l51 is an ion necessary to
compensate for an intramolecular charge; n51 and n52 each are 0, 1
or 2, provided that n51 and n52 are not 0 at the same time;
[0038] 14. The photographic material described in 6 above, wherein
the photosensitive layer further contains an organic silver salt
and a reducing agent;
[0039] 15. The photographic material described in 14 above, wherein
the compound is represented by the formula (1) or (2) described
above;
[0040] 16. The photographic material described in 15 above, wherein
the compound is represented by the formula (1-1) or (2-1) described
above;
[0041] 17. The photographic material described in 14 above, wherein
the compound is represented by the formula (3) or (4) described
above;
[0042] 18. The photographic material described in 17, wherein the
compound is represented by the formula (3) described above;
[0043] 19. The photographic material described in 18 above, wherein
the photosensitive layer further contains a compound represented by
the formula (5) described above;
[0044] 20. The photographic material described in 17 above, wherein
the compound is represented by the formula (4) described above;
[0045] 21. The photographic material described in 20 above, wherein
the photosensitive layer further contains a compound represented by
the formula (6)described above;
[0046] 22. The photographic material described in 14 above, wherein
the photographic material further has a non-photosensitive layer,
said non-photosensitive layer containing a binder, a phthalazine
compound, a benzenepolycarboxylic acid or an acid anhydride
compound;
[0047] 23. An image forming method comprising exposing a
photosensitive material to laser, the photosensitive material
comprising a support having thereon at least a photosensitive layer
containing a compound represented by the formulas (1) to (4)
described above;
[0048] 24. The image forming method described in 23 above, wherein
the compound is represented by the formula (1) or (2) described
above;
[0049] 25. The image forming method described in 24 above, wherein
said compound is represented by the formula (1-1) or (2-1 described
above.
DETAILED DESCRIPTION OF THE INVENTION
[0050] The invention will be further described. It was found
according to the inventors of the invention that the invention was
accomplished by the use of the compounds represented by formulas
(1) to (6) as an infrared sensitizing dye or an infrared sensitizer
dye.
[0051] One feature of the infrared sensitizing dye according to the
invention concerns a three ring-condensed heterocyclic nucleus
formed by bonding between a nitrogen atom contained in a
benzothiazole ring and a carbon atom at the peri-position; and
another feature is a long chain polymethine dye, in which a
sulfonyl group is substituted on the benzene ring of the
benzothiazole ring, leading to high sensitivity, low fogging and
superior storage stability.
[0052] The infrared sensitive silver halide emulsion used in the
invention refers to a silver halide emulsion exhibiting sensitivity
to light having the wavelengths longer than the visible light
wavelengths of 400 to 700 nm. The infrared sensitive silver halide
light sensitive material used in the invention refers to a light
sensitive material capable of forming a black-and-white image
through developing, fixing and washing; a light sensitive material
having an emulsion layer containing a coupler, a colored coupler or
a DIR compound and capable of forming a color image through
developing, bleach-fixing and washing; or a light sensitive
material capable of forming an image upon thermal development
without being subjected to wet processing, i.e., thermally
developable photosensitive material.
[0053] The compounds represented by formula (1) to (6) will be
described below.
[0054] The 5- or 6-membered condensed rings completed by an atomic
group represented by Z.sub.1 include a condensed cyclohexene ring,
a condensed benzene ring, a condensed thiophene ring, a condensed
pyridine ring, and a condensed naphthalene ring. Exemplary examples
thereof include a benzoxazole ring, tetrahydrobenzoxazole ring,
naphthooxazole ring, benzonephthooxazole ring, benzothiazole ring,
tetrahydrobenzothiazole ring, naphthothiazole ring,
benzonaphthothiazole ring; thienothiazole ring,
thianaphthenothiazole ring, pyridothiazole ring, benzoselenazole
ring, tetrahydrobenzoselenazole ring, naphthoselenazole ring,
benzonaphthoselenazole ring, quinoline ring, 3,3-dialkylindolenine
and 3,3-dialkylpyridopyrroline. Any substituent such as one
represented by W.sub.1 to W.sub.4 described later can be
substituted on the ring described above.
[0055] Examples of the aliphatic group represented by R.sub.1,
R.sub.11, R.sub.21, R.sub.22, R.sub.31, R.sub.32, R.sub.41,
R.sub.42, R.sub.51 and R.sub.52 include a branched or
straight-chained alkyl group having 1 to 10 carbon atoms (e.g.,
methyl, ethyl, propyl, butyl, pentyl, I-pentyl, 2-ethyl-hexyl,
octyl, decyl), an alkenyl group having 3 to 10 carbon atoms (e.g.,
2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl,
1-methyl-3-butenyl, 4-hexenyl), and an aralkyl group having 7 to 10
carbon atoms (e.g., benzyl, phenethyl). These groups may further be
substituted with a substituent, including groups such as a lower
alkyl group (e.g., methyl, ethyl, propyl), a halogen atom (e.g.,
fluorine atom, chlorine atom, or bromine atom), a vinyl group, an
aryl group (e.g., phenyl, p-tolyl, p-bromophenyl), trifluoromethyl,
an alkoxy group (e.g., methoxy, ethoxy, methoxyethoxy), an aryloxy
group (e.g., phenoxy, p-tolyloxy), cyano, a sulfonyl group (e.g.,
methanesulfonyl, trifluoromethansulfonyl), p-toluenesulfonyl), an
alkoxycarbonyl group (e.g., ethoxycarbonyl, butoxycarbonyl), an
amino group (e.g., amino, biscarboxymethylamino), an aryl group
(e.g., phenyl, carboxyphenyl), a heterocyclic group (e.g.,
tetrahydrofurfuryl, 2-pyrrolidinone-1-yl), an acyl group (e.g.,
acetyl, benzoyl), an ureido group (e.g., ureido, 3-methylureido,
3-phenylureido), a thioureido group (e.g., thioureido,
3-methylthioureido), an alkylthio group (e.g., methylthio,
ethylthio), an arylthio group (e.g., phenylthio), a
heterocyclic-thio group (e.g., 2-thienythio, 3-thienylthio,
2-imidazolylthio), a carbonyloxy group (e.g., acetyloxy,
propanoyloxy, benzoyloxy), an acylamino group (e.g., acetylamino,
benzoylamino); and hydrophilic groups, such as a sulfo group, a
carboxy group, a phosphono group, a sulfate group, hydroxy,
mercapto, sulfino group, a carbamoyl group (e.g., carbamoyl,
n-methylcarbamoyl, N,N-tetramethylenecarbamoyl), a sulfamoyl group
(e.g., sulfamoyl, N,N-3-oxapentamethylenaminosulfonyl), a
sulfonamido group (e.g., methanesulfonamido, butanesulfoneamido), a
sulfonylaminocarbonyl group(e.g., methanesulfonylaminocarbonyl,
ethanesulfonylaminocarbonyl), an acylaminosulfonyl group (e.g.,
acetoamidosulfonyl, methoxyacetoamidosulfonyl), an
acylaminocarbonyl group (e.g., acetoamidocarbonyl,
methoxyacetoamidocarbonyl), and a sulfinylaminocarbonyl group
(e.g., methasulfinylaminocarbonyl, ethanesulfinylaminocarbonyl).
Examples of aliphatic groups substituted by a hydrophilic group
include carboxymethyl, carboxypentyl, 3-sulfatobutyl,
3-sulfopropyl, 2-hydroxy-3-sulfopropyl, 4-sulfobutyl,
5-sulfopentyl, 3-sulfopentyl, 3-sulfinobutyl, 3-phosphonopropyl,
hydroxyethyl, N-methanesulfonylcarbamoylmethyl,
2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfobenzyl and
p-carboxybenzyl.
[0056] The lower alkyl group represented by R include a
straight-chained or branched one having 1 to 5 carbon atoms, such
as methyl, ethyl, @propyl, pentyl and isopropyl. The cycloalkyl
group includes, e.g., cyclopropyl, cyclobutyl and cyclopentyl. The
aralkyl group includes, e.g., benzyl, phenethyl,
p-methoxyphenylmethyl and o-acetylaminophenylethyl; the lower
alkoxy group includes one having 1 to 4 carbon atoms, including
methoxy, ethoxy, propoxy and i-propoxy; the aryl group includes
substituted or unsubstituted one, such as phenyl, 2-naphthyl,
1-naphthyl, o-tolyl, o-methoxyphenyl, m-chlorophenyl,
m-bromophenyl, p-tolyl and p-ethoxyphenyl. These groups may be
substituted by a substituent group, such as a phenyl group, a
halogen atom (e.g., fluorine atom, chlorine atom, bromine atom,
iodine atom), an alkoxy group or hydroxy.
[0057] The unsubstituted lower alkyl group represented by Ra or Rb
includes those which are cited in R described above.
[0058] The lower alkyl group represented by Rc, Rd, Re or Rf
includes a straight-chained or branched one having 1 to 5 carbon
atoms, such as methyl, ethyl, @propyl, pentyl and isopropyl. The
cycloalkyl group includes, e.g., cyclopropyl, cyclobutyl and
cyclopentyl. The aralkyl group includes, e.g., benzyl, phenethyl,
p-methoxyphenylmethyl and o-acetylaminophenyl-ethyl; the aryl group
includes substituted or unsubstituted one, such as phenyl,
2-naphthyl, 1-naphthyl, o-tolyl, o-methoxyphenyl, m-chlorophenyl,
m-bromophenyl, p-tolyl and p-ethoxyphenyl; and the heterocyclic
group includes substituted or unsubstituted one, such as 2-furyl,
5-methyl-2-furyl, 2-thienyl, 2-imidazolyl, 2-methyl-1-imidazolyl,
4-phenyl-2-thiazolyl, 5-hydroxy-2-benzothiazolyl, 2-pyridyl and
1-pyrrolyl. These groups, as described above, may be substituted by
a substituent group, such as a phenyl group, a halogen atom, an
alkoxy group or hydroxy.
[0059] Examples of the substituents represented by W.sub.1 to
W.sub.4, W.sub.11to W.sub.14, W.sub.21 to W.sub.24, W.sub.31 to
W.sub.34, W.sub.41 to W.sub.44 and W.sub.51 to W.sub.54 include an
alkyl group (e.g., methyl, ethyl, butyl, I-butyl), an aryl group
(including monocyclic and polycyclic ones such as phenyl and
naphthyl), a heterocyclic group (e.g., thienyl, furyl, pyridyl,
carbazolyl, pyrrolyl, indolyl), a halogen atom (e.g., fluorine
atom, chlorine atom, bromine atom, iodine atom), a vinyl group,
trifluoromethyl, an alkoxy group (e.g., methoxy, ethoxy,
methoxyethoxy), an aryloxy group (e.g., phenoxy, p-tolyloxy), a
sulfonyl group (e.g., methanesulfonyl, p-toluenesulfonyl), an
alkoxycarbonyl group (e.g., ethoxycarbonyl, butoxycarbonyl), an
amino group (e.g., amino, biscarboxymethylamino), an acyl group
(e.g., acetyl, benzoyl), an ureido group (e.g., ureido,
3-methylureido), a thioureido group (e.g., thioureido,
3-methylthioureido), an alkylthio group (e.g., methylthio,
ethylthio), an alkenyl thio group, an arylthio group (e.g.,
phenylthio), hydroxy and styryl.
[0060] These groups may be substituted by the same substituents as
described in the aliphatic group represented by R.sub.1. Examples
of substituted alkyl group include 2-methoxyethyl, 2-hydroxyethyl,
3-ethoxycarbonylpropyl, 2-carbamoylethyl, 2-methanesulfonylethyl,
3-methanesulfonylaminopropyl, benzyl, phenethyl, carboxymethyl,
carboxyethyl, allyl, and 2-furylethyl. Examples of substituted aryl
groups include p-carboxyphenyl, p-N,N-dimethylaminophenyl,
p-morpholinophenyl, p-methoxyphenyl, 3,4-dimethoxyphenyl,
3,4-methylenedioxyphenyl, 3-chlorophenyl, and p-nitrophenyl.
Further, examples of substituted heterocyclic group include
5-chloro-2-pyridyl, 2-ethoxycarbonyl-2-pyridyl and
5-carbamoyl-2-pyridyl. W.sub.1 and W.sub.2, W.sub.3 and W.sub.4,
W.sub.11 and W.sub.12, W.sub.13 and W.sub.14, W.sub.21 and
W.sub.22, W.sub.23 and W.sub.24, W.sub.31 and W.sub.32, W.sub.33
and W.sub.34, W.sub.41 and W.sub.42, W.sub.43 and W.sub.44,
W.sub.51 and W.sub.52 or W.sub.53 and W.sub.54 each pair may
combine to form a condensed ring, such as 5- or 6-membered
saturated or unsaturated condensed carbon rings, which are further
substituted by substituents as described in the aliphatic
group.
[0061] Among the groups represented by V.sub.1 to V.sub.9, V.sub.11
to V.sub.13, V.sub.21 to V.sub.29, and V.sub.31 to V.sub.33, the
halogen atom includes, e.g., a fluorine atom, chlorine atom,
bromine atom and iodine atom; the amino group includes, e.g.,
amino, dimethylamino, diphenylamino, and methylphenylamino; the
alkylthio group includes substituted and substituted ones, such as
phenylthio or m-fluorphenylthio; the lower alkyl group includes
straight-chained or branched one having five or less carbon atoms,
such as methyl, ethyl, propyl, butyl, pentyl or isopropyl; the
lower alkoxy group includes one having four or less carbon atoms,
such as methoxy, ethoxy, propoxy, or isopropoxy; the aryl group
includes substituted and unsubstituted ones, such as phenyl,
2-naphthyl, 1-naphthyl, o-tolyl, o-methoxyphenyl, m-chlorophenyl,
m-bromophenyl, p-tolyl, and p-ethoxyphenyl; the aryloxy group
includes substituted and unsubstituted ones, such as phenoxy,
p-tolyloxy, and m-carboxyphenyloxy; and the heterocyclic group
includes substituted or unsubstituted ones, such as 2-furyl,
5-methyl-2-furyl2-thienyl, 2-imidazolyl, 2-methyl-1-imidazolyl,
4-phenyl-2-thiazolyl, 5-hydroxy-2-benzothiazolyl, 2-pyridyl, and
1-pyrrolyl. These groups may further be substituted by a
substituent group, such as a phenyl group, a halogen atom, alkoxy
group, or hydroxy. V.sub.1 and V.sub.3, V.sub.2 and V.sub.4,
V.sub.3 and V.sub.5, V.sub.4 and V.sub.6, V.sub.5 and V.sub.7,
V.sub.6 and V.sub.8, V.sub.7 and V.sub.9, V.sub.11 and V.sub.13,
V.sub.21 and V.sub.23, V.sub.22 and V.sub.24, V.sub.23 and
V.sub.25, V.sub.24 and V.sub.26, V.sub.25 and V.sub.27, V.sub.26
and V.sub.28, V.sub.27 and V.sub.29, and V.sub.31 and V.sub.33 each
pair may combine to form a 5- to 7-membered ring, such as a
cyclopentene ring, cyclohexene ring, cycloheptene ring, and decalin
ring, each of which may further be substituted by a lower alkyl
group, lower alkoxy group or aryl group, as described in R.
[0062] The methylene group represented by L.sub.1 to L.sub.9,
L.sub.11 to L.sub.15, L.sub.41 to L.sub.49 and L.sub.51 to L.sub.55
each are a substituted or unsubstituted methylene group. Examples
of the substituent thereof include fluorine and chlorine atoms, a
substituted or unsubstituted lower alkyl group(e.g., methyl, ethyl,
I-propyl, benzyl), and a substituted or unsubstituted alkoxy group
(e.g., methoxy, ethoxy), a substituted or unsubstituted aryloxy
group (e.g., phenoxy, naphthoxy), a substituted or unsubstituted
aryl group (e.g., phenyl, naphthyl, p-tolyl, o-carboxyphenyl),
N(U.sub.1) (U.sub.2), -SRg, a substituted or unsubstituted
heterocyclic group [e.g., 2-thienyl, 2-furyl,
N,N'-bis(methoxyethyl)barbituric acid], in which Rg is a lower
alkyl group, an aryl group or a heterocyclic group and examples of
-SRg include methylthio, ethylthio, benzylthio, phenylthio and
tolylthio groups; U.sub.1 and U.sub.2 are each a substituted or
unsubstituted lower alkyl group or aryl group, provided that
V.sub.1 and V.sub.2 may combine to form a 5- or 6-membered nitrogen
containing heterocyclic ring (e.g., pyrazole ring, pyrrole ring,
pyrrolidine ring, morpholine ring, pyperizine ring, pyridine,
pyrimidine ring, etc.). Methylene groups which are adjacent or
distant by one may combine to form a 5- or 6-membered ring.
[0063] In cases where the compound represented by formulas (1) to
(6) is substituted with a cationic- or anionic-charged group, a
counter ion is formed by an anionic or cationic equivalent to
compensate an intramolecular charge. As an ion necessary to
compensate the intramolecular charge, which is represented by
X.sub.1, X.sub.11 , X.sub.21, X.sub.31, X.sub.41 or X.sub.51,
examples of cations include a proton, an organic ammonium ion
(e.g., triethylammonium, triethanolammonium) and inorganic cations
(e.g., cations of lithium, sodium and potassium); and examples of
acid anions include halide ions (e.g., chloride ion, bromide ion,
iodide ion), p-toluenesulfonate ion, perchlorate ion,
tetrafluoroborate ion, sulfate ion, methylsulfate ion, ethylsulfate
ion, methanesulfonate ion, trifluoromethanesulfonate ion).
[0064] The infrared sensitizing dye according to the invention is
characterized in that a three ring-condensed heterocyclic nucleus
is formed by bonding between a nitrogen atom contained in a
benzothiazole ring and a carbon atom at a peri-position; and that
the dye is a long chain polymethine dye, in which a sulfonyl group
is substituted on the benzene ring of the benzothiazole ring. It is
not definitely clarified why the use of these dyes leads to high
sensitivity, low fogging and superior storage stability. It is
assumed that the dye containing a three ring-condensed heterocyclic
ring easily form an aggregate of a stacking structure when forming
a dye structure. It is further assumed that a benzoazole ring
substituted with a sulfinyl or sulfonyl group contains a sulfur
atom exhibiting higher hydrophilicity and less interaction with
silver than a thioether, and an electron-withdrawing action of this
group lowers the ground state of the dye to advantageously prevent
direct influences such as fogging, leading to advantageous effects
such as antifogging or stabilization. Furthermore, the polarized
structure between an oxygen atom and a sulfur atom may
advantageously act on interaction between dye molecules,
stabilizing the dye aggregate.
[0065] Of spectral sensitizing dyes represented by formulas (3) to
(5) and (6), those which have a substituted methine chain are
preferred; and those which have a structure of forming a ring on
the methine chain are also preferred.
[0066] Exemplary examples of the sensitizing dyes represented by
formulas (1) to (4) and the sensitizing dyes represented by by
formulas (5) and (6) are shown below, but are not limited to these.
7 8
[0067] The infrared sensitizing dyes and spectral sensitizing dyes
described above can be readily synthesized according to the methods
described in F. M. Hammer, The Chemistry of Heterocyclic Compounds
vol.18, "The cyanine Dyes and Related Compounds" (A. Weissberger
ed. Interscience Corp., New York, 1964); J. Ber., 64, 1664-1674
(1931); Ukrain. Khim. Zhur., 21, 744-749 (1955); British patents
625,245 and 895,930; U.S. Pat. Nos. 2,320,439 and 2,398,999.
[0068] Synthesis of the compounds described above are exemplarily
explained as below.
Synthesis Example 1 Synthesis of Compound No. S-4
[0069] In 2.5 ml of m-cresol was dissolved 4.51 g (0.02 molw) of
5,6-dihydro-2-methyl-4H-thoazolo[5,4,3-ij]quinolinium hydrochloric
acid salt, which was synthesized according to the method described
in Ukrain. Khim. Zhur., 21, 744-749 (1955) and 2.0 g (0.01 mole) of
2,7-dimethoxy-1,4,5,8-tetrahydronaphthalene was added thereto and
heated in an oil bath at 120.degree. C. for 10 min., while
stirring. Subsequently, 50 ml ethanol and 1 g triethylamine was
further added thereto and heated in a water bath at 70.degree. C.
for 30 min., while stirring. To the reaction mixture was added 1 g
of sodium tetrafluoroborate and cooled with stirring to form
precipitates. The resulting crystals were separated from the
solution by filtration and were recrystallized from a mixed solvent
of fluoroalcohol and methanol to obtain 0.41 g purified product.
Mass spectrum gave a molecular ion peak at 507, which was in
agreement with a molecular weight of the intended structure. The
absorption maximum in methanol was 744.4 nm (.epsilon.:
221,000).
Synthesis Example 2 Synthesis of Compound No. S-11
[0070] Synthesis of intermediate
{3-ethyl-2-[(7-methoxy-3,4,5,6-tetrahydro-
-1H-2-naphthylidene)methyl]-5-methylthiobenzothiazolium-p-toluenesulfonate-
}
[0071]
3-ethyl-2-methyl-5-methylthiobenzothiazolium-p-tolyenesulfonate of
19.75 g (0.05 mole) and 2,7-dimethoxy-1,4,5,8-tetrahydronaphthalene
of 28.8 g (0.15 mole) were mixed in 40 ml dimethylsulfoxide and
heated in a oil bath at 120.degree. C. for 15 min, while stirring.
The reaction mixture was added with ethyl acetate, diluted to five
times and crystallized out of solution upon sufficiently cooling.
The crystals was separated from the solution by filtration and
washed with ethyl acetate to obtain 16.2 g of substituted product.
The produced intermediate exhibited an absorption maximum at 496 nm
in methanol(.epsilon.: 57,700).
[0072] Dye condensation
[0073] 5,6-Dihydroxy-2-methyl-4H-thiazolo[5,4,3-ij]quinolinium
hydrochloric acid salt of 10.4 g, p-toluenesulfonic acid ethyl
ester of 2.26 g (0.01 mole) and
3-ethyl-2-[(7methyl-3,4,5,6-tetrahydro-1H-2-naphth-
ylidene)methyl]-5-methylthiobenzothiazolium-p-toluenesulfonate of
5.56 g (0.01 mole) were dissolved in 5.0 ml m-cresol and heated in
an oil bath at 120.degree. C. for 15 min., while stirring.
Subsequently, 100 ml ethanol and 2 g triethylamine were added
thereto and heated in a water bath at 80.degree. C. for 30 min.,
while stirring. The reaction mixture was added with 2 g of sodium
tetrafluoroborate and crystallized out of solution upon cooling
with stirring. The crystals were separated from the solution by
filtration, washed with water and recrystallized from mixed
solvents of fluoroalcohol and methanol to obtain 1.1 g purified
product. Mass spectrum gave a molecular ion peak at 541, which was
in agreement with a molecular weight of the intended structure. The
absorption maximum in methanol was 749.50 nm (.epsilon.:
193,000).
Synthesis Example 3 Synthesis of Compound No. S-43
[0074] Synthesis of intermediate 1
(2-methyl-5-methylsulfonyl-benzothiazol- e)
[0075] In 100 ml methanol was dissolved 3.9 g (0.02 mole) of
2-methyl-5-methylthiobenzothiazole and 100 ml aqueous solution
containing 5.2 g (0.024 mole) sodium periodate was added thereto
and stirred at room temperature for 1 hr. The reaction mixture was
condensed under reduced pressure to remove methanol, an aqueous 5%
sodium hydrogen carbonate solution was added to make weak alkaline,
was further added with sodium chloride and extracted with ethyl
acetate. The extracted solution was condensed and the resulting
precipitates were separated from solution by filtration. Crystals
were purified by recrystallization from mixed solvents of ethyl
acetate and n-hexane (at a yield of 75%), exhibiting a melting
point of 95.97.degree. C.
[0076] Synthesis of intermediate 2
(3-ethyl-2-methyl-5-methylsulfinylbenzo-
thiazolium-p-toluenesulfonate)
[0077] 2-Methyl-5-methylsulfinylbenzothiazole of 2.1 g (0.01 mole)
and ethyl p-toluenesulfonate of 2.4 g (0.012 mole) were mixed and
heated in an oil bath at 120 to 130.degree. C. for 8 hrs. The
reaction mixture was separated by means of column chromatography
using silica gel and mixed solvents of ethyl acetate/methanol (2:1)
and eluted with methanol solution. To the methanol eluate was added
activated carbon, stirred and separated by filtration. The
resulting filtrate was condensed under reduced pressure and dried
to obtain 1.7 g of intended viscous solid substance. This
intermediate compound was used in the following dye condensation
reaction without purification.
[0078] Dye condensation
[0079]
3-ethyl-2-methyl-5-methylsulfinylbenzothiazolium-p-toluenesulfonate
of 1.6 g (0.004 mole) and
2,7-dimethoxy-1,4,5,8-tetrahydronaphthalene of 0.3 g (0.0015 mole)
were dissolved in 0.5 m-cresol and heated in an oil bath at
120.degree. C. for 15 min., while stirring. Subsequently, 5 ml
ethanol and 0. g triethylamine were added thereto and heated in a
water bath at 80.degree. C. for 10 min., while stirring. The
reaction mixture was added with 4 ml of aqueous 50% ethanol
solution containing 0.4 g of sodium tetrafluoroborate and
crystallized out of solution upon cooling with stirring. The
crystals were separated from the solution by filtration, washed
with water and recrystallized from mixed solvents of fluoroalcohol
and methanol to obtain 0.15 g purified product. Mass spectrum gave
a molecular ion peak at 607, which was in agreement with a
molecular weight of the intended structure. The absorption maximum
in methanol was 747.30 nm (.epsilon.: 228,000).
[0080] The sensitizing dye used in the invention may be used alone
or in combination. Specifically, a combination of dyes represented
by formula (3) and (5), and a combination of dyes represented by
formulas (4) and (6) are preferred. In either case when used alone
or used in combination, the total amount of the dye(s) to be
incorporated is preferably 1.times.10.sup.-6 to 5.times.10.sup.-3,
more preferably 1.times.10.sup.-5 to 2.5.times.10.sup.-3, and still
more preferably 4.times.10.sup.-5 to 1.times.10.sup.-3 mol per mol
of silver halide.
[0081] In cases when dyes are used in combination, the dyes can be
incorporated in any proportion. The dye may be directly dispersed
in a silver halide emulsion. Alternatively, the may be dissolved in
an appropriate solvent such as methanol, ethanol, n-propanol,
methyl cellosolve, acetone, water, pyridine, or a mixture thereof
and added to the emulsion in the form of a solution. Ultrasonic can
also be employed. The sensitizing dye can be added in such a manner
that a dye is dissolved in a volatile organic solvent, the
resulting solution is dispersed in a hydrophilic colloidal medium
and the dispersion is added to the emulsion, as described in U.S.
Pat. No. 3,469,987; a water-insoluble dye is dispersed in aqueous
medium without being dissolved and the dispersion is added to the
emulsion, as described in JP-B 46-24185 (hereinafter, the term,
JP-B means a published Japanese Patent); a dye is dissolved using a
surfactant and the resulting solution is added to the emulsion, as
described in U.S. Pat. No. 3,822,135; a dye is dissolved using a
compound capable of shifting to longer wavelengths and the solution
is added to the emulsion, as described in JP-A 51-74624; or a dye
is dissolved in an acid substantially containing no water and the
solution is added to the emulsion, as described in JP-A 50-80826.
Further, the dye may be added according to the method described in
U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287 and 3,492,835. The
dye may be homogeneously dispersed in a silver halide emulsion
before coating on a support, or may be dispersed at any stage of
preparing the silver halide emulsion.
[0082] In cases when used in combination, the dyes can be
independently or in the form of a mixture dispersed in a silver
halide emulsion. Together with the dye(s), a visible
region-absorbing dye capable of exhibiting supersensitization, a
dye not exhibiting supersensitization, or a compound having no
absorption in the visible region may be incorporated into the
emulsion. Usable sensitizing dyes and substances exhibiting
supersensitization in combination with the dye are described in
Research Disclosure (hereinafter, also denoted as "RD") vol. 176,
item 17643 (December, 1978) page 23, section IV-J; JP-B 49-15500
and 43-4933; and JP-A 59-19032, 3-15049 and 62-123454.
[0083] Techniques described in Research Disclosure No. 308119
(hereinafter, also denoted such as RD 308119) are applicable to the
silver halide emulsions used in the invention, as shown below. The
silver halide emulsions include those which are used in color and
black-and-white photographic light sensitive materials.
1 Item RD 308119 Iodide 993, I-A Preparing method 993, I-A; 994,
I-E Crystal habit (regular crystal) 993, I-A Crystal habit (twinned
crystal) 993, I-A Epitaxial 993, I-A Halide composition (uniform)
993, I-B Halide composition (non-uniform) 993, I-B Halide
conversion 994, I-C Halide substitution 994, I-C Metal occlusion
994, I-D Grain size distribution 995, I-F Solvent addition 995, I-F
Latent image forming site (surface) 995, I-G Latent image forming
site (internal) 995, I-G Photographic material (negative) 995, I-H
Photographic material (positive) 995, I-H Emulsion blending 995,
I-J Desalting 995, II-A
[0084] The silver halide emulsion according to the invention is
subjected to physical ripening, chemical ripening and spectral
sensitization. As additives used in these processes are shown
compounds described in Research Disclosure No. 17643, No. 18716 and
No. 308119 (hereinafter, denoted as RD 17643, RD 18716 and RD
308119), as below.
2 Item RD 308119 RD 17643 RD 18716 Chemical Sensitizer 996, III-A
23 648 Spectral Sensitizer 996, IV-A-A,B,C, 23-24 648-9 D,H,I,J
Super Sensitizer 996, IV-A-E,J 23-24 648-9 Antifoggant 998, VI
24-25 649 Stabilizer 998, VI 24-25 649
[0085] Photographic additives usable in the invention are also
described, as below.
3 Item RD 308119 RD 17643 RD 18716 Anti-staining agent 1002, VII-I
25 650 Dye Image-Stabilizer 1001, VII-J 25 Whitening Agent 998, V
24 U.V. Absorbent 1003, VIII-C, 25-26 XIII-C Light Absorbent 1003,
VIII 25-26 light-Scattering 1003, VIII Agent Filter Dye 1003, VIII
25-26 Binder 1003, IX 26 651 Antistatic Agent 1006, XIII 27 650
Hardener 1004, X 26 651 Plasticizer 1006, XII 27 650 Lubricating
Agent 1006, XII 27 650 Surfactant, Coating aid 1005, XI 26-27 650
Matting Agent 1007, XVI Developing Agent 1001, XXB (included in
photographic material)
[0086] A variety of couplers can be employed in the invention and
examples thereof are described in research Disclosures described
above. Relevant description portions are shown below.
4 Item RD 308119 RD 17643 Yellow coupler 1001, VII-D 25,
VII-C.about.G Magenta coupler 1001, VII-D 25, VII-C.about.G Cyan
coupler 1001, VII-D 25, VII-C.about.G Colored coupler 1002, VII-G
25, VII-G DIR coupler 1001, VII-F 25, VII-F BAR coupler 1002, VII-F
PUG releasing coupler 1001, VII-F Alkali-soluble coupler 1001,
VII-E
[0087] Additives used in the invention can be added by dispersing
methods described in RD 308119 XIV. In the invention are employed
supports described in RD 17643, page 28; RD 18716, page 647-648;
and RD 308119 XIX. In the photographic material according to the
invention, there can be provided auxiliary layers such as a filter
layer and interlayer, as described in RD 308119 VII-K, and arranged
a variety of layer orders such as normal layer order, reverse layer
order and unit layer arrangement.
[0088] Silver halide photographic light sensitive materials used in
the invention can be processed by use of commonly known developing
agents described in T. H. James, The Theory of the Photographic
Process, Fourth edition, page 291 to 334; and Journal of American
Chemical Society, 73, 3100 (1951), including, e.g., hydroquinone,
p-aminophenol, N-methyl-p-aminophenol, 2,4-aminophenol,
2,4-diaminophenol as described in JP-A 4-15641;
1-phenyl-3-pyrazolidones such as 1-phenyl-3-pyrazolidone- ,
1-phenyl-4-methyl4-hydroxymethyl-3-pyrazolidone, and
5,5-dimethyl-1-phenyl-3-pyrazolidone and according the conventional
method described in RD17643, pages 28-29, RD18716, page 615 and
RD308119, XIX.
[0089] Infrared sensitizing dyes used in the invention can also be
advantageously applicable to thermally developable photosensitive
materials. As is conducted in the techniques of conventional silver
halide emulsions, after the dye is allowed to adsorb onto silver
halide grains, the silver halide grain emulsion may be mixed with
an organic silver salt. Alternatively, after an organic silver salt
and silver halide are mixed, the dye may be added thereto in a
manner similar to the conventional silver halide emulsions
described above. Plural dyes may be used to perform
supersensitization. For example, the infrared sensitizing dye may
be used in combination with sensitizing dyes described in RD17643
section IV-X (December 1978, page 23) and Rd18431, section X
(August 1979, page 437), or other sensitizing dyes. Further, a
supersensitizer exhibiting no absorption in the visible region may
be used in combination, as used in conventional silver halide
techniques. As described later, instead of preparing silver halide
in ex citu and mixing it with the dye, spectral sensitization can
be achieved by converting a part of the organic silver salt to
silver halide and by further adding the dye thereto.
[0090] The present invention also relates to thermally developable
photosensitive materials containing an infrared sensitizing dye
represented by formulas (1) to (4), a preparation method thereof
and an image recording method and image forming method by use
thereof.
[0091] These infrared sensitizing dyes are superior in adsorption
to silver halide and enhancing sensitivity and storage stability,
as compared to conventionally used infrared sensitizing dyes.
However, there still remains problems such that in cases when
applied to thermally developable photosensitive materials, marked
reduction in sensitivity after pre-exposure storage of the
photosensitive material or being allowed to stand in the form a
solution at the stage of preparing a coating solution; and
improvements thereof are desired. It is contemplated that such
problems are caused due to the fact that the thermally developable
photosensitive material is difference in constitution from the
conventional silver halide photographic material, which is to be
subjected to liquid processing. The present invention was
accomplished as a result of the inventor's study to solve the
problems.
[0092] Thermally developable photosensitive materials comprise a
photosensitive silver halide, an organic silver salt, a reducing
agent, adjuvants such as a tone modifier (also called image
tone-providing agent or activator toner) and a binder.
Specifically, the tone modifier also promotes development and
compounds having a strong affinity for a silver ion are employed.
Examples of representative tone modifiers include phthalazines,
phthalazinones, and benzenepolycarboxylic acids and their
anhydrides. The tone modifier concerns oxidation-reduction reaction
of the organic silver salt and reducing agent, having a function of
enhancing silver image density or blackening image tone. The tone
modifier may be incorporated into a non-photosensitive layer or a
photosensitive silver halide layer. In any case thereof, it was
found that adding the tone modifier immediately before coating a
photosensitive coating solution was preferred, enhancing
sensitivity and reducing variation in photographic performance
during standing of the photosensitive coating solution. It is
contemplated that these advantageous effects are related to
infrared sensitizing dyes used in the invention. Such effects are
also unexpected and surprising.
[0093] The reason for the effects is not definitely clarified. It
is contemplated that these compounds have a high affinity for a
silver compound, affecting adsorption of a sensitizing dye, and a
protic compound of the tone modifier undergoes protonation to a
sensitizing dye, possibly affecting absorption and stability of the
sensitizing dye. In fact, there was found a difference in
sensitivity spectrum (or spectral sensitivity distribution) between
a photosensitive material which was coated after standing a coating
solution added with a toner modifier and a photosensitive material
which was coated immediately after adding the toner modifier.
[0094] Phthalazines and phthalazinones may be substituted and
preferred substituents include substituted alkyl, substituted aryl,
hydroxy, halogen, substituted amino, substituted amido, substituted
ester, substituted nitro and substituted alkoxy. Exemplary examples
thereof include phthalazine, phthalazinone,
4-(1-naphthyl)phthalazine, 4-(1-naphthyl)phthalazinone,
6-chlorophthalazine, 60chlorophthalazinone,
5,7-dimethyloxyphthalazine, 5,7-dimethyloxuphthalazinone,
4-phthalazine and 4-phthalazinone. Benzenepolycarboxylic acids may
be substituted and preferred substituents include substituted
alkyl, substituted aryl, hydroxy, halogen, substituted amino,
substituted amido, substituted ester, substituted nitro and
substituted alkoxy. Preferred benzenepolycarboxylic acids are
substituted or unsubstituted benzenedicarboxylic acids, substituted
or unsubstituted benzenetricarboxylic acids, including phthalic
acids, terephthalic acids, isophthalic acids and trimellitic acids.
Substituted or unsubstituted benzenedicarboxylic acids are
specifically preferred and phthalic acids are most preferred.
[0095] Phthalic acids may be substituted and preferred substituents
include substituted alkyl, substituted aryl, hydroxy, halogen,
substituted amino, substituted amido, substituted ester,
substituted nitro and substituted alkoxy. The benzenepolycarboxylic
acids may be in the form of an anhydride, such as phthalic acid and
its anhydride, 4-methylphthalic acid and its anhydride,
4-nitrophthalic acid and its anhydride, and tetrachlorophthalic
acid and its anhydride.
[0096] In the photosensitive material according to the invention,
at least one of these compounds is incorporated into a
photosensitive silver halide layer or a non-photosensitive layer.
The non-photosensitive layer refers to a layer containing no
photosensitive silver halide and provided on the same side as the
layer containing photosensitive silver halide, including a
protective layer.
[0097] In cases when added into the non-photosensitive layer, the
tone modifier may be at any time between after the start of
preparation of the photosensitive layer coating solution and
immediately before coating. In cases when added into the
photosensitive layer, it is preferred to add the tone modifier into
a coating solution of the photosensitive layer immediately before
coating. In this case, the expression "immediately before" means 2
hrs to 1 sec., and 1 hr. to 10 sec. before the start of coating. In
cases when incorporated into the photosensitive layer, the
phthalazine, phthalazinones, or benzenepolycarboxylic acids, the
amount thereof is preferably 0.1 to 20% by weight, and more
preferably 0.2 to 15% by weight, based on total silver including
organic silver salts and silver halide. In cases when incorporated
into another layer such as non-photosensitive protective layer, the
same or more amount to be incorporated is preferred. In cases when
incorporated into a protective layer, 1.1 to 3 times the amount to
be incorporated into the photosensitive layer is preferred. A large
excess of the tone modifier causes bleeding on thermal development
to stain a heated drum, causing stains in the photosensitive
material. In cases when the tone modifier is incorporated into an
infrared sensitizing dye-containing layer or another layer,
photosensitive materials with high sensitivity and superior storage
stability can be obtained by adding the tone modifier and promptly
making completion of coating and drying within a period of time
after adding it.
[0098] The compounds described above are most effective as a tone
modifier. Further, compounds described below are also effective as
a tone modifier. Thus, other preferred tone modifiers usable in the
invention are disclosed in Research Disclosure 176, item 17029.
Exemplary examples thereof include:
[0099] imides (for example, phthalimide), cyclic imides,
pyrazoline-5-one, and quinazolinone (for example, succinimide,
3-phenyl-2-pyrazoline-5-on, 1-phenylurazole, quinazoline and
2,4-thiazolidione); naphthalimides (for example,
N-hydroxy-1,8-naphthalimide); cobalt complexes (for example, cobalt
hexaminetrifluoroacetate), mercaptans (for example,
3-mercapto-1,2,4-triazole); N-(aminomethyl)aryldicarboxyimides (for
example, N-(dimethylaminomethyl)phthalimide); blocked pyrazoles,
isothiuronium derivatives and combinations of certain types of
light-bleaching agents (for example, combination of
N,N'-hexamethylene(1-carbamoyl-3,5-dimethylpyrazole),
1,8-(3,6-dioxaoctane)bis-(isothiuroniumtrifluoroacetate), and
2-(tribromomethyl-sulfonyl)benzothiazole; merocyanine dyes (for
example,
3-ethyl-5-((3-etyl-2-benzothiazolinylidene-(benzothiazolinylidene))-1-met-
hylethylidene-2-thio-2,4-oxazolidinedione); phthalazinone,
phthalazinone derivatives or metal salts thereof (for example,
4-(1-naphthyl)phthalazin- one, 6-chlorophthalazinone,
5,7-dimethylphthalazinone, and 2,3-dihydro-1,4-phthalazinedione);
combinations of phthalazinone and sulfinic acid derivatives (for
example, 6-chlorophthalazinone and benzenesulfinic acid sodium, or
8-methylphthalazinone and p-trisulfonic acid sodium); combinations
of phthalazine and phthalic acid; combinations of phthalazine
(including phthalazine addition products) with at least one
compound selected from maleic acid anhydride, and phthalic acid,
2,3-naphthalenedicarboxylic acid or o-phenylenic acid derivatives
and anhydrides thereof (for example, phthalic acid,
4-methylphthalic acid, 4-nitrophthalic acid, and
tetrachlorophthalic acid anhydride); quinazolinediones,
benzoxazine, naphthoxazine derivatives, benzoxazine-2,4-diones (for
example, 1,3-benzoxazine-2,4-dione); pyrimidines and
asymmetry-triazines (for example, 2,4-dihydroxypyrimidine- ), and
tetraazapentalene derivatives (for example,
3,6-dimercapto-1,4-diph- enyl-1H,4H-2,3a,5,6a-tatraazapentalene).
Preferred image color control agents include phthalazone or
phthalazine.
[0100] It is preferred to apply a heteroatom-containing macrocyclic
compound to the thermally developable photosensitive materials used
in the invention. The heteroatom containing macrocyclic compound
refers to a nine- or more membered macrocyclic compound containing
at least a heteroatom selected from a nitrogen atom, an oxygen
atom, a sulfur atom and a selenium atom. The macrocyclic compound
is preferably a 12- to 18-membered ring. Representative compounds
thereof include compounds commonly known as a crown ether, which
was synthesized by Pederson in 1967 and a number of which have been
synthesized since its specific report. The compounds are detailed
in C. J. Pederson, Journal of American Chemical Society vol. 86
(2495), 7017-7036 (1967); G. W. Gokel & S. H. Korzeniowski,
"Macrocyclic Polyether Synthesis", Springer-Vergal (1982);
"Chemistry of Crown Ether" edited by Oda, Shono & Tabuse,
published by Kyoritsu Shuppan (1978); "Host-Guest" edited by
Tabuse, published by Kyoritsu Shuppan (1979); and Suzuki &
Koga, Yuki Gosei Kagaku ( Journal of Organic Synthetic Chemistry)
vol. 45 (6) 571-582 (1987).
[0101] Exemplary examples of the heteroatom containing macrocyclic
compounds used in the invention are shown below, but are not
limited to these examples. 9
[0102] The heteroatom containing macrocyclic compound may be added
at any stage after forming silver halide and until preparing a
coating solution, and is added preferably prior to adding the
sensitizing dye. The heteroatom containing macrocyclic compounds
are generally incorporated into the thermally developable
photosensitive layer through solution in organic solvents such as
methanol, ethanol or fluorinated alcohols, or water. In cases where
solubility is not sufficient, dissolution-promoting agent may be
used in combination, including potassium acetate, potassium iodide,
potassium fluoride, potassium p-toluenesulfonate, KBF.sub.4,
KPF.sub.6, NH.sub.4BF.sub.4 and NH.sub.4PF.sub.6. Any compound
containing an ion capable of forming an inclusion compound together
with the heteroatom containing macrocyclic compound, which is able
to improve solubility may be usable as the dissolution-promoting
agent.
[0103] Thermally developable photosensitive materials are
disclosed, for example, in U.S. Pat. Nos. 3,152,904 and 3,457,075,
and D. Morgan, "Dry Silver Photographic Material" and D. Morgan and
B. Shely, "Thermally Processed Silver Systems" (Imaging Processes
and Materials) Neblette, 8th Edition, edited by Sturge, V.
Walworth, and A. Shepp, page 2, 1969), etc. Of these, the thermally
developable photosensitive material used in the invention is
characterized in that they are thermally developed at temperature
of 80 to 140 .degree. C. so as to obtain images without
fixation.
[0104] Silver halide grains of photosensitive silver halide in the
present invention work as a light sensor. In order to minimize
cloudiness after image formation and to obtain excellent image
quality, the less the average grain size, the more preferred, and
the average grain size is preferably less than 0.1 .mu.m, more
preferably between 0.01 and 0.1 .mu.m, and still more preferably
between 0.02 and 0.08 .mu.m. The average grain size as described
herein is defined as an average edge length of silver halide
grains, in cases where they are so-called regular crystals in the
form of cube or octahedron. Furthermore, in cases where grains are
not regular crystals, for example, spherical, cylindrical, and
tabular grains, the grain size refers to the diameter of a sphere
having the same volume as the silver grain. Furthermore, silver
halide grains are preferably monodisperse grains. The monodisperse
grains as described herein refer to grains having a
monodispersibility obtained by the formula described below of less
than 40%; more preferably less than 30%, and most preferably from
0.1 to 20%.
[0105] Monodispersibility=(standard deviation of grain
diameter)/(average grain diameter).times.100(%)
[0106] The silver halide grain shape is not specifically limited,
but a high ratio accounted for by a Miller index [100] plane is
preferred. This ratio is preferably at least 50%; is more
preferably at least 70%, and is most preferably at least 80%. The
ratio accounted for by the Miller index [100] face can be obtained
based on T. Tani, J. Imaging Sci., 29, 165 (1985) in which
adsorption dependency of a [111] face or a [100] face is
utilized.
[0107] Furthermore, another preferred silver halide shape is a
tabular grain. The tabular grain as described herein is a grain
having an aspect ratio represented by r/h of at least 3, wherein r
represents a grain diameter in .mu.m defined as the square root of
the projection area, and h represents thickness in .mu.m in the
vertical direction. Of these, the aspect ratio is preferably
between 3 and 50. The grain diameter is preferably not more than
0.1 .mu.m, and is more preferably between 0.01 and 0.08 .mu.m.
These are described in U.S. Pat. Nos. 5,264,337, 5,314,789,
5,320,958, and others. In the present invention, when these tabular
grains are used, image sharpness is further improved. The
composition of silver halide may be any of silver chloride, silver
chlorobromide, silver iodochlorobromide, silver bromide, silver
iodobromide, or silver iodide.
[0108] Silver halide emulsions used in the invention can be
prepared according to the methods described in P. Glafkides, Chimie
Physique Photographique (published by Paul Montel Corp., 19679; G.
F. Duffin, Photographic Emulsion Chemistry (published by Focal
Press, 1966); V. L. Zelikman et al., Making and Coating of
Photographic Emulsion (published by Focal Press, 1964). Any one of
acidic precipitation, neutral precipitation and ammoniacal
precipitation is applicable and the reaction mode of aqueous
soluble silver salt and halide salt includes single jet addition,
double jet addition and a combination thereof. Silver halide may be
incorporated into the image forming layer by any means so that the
silver halide is arranged so as to be close to reducible silver
source. Silver halide may be mixed with a previously-prepared
organic silver salt. Alternatively, silver halide may be added into
a solution used for preparing an organic silver salt so that silver
halide is arranged closely to the organic silver salt prepared.
[0109] Photosensitive silver halide emulsions usable in the
thermally developable photosensitive materials according to the
invention can be prepared according to the methods commonly known
in the photographic art, such as single jet or double jet addition,
or ammoniacal, neutral or acidic precipitation. Thus, the silver
halide emulsion is prepared in advance and then the emulsion is
mixed with other components of the invention to be incorporated
into the composition used in the invention. To sufficiently bring
the photosensitive silver halide into contact with an organic
silver salt, there can be applied such techniques that polymers
other than gelatin, such as polyvinyl acetal are employed as a
protective colloid in the formation of photosensitive silver
halide, as described in U.S. Pat. Nos. 3,706,564, 3,706,565,
3,713,833 and 3,748,143, British Patent 1,362,970; gelatin
contained in a photosensitive silver halide emulsion is degraded
with an enzyme, as described in British Patent 1,354,186; or
photosensitive silver halide grains are prepared in the presence of
a surfactant to save the use of a protective polymer, as described
in U.S. Pat. No. 4,076,5390149.
[0110] It is preferred to prepare silver halide in advance and mix
it with an organic silver salt. Alternatively, silver halide may be
formed by reaction of an organic silver salt and a halide ion to
convert a part of the organic silver salt to silver halide. A
combination of these may be applicable. The content of silver
halide is preferably 0.75 to 30% by weight, based on an organic
silver salt.
[0111] Silver halide preferably occludes ions of metals belonging
to Groups 6 to 11 of the Periodic Table. Preferred as the metals
are W; Fe, Co, Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, Pt and Au. These
metals may be introduced into silver halide in the form of a
complex. In the present invention, regarding the transition metal
complexes, six-coordinate complexes represented by the general
formula described below are preferred:
Formula: (ML.sub.6).sup.m:
[0112] wherein M represents a transition metal selected from
elements in Groups 6 to 11 of the Periodic Table; L represents a
coordinating ligand; and m represents 0, 1-, 2-, 3- or 4-.
Exemplary examples of the ligand represented by L include halides
(fluoride, chloride, bromide, and iodide), cyanide, cyanato,
thiocyanato, selenocyanato, tellurocyanato, azido and aquo,
nitrosyl, thionitrosyl, etc., of which aquo, nitrosyl and
thionitrosyl are preferred. When the aquo ligand is present, one or
two ligands are preferably coordinated. L may be the same or
different. Particularly preferred examples of M include rhodium
(Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium
(Os).
[0113] Exemplary examples of transition metal ligand complexes are
shown below.
[0114] 1: [RhCl.sub.6].sup.3-
[0115] 2: [RuCl.sub.6].sup.3-
[0116] 3: [ReCl.sub.6].sup.3-
[0117] 4: [RuBr.sub.6].sup.3-
[0118] 5: [OSCl.sub.6].sup.3-
[0119] 6: [IrCl.sub.6].sup.2-
[0120] 7: [Ru(NO)Cl.sub.5].sup.2-
[0121] 8: [RuBr.sub.4(H.sub.2O)].sup.2-
[0122] 9: [Ru(NO)(H.sub.2O)Cl.sub.4].sup.-
[0123] 10: [RhCl.sub.5(H.sub.2O)].sup.2-
[0124] 11: [Re(NO)Cl.sub.5].sup.2-
[0125] 12: [Re(NO)(CN).sub.5].sup.2-
[0126] 13: [Re(NO)Cl(CN).sub.4].sup.2-
[0127] 14: [Rh(NO).sub.2Cl.sub.4].sup.-
[0128] 15: [Rh(NO)(H.sub.2O)Cl.sub.4].sup.-
[0129] 16: [Ru(NO)(CN).sub.5].sup.2-
[0130] 17: [Fe(CN).sub.6].sup.3-
[0131] 18: [Rh(NS)Cl.sub.5].sup.2-
[0132] 19: [Os(NO)Cl.sub.5].sup.2-
[0133] 20: [Cr(NO)Cl.sub.5].sup.2-
[0134] 21: [Re(NO)Cl.sub.5].sup.-
[0135] 22: [Os(NS)Cl.sub.4(TeCN)].sup.2-
[0136] 23: [Ru(NS)Cl.sub.5].sup.2-
[0137] 24: [Re(NS)Cl.sub.4(SeCN)].sup.2-
[0138] 25: [Os(NS)Cl(SCN).sub.4].sup.2-
[0139] 26: [Ir(NO)Cl.sub.5].sup.2-
[0140] 27: [Ir(NS)Cl.sub.5].sup.2-
[0141] One type of these metal ions or complex ions may be employed
and the same type of metals or the different type of metals may be
employed in combinations of two or more types. Generally, the
content of these metal ions or complex ions is suitably between
1.times.10.sup.-9 and 1.times.10.sup.-2 mole per mole of silver
halide, and is preferably between 1.times.10.sup.-8 and
1.times.10.sup.-4 mole. Compounds, which provide these metal ions
or complex ions, are preferably incorporated into silver halide
grains through addition during the silver halide grain formation.
These may be added during any preparation stage of the silver
halide grains, that is, before or after nuclei formation, growth,
physical ripening, and chemical ripening. However, these are
preferably added at the stage of nuclei formation, growth, and
physical ripening; furthermore, are preferably added at the stage
of nuclei formation and growth; and are most preferably added at
the stage of nuclei formation. These compounds may be added several
times by dividing the added amount. Uniform content in the interior
of a silver halide grain can be carried out. As disclosed in JP-A
No. 63-29603, 2-306236, 3-167545, 4-76534, 6-110146, 5-273683, the
metal can be non-uniformly occluded in the interior of the
grain.
[0142] These metal compounds can be dissolved in water or a
suitable organic solvent (for example, alcohols, ethers, glycols,
ketones, esters, amides, etc.) and then added. Furthermore, there
are methods in which, for example, an aqueous metal compound powder
solution or an aqueous solution in which a metal compound is
dissolved along with NaCl and KCl is added to a water-soluble
silver salt solution during grain formation or to a water-soluble
halide solution; when a silver salt solution and a halide solution
are simultaneously added, a metal compound is added as a third
solution to form silver halide grains, while simultaneously mixing
three solutions; during grain formation, an aqueous solution
comprising the necessary amount of a metal compound is placed in a
reaction vessel; or during silver halide preparation, dissolution
is carried out by the addition of other silver halide grains
previously doped with metal ions or complex ions. Specifically, the
preferred method is one in which an aqueous metal compound powder
solution or an aqueous solution in which a metal compound is
dissolved along with NaCl and KCl is added to a water-soluble
halide solution. When the addition is carried out onto grain
surfaces, an aqueous solution comprising the necessary amount of a
metal compound can be placed in a reaction vessel immediately after
grain formation, or during physical ripening or at the completion
thereof or during chemical ripening.
[0143] Silver halide grain emulsions used in the invention may be
desalted after the grain formation, using the methods known in the
art, such as the noodle washing method and flocculation
process.
[0144] The photosensitive silver halide grains used in the
invention is preferably subjected to a chemical sensitization. As
preferable chemical sensitizations, well known chemical
sensitizations in this art such as a sulfur sensitization, a
selenium sensitization and a tellurium sensitization are usable.
Furthermore, a noble metal sensitization using gold, platinum,
palladium and iridium compounds and a reduction sensitization are
available. As the compounds preferably used in the sulfur
sensitization, the selenium sensitization and the tellurium
sensitization, well known compounds can be used and the compounds
described in JP-A 7-128768 is usable. Examples of the compounds
used in the noble metal sensitization include chloroauric acid,
potassium chloroaurate, potassium aurothiocyanate, gold sulfide,
gold selenide, compounds described U.S. Pat. No. 2,448,060 and
British Patent No. 618,061. Examples of the compounds used in the
reduction sensitization include ascorbic acid, thiourea dioxide,
stannous chloride, aminoiminomethane-sulfinic acid, hydrazine
derivatives, borane compounds, silane compounds and polyamine
compounds. The reduction sensitization can be carried out by
ripening an emulsion with keeping the pH and pAg at not less than 7
and not more than 8.3, respectively. Furthermore, the reduction
sensitization can be carried out by introducing a silver ion alone
at a time during the grain formation.
[0145] Halide composition of silver halide used in the invention is
not specifically limited, including silver chloride, silver
chlorobromide, silver iodochlorobromide, silver bromide, silver
iodobromide, and silver iodide. Of these, silver iodobromide is
preferred to improve adsorption property. Silver halide grains used
in the thermally developable photosensitive material are preferably
those which have an average iodide content in the vicinity of the
grain surface of 0.1 to 10 mol %, and more preferably 1 to 7 mol %.
In the thermally developable photosensitive materials, higher
iodide silver halide is preferred in terms of adsorption of a
sensitizing dye, as compared to conventional silver halide
photographic materials. The average iodide content in the vicinity
of the grain surface refers to an average iodide content to a depth
of 5 nm from the surface, which can be determined by the XPS method
(i.e., X-ray Photoelectron Spectroscopy), according to the
following procedure. A sample is cooled to a temperature of not
higher than -110.degree. C. under ultra-high vacuum of not more
than 1.times.10.sup.-8 torr, exposed to MgK.alpha.-line as X-ray
for probe at a X-ray source voltage of 15 kV and X-ray source
current of 40 mA and measured with respect to Ag3d5/2, Br3d and
I3d3/2 electrons. The thus measured integrated peak intensity is
corrected with a sensitivity factor and from the obtained intensity
ratio can be determined halide composition in the vicinity of the
grain surface. Cooling the sample reduces measurement errors, which
are due to destruction of the sample occurred when exposed at room
temperature, enhancing measurement precision. Cooling to a
temperature of -110.degree. C. prevents destruction of the sample
at an acceptable level in the measurement.
[0146] The amount of silver halide used in the thermally
developable photosensitive material is preferably not more than
50%, more preferably 0.1 to 25%, and still more preferably 0.1 to
15%, based on the total amount of silver halide and organic silver
salt.
[0147] Photosensitive silver halide used in the thermally
developable photosensitive material of the invention can be formed
simultaneously with the formation of organic silver salt by
allowing a halide component such as a halide ion to concurrently be
present together with organic silver salt-forming components and
further introducing a silver ion thereinto during the course of
preparing the organic silver salt.
[0148] Alternatively, a silver halide-forming component is allowed
to act onto a pre-formed organic silver salt solution or dispersion
or a sheet material containing an organic silver salt to convert a
part of the organic silver salt to photosensitive silver halide.
The thus formed silver halide is effectively in contact with the
organic silver salt, exhibiting favorable actions. In this case,
the silver halide-forming component refers to a compound capable of
forming silver salt upon reaction with the organic silver salt.
Such a compound can be distinguished by the following simple test.
Thus, a compound to be tested is to be mixed with the organic
silver salt, and if necessary, the presence of a peal specific to
silver halide can be confirmed by the X-ray diffractometry, after
heating. Compounds that have been confirmed to be effective as a
silver halide-forming component include inorganic halide compounds,
onium halides, halogenated hydrocarbons, N-halogeno compounds and
other halogen containing compounds. These compounds are detailed in
U.S. Pat. Nos. 4,009,039, 3,457,075 and 4,003,749, British Patent
1,498,956 and JP-A 53-27027 and 53-25420. Exemplary examples
thereof are shown below:
[0149] (1) Inorganic halide compound: e.g., a halide compound
represented by formula, MXn, in which M represents H, NH4 or a
metal atom; n is 1 when M is H or NH4 and a number equivalent to a
valence number of the metal atom when M is the metal atom; the
metal atom includes lithium, sodium, potassium, cesium, magnesium,
calcium, strontium, barium, zinc, cadmium, mercury, tin, antimony,
chromium, manganese, cobalt, rhodium, and cerium, and molecular
halogen such as aqueous bromine being also effective;
[0150] (2) Onium halide: e.g., quaternary ammonium halides such as
trimethylphenylammonium bromide, cetylethyldimethylammonium
bromide, and trimethylbenzylammonium bromide; and tertiary
sulfonium halides such as trimethylsulfonium iodide;
[0151] (3) Halogenated hydrocarbons: e.g., iodoform, bromoform,
carbon tetrachloride and 2-brom-2-methylpropane;
[0152] (4) N-halogeno compounds: e.g., N-chlorosuccinimide,
N-bromosucciimde, N-bromophthalimide, N-bromoacetoamide,
N-iodosuccinimide, N-bromophthalazinone, N-bromooxazolinone,
N-chlorophthalazinone, N-bromoacetoanilide,
N,N-dibromobenzenesulfonamide- ,
N-bromo-N-methylbenzenesulfonamide,
1,3-dibromo-4,4-dimethylhydantoin and N-bromourazole;
[0153] (5) Other halogen containing compounds: e.g.,
triphenylmethyl chloride, triphenylmethyl bromide 2-bromoacetic
acid, 2-bromoethanol and dichlorobenzophenone.
[0154] The silver halide forming component is used
stoichiometrically in a small amount per organic silver salt. Thus,
it is preferably 0.001 to 0.7 mol, and more preferably 0.03 to 0.5
mol per mol of organic silver salt. The silver halide-forming
component may be used in combination. Conditions including a
reaction temperature, reaction time and reaction pressure during
the process of converting a part of the organic silver salt to
silver halide using the silver halide forming component can be
appropriately set in accordance with the purpose of preparation.
The reaction temperature is preferably -20.degree. C. to 70.degree.
C., the reaction time is preferably 0.1 sec to 72 hrs. and the
reaction pressure is preferably atmospheric pressure. The reaction
is performed preferably in the presence of polymer as a binder,
wherein the polymer to be used is preferably 0.01 to 100 weight
parts, and more preferably 0.1 to 10 weight parts per 1 weight part
of an organic silver salt.
[0155] The thus formed photosensitive silver halide can be
chemically sensitized with a sulfur containing compound, gold
compound, platinum compound, palladium compound, silver compound,
tin compound, chromium compound or their combination. The method
and procedure for chemical sensitization are described in U.S. Pat.
No. 4,036,650, British Patent 1,518,850, JP-A 51-22430, 51-78319
and 51-81124. As described in U.S. Pat. No. 3,980,482, a low
molecular weight amide compound may be concurrently present to
enhance sensitivity at the time of converting a part of the organic
silver salt to photosensitive silver halide.
[0156] To improve reciprocity law failure or adjust contrast, the
photosensitive silver halide may be contained with metal ions of
the 6th group to 10th group in the periodical table, such as Rh,
Ru, Re, Ir, Os, Fe and their complexes and complex ions.
Specifically, complex ions are preferred, e.g., Ir complex ions
such as IrCl.sub.6.sup.2- are preferably contained to improve
reciprocity law failure.
[0157] Organic silver salts used in the invention are reducible
silver source, and silver salts of organic acids or organic
heteroacids are preferred and silver salts of long chain fatty acid
(preferably having 10 to 30 carbon atom and more preferably 15 to
25 carbon atoms) or nitrogen containing heterocyclic compounds are
more preferred. Specifically, organic or inorganic complexes,
ligand of which have a total stability constant to a silver ion of
4.0 to 10.0 are preferred. Exemplary preferred complex salts are
described in RD17029 and RD29963, including organic acid salts (for
example, salts of gallic acid, oxalic acid, behenic acid, stearic
acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salts
(for example, 1-(3-carboxypropyl)thiourea,
1-(3-caroxypropyl)-3,3-dimethylthiourea, etc.); silver complexes of
polymer reaction products of aldehyde with hydroxy-substituted
aromatic carboxylic acid (for example, aldehydes (formaldehyde,
acetaldehyde, butylaldehyde, etc.), hydroxy-substituted acids (for
example, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid,
5,5-thiodisalicylic acid, silver salts or complexes of thiones (for
example, 3-(2-carboxyethyl)-4-hydroxymethyl-4-(thiazoline-2-thione
and 3-carboxymethyl-4-thiazoline-2-thione), complexes of silver
with nitrogen acid selected from imidazole, pyrazole, urazole,
1.2,4-thiazole, and 1H-tetrazole,
3-amino-5-benzylthio-1,2,4-triazole and benztriazole or salts
thereof; silver salts of saccharin, 5-chlorosalicylaldoxime, etc.;
and silver salts of mercaptides. Of these organic silver salts,
silver salts of fatty acids are preferred, and silver salts of
behenic acid, arachidinic acid and stearic acid are specifically
preferred.
[0158] The organic silver salt compound can be obtained by mixing
an aqueous-soluble silver compound with a compound capable of
forming a complex. Normal precipitation, reverse precipitation,
double jet precipitation and controlled double jet precipitation
described in JP-A 9-127643 are preferably employed. For example, to
an organic acid is added an alkali metal hydroxide (e.g., sodium
hydroxide, potassium hydroxide, etc.) to form an alkali metal salt
soap of the organic acid (e.g., sodium behenate, sodium
arachidinate, etc.), thereafter, the soap and silver nitrate are
mixed by the controlled double jet method to form organic silver
salt crystals. In this case, silver halide grains may be
concurrently present.
[0159] In the present invention, organic silver salts have an
average grain diameter of 2 .mu.m or less and are monodispersed.
The average diameter of the organic silver salt as described herein
is, when the grain of the organic salt is, for example, a
spherical, cylindrical, or tabular grain, a diameter of the sphere
having the same volume as each of these grains. The average grain
diameter is preferably between 0.05 and 1.5 .mu.m, and more
preferably between 0.05 and 1.0 .mu.m. Furthermore, the
monodisperse as described herein is the same as silver halide
grains and preferred monodispersibility is between 1 and 30%.
[0160] It is also preferred that at least 60% of the total of the
organic silver salt is accounted for by tabular grains. The tabular
grains refer to grains having a ratio of an average grain diameter
to grain thickness, i.e., aspect ratio (denoted as AR) of 3 or
more:
AR=average diameter (.mu.m)/thickness (.mu.m)
[0161] To obtain such tabular organic silver salts, organic silver
salt crystals are pulverized together with a binder or surfactant,
using a ball mill. Thus, using these tabular grains, photosensitive
materials exhibiting high density and superior image fastness are
obtained.
[0162] To prevent hazing of the photosensitive material, the total
amount of silver halide and organic silver salt is preferably 0.5
to 2.2 g in equivalent converted to silver per m.sup.2, leading to
high contrast images. The amount of silver halide is preferably 50%
by weight or less, more preferably 25% by weight or less, and still
more preferably 0.1 to 15% by weight, based on the total silver
amount.
[0163] Reducing agents are preferably incorporated into the
thermally developable photosensitive material of the present
invention. Examples of suitable reducing agents are described in
U.S. Pat. Nos. 3,770,448, 3,773,512, and 3,593,863, and Research
Disclosure Items 17029 and 29963, and include the following:
aminohydroxycycloalkenone compounds (for example,
2-hydroxypiperidino-2-cyclohexane); esters of amino reductones as
the precursor of reducing agents (for example, piperidinohexose
reducton monoacetate); N-hydroxyurea derivatives (for example,
N-p-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones
(for example, anthracenealdehyde phenylhydrazone;
phosphamidophenols; phosphamidoanilines; polyhydroxybenzenes (for
example, hydroquinone, t-butylhydroquinone, isopropylhydroquinone,
and (2,5-dihydroxyphenyl)meth- ylsulfone); sulfydroxamic acids (for
example, benzenesulfhydroxamic acid); sulfonamidoanilines (for
example, 4-(N-methanesulfonamide)aniline);
2-tetrazolylthiohydroquinones (for example,
2-methyl-5-(1-phenyl-5-tetraz- olylthio)hydroquinone);
tetrahydroquionoxalines (for example,
1,2,3,4-tetrahydroquinoxaline); amidoxines; azines (for example,
combinations of aliphatic carboxylic acid arylhydrazides with
ascorbic acid); combinations of polyhydroxybenzenes and
hydroxylamines, reductones and/or hydrazine; hydroxamic acids;
combinations of azines with sulfonamidophenols;
.alpha.-cyanophenylacetic acid derivatives; combinations of
bis-.beta.-naphthol with 1,3-dihydroxybenzene derivatives;
5-pyrazolones, sulfonamidophenol reducing agents,
2-phenylindane-1,3-dione, etc.; chroman; 1,4-dihydropyridines (for
example, 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine);
bisphenols (for example,
bis(2-hydroxy-3-t-butyl-5-methylphenyl)methane,
bis(6-hydroxy-m-tri)mesitol,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
4,5-ethylidene-bis(2-t-butyl-6-methyl)phenol, UV-sensitive ascorbic
acid derivatives and 3-pyrazolidones. Of these, particularly
preferred reducing agents are hindered phenols. As hindered
phenols, listed are compounds represented by the general formula
(A) described below: 10
[0164] wherein R represents a hydrogen atom or an alkyl group
having from 1 to 10 carbon atoms (for example, --C.sub.4H.sub.9,
2,4,4-trimethylpentyl), and R' and R" each represents an alkyl
group having from 1 to 5 carbon atoms (for example, methyl, ethyl,
t-butyl).
[0165] Exemplary examples of the compounds represented by the
formula (A) are shown below. 11
[0166] The used amount of reducing agents represented by the
above-mentioned general formula (A) is preferably between
1.times.10.sup.-2 and 10 moles, and is more preferably between
1.times.10.sup.-2 and 1.5 moles per mole of silver.
[0167] Binders suitable for the thermally developable
photosensitive material to which the present invention is applied
are transparent or translucent, and generally colorless. Binders
are natural polymers, synthetic resins, and polymers and
copolymers, other film forming media; for example, gelatin, gum
arabic, poly(vinyl alcohol), hydroxyethyl cellulose, cellulose
acetate, cellulose acetatebutylate, poly(vinyl pyrrolidone),
casein, starch, poly(acrylic acid), poly(methyl methacrylic acid),
poly(vinyl chloride), poly(methacrylic acid), copoly(styrene-maleic
acid anhydride), copoly(styrene-acrylonitrile,
copoly(styrene-butadiene, poly(vinyl acetal) series [e.g.,
poly(vinyl formal)and poly(vinyl butyral), polyester series,
polyurethane series, phenoxy resins, poly(vinylidene chloride),
polyepoxide series, polycarbonate series, poly(vinyl acetate)
series, cellulose esters, poly(amide) series. Of these binders are
preferred aqueous-insoluble polymers such as cellulose acetate,
cellulose acetate-butylate and poly(vinyl butyral); and poly(vinyl
formal) and poly(vinyl butyral) are specifically preferred as a
polymer used in the thermally developable photosensitive layer; and
cellulose acetate and cellulose acetate-butylate are preferably
used in a protective layer and backing layer.
[0168] A non-photosensitive layer may be provided on the
photosensitive layer to protect the surface or prevent abrasion
marks. Binder used in the non-photosensitive layer may be the same
as or different from the binder used in the photosensitive
layer.
[0169] The amount of the binder in a photosensitive layer is
preferably between 1.5 and 6 g/m.sup.2, and is more preferably
between 1.7 and 5 g/m.sup.2. The binder content of less than 1.5
g/m.sup.2 tends to increase a density of unexposed area to levels
unacceptable to practical use.
[0170] In the present invention, a matting agent is preferably
incorporated into the image forming layer side. In order to
minimize the image abrasion after thermal development, the matting
agent is provided on the surface of a photosensitive material and
the matting agent is preferably incorporated in an amount of 0.5 to
30 per cent in weight ratio with respect to the total binder in the
emulsion layer side.
[0171] In cases where a non photosensitive layer is provided on the
opposite side of the support to the photosensitive layer, it is
preferred to incorporate a matting agent into at least one of the
non-photosensitive layer (and more preferably, into the surface
layer) in an amount of 0.5 to 40% by weight, based on the total
binder on the opposite side to the photosensitive layer.
[0172] Materials of the matting agents employed in the present
invention may be either organic substances or inorganic substances.
Examples of the inorganic substances include silica described in
Swiss Patent No. 330,158, etc.; glass powder described in French
Patent No. 1,296,995, etc.; and carbonates of alkali earth metals
or cadmium, zinc, etc. described in U.K. Patent No. 1,173,181, etc.
Examples of the organic substances include starch described in U.S.
Pat. No. 2,322,037, etc.; starch derivatives described in Belgian
Patent No. 625,451, U.K. Patent No. 981,198, etc.; polyvinyl
alcohols described in Japanese Patent Publication No. 44-3643,
etc.; polystyrenes or polymethacrylates described in Swiss Patent
No. 330,158, etc.; polyacrylonitriles described in U.S. Pat. No.
3,079,257, etc.; and polycarbonates described in U.S. Pat. No.
3,022,169.
[0173] The shape of the matting agent may be crystalline or
amorphous. However, a crystalline and spherical shape is preferably
employed. The size of a matting agent is expressed in the diameter
of a sphere having the same volume as the matting agent. The
particle diameter of the matting agent in the present invention is
referred to the diameter of a spherical converted volume. The
matting agent employed in the present invention preferably has an
average particle diameter of 0.5 to 10 .mu.m, and more preferably
of 1.0 to 8.0 .mu.m. Furthermore, the variation coefficient of the
size distribution is preferably not more than 50 percent, is more
preferably not more than 40 percent, and is most preferably not
more than 30 percent. The variation coefficient of the size
distribution as described herein is a value represented by the
formula described below:
[0174] (Standard deviation of particle diameter)/(average particle
diameter).times.100
[0175] The matting agent according to the present invention can be
incorporated into any layer. In order to accomplish the object of
the present invention, the matting agent is preferably incorporated
into the layer other than the photosensitive layer layer, and is
more preferably incorporated into the farthest layer from the
support.
[0176] Addition methods of the matting agent include those in which
a matting agent is previously dispersed into a coating composition
and is then coated, and prior to the completion of drying, a
matting agent is sprayed. When plural matting agents are added,
both methods may be employed in combination.
[0177] The thermally developable photosensitive material according
to the invention comprises a support having thereon at least one
photosensitive layer, and the photosensitive layer may only be
formed on the support. The photosensitive layer may be composed of
a plurality of layers. To adjust gradation, layers may be arranged
in such a manner as a high-speed layer/low-speed layer or a
low-speed layer/high-speed layer. Further, at least one
non-photosensitive layer is preferably formed on the photosensitive
layer. In order to control the amount or wavelength distribution of
light transmitted through the photosensitive layer, a filter layer
may be provided on the same side as the photosensitive layer,
and/or an antihalation layer, that is, a backing layer on the
opposite side. Dyes or pigments may also be incorporated into the
photosensitive layer. As the usable dyes, those which can absorb
aimed wavelength in desired wavelength region can be used,
preferred are compounds described in JP-A Nos. 59-6481, 59-182436,
U.S. Pat. No. 4,594,312, European Patent Publication Nos. 533,008,
652,473, JP-A Nos. 2-216140, 4-348339, 7-191432, 7-301890.
Furthermore, these non-photosensitive layers may contain the
above-mentioned binder, a matting agent and a lubricant such as a
polysiloxane compound, a wax and liquid paraffin.
[0178] Suitable tone modifiers usable in the invention a) include
those used in the invention b). Tone mdifiers are preferably
incorporated into the thermally developable photosensitive material
used in the present invention. Examples of preferred tone
modifiers, which are disclosed in Research Disclosure Item 17029,
include the following:
[0179] imides (for example, phthalimide), cyclic imides,
pyrazoline-5-one, and quinazolinone (for example, succinimide,
3-phenyl-2-pyrazoline-5-on, 1-phenylurazole, quinazoline and
2,4-thiazolidione); naphthalimides (for example,
N-hydroxy-1,8-naphthalimide); cobalt complexes (for example, cobalt
hexaminetrifluoroacetate), mercaptans (for example,
3-mercapto-1,2,4-triazole); N-(aminomethyl)aryldicarboxyimides (for
example, N-(dimethylaminomethyl)phthalimide); blocked pyrazoles,
isothiuronium derivatives and combinations of certain types of
light-bleaching agents (for example, combination of
N,N'-hexamethylene(1-carbamoyl-3,5-dimethylpyrazole),
1,8-(3,6-dioxaoctane)bis-(isothiuroniumtrifluoroacetate), and
2-(tribromomethyl-sulfonyl)benzothiazole; merocyanine dyes (for
example,
3-ethyl-5-((3-etyl-2-benzothiazolinylidene-(benzothiazolinylidene))-1-met-
hylethylidene-2-thio-2,4-oxazolidinedione); phthalazinone,
phthalazinone derivatives or metal salts thereof (for example,
4-(1-naphthyl)phthalazin- one, 6-chlorophthalazinone,
5,7-dimethylphthalazinone, and 2,3-dihydro-1,4-phthalazinedione);
combinations of phthalazinone and sulfinic acid derivatives (for
example, 6-chlorophthalazinone and benzenesulfinic acid sodium, or
8-methylphthalazinone and p-trisulfonic acid sodium); combinations
of phthalazine and phthalic acid; combinations of phthalazine
(including phthalazine addition products) with at least one
compound selected from maleic acid anhydride, and phthalic acid,
2,3-naphthalenedicarboxylic acid or o-phenylenic acid derivatives
and anhydrides thereof (for example, phthalic acid,
4-methylphthalic acid, 4-nitrophthalic acid, and
tetrachlorophthalic acid anhydride); quinazolinediones,
benzoxazine, naphthoxazine derivatives, benzoxazine-2,4-diones (for
example, 1,3-benzoxazine-2,4-dione); pyrimidines and
asymmetry-triazines (for example, 2,4-dihydroxypyrimidine- ), and
tetraazapentalene derivatives (for example,
3,6-dimercapto-1,4-diph- enyl-1H,4H-2,3a,5,6a-tatraazapentalene).
Preferred tone modifiers include phthalazone or phthalazine.
[0180] In the present invention, to restrain or accelerate
development for the purpose of controlling the development, to
enhance the spectral sensitive efficiency, or to enhance the
reservation stability before and after the development, a mercapto
compound, a disulfide compound and a thione compound can be
incorporated in the photosensitive material. In cases where the
mercapto compound is used in the present invention, any compound
having a mercapto group can be used, but preferred compounds are
represented by the following formulas, Ar-SM and Ar-S-S-Ar, wherein
M represents a hydrogen atom or an alkaline metal atom, Ar
represents an aromatic ring compound or a condensed aromatic ring
compound having at least a nitrogen, sulfur, oxygen, selenium or
tellurium. Preferable aromatic heterocyclic ring compounds include
benzimidazole, naphthoimidazole, benzothiazole, naphthothiazole,
benzoxazole, naphthooxazole, benzoselenazole, benzotellurazole,
imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole,
triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine,
quinoline or quinazoline. These aromatic heterocyclic ring
compounds may contain a substituent selected from a halogen atom
(e.g., Br and Cl), a hydroxy group, an amino group, a carboxy
group, an alkyl group (e.g., alkyl group having at least a carbon
atom, preferably 1 to 4 carbon atoms) and an alkoxy group (e.g.,
alkoxy group having at least a carbon atom, preferably 1 to 4
carbon atoms). Examples of mercapto-substituted aromatic
heterocyclic ring compounds include 2-mercaptobenzimidazole,
2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole,
2-mercaptoquinoline, 8-mercaptopurine,
2,3,5,6-tetrachloro-4-pyridinethiol, 4-hydroxy-2-mercaptopyrimidine
and 2-mercapto-4-phenyloxazole, but the exemplified compounds
according to the present invention are not limited thereto.
[0181] Antifoggants may be incorporated into the thermally
developable photosensitive material to which the present invention
is applied. The substance which is known as the most effective
antifoggant is a mercury ion. The incorporation of mercury
compounds as the antifoggant into photosensitive materials is
disclosed, for example, in U.S. Pat. No. 3,589,903. However,
mercury compounds are not environmentally preferred. As
mercury-free antifoggants, preferred are those antifoggants as
disclosed in U.S. Pat. Nos. 4,546,075 and 4,452,885, and JP-A
59-57234. Particularly preferred mercury-free antifoggants are
heterocyclic compounds having at least one substituent, represented
by -C(X1)(X2)(X3) (wherein X1 and X2 each represent halogen, and X3
represents hydrogen or halogen), as disclosed in U.S. Pat. Nos.
3,874,946 and 4,756,999. As examples of suitable antifoggants,
employed preferably are compounds described in paragraph numbers
[0030] through [0036] of JP-A 9-288328. Further, as another
examples of suitable antifoggants, employed preferably are
compounds described in paragraph numbers [0062] and [0063] of JP-A
9-90550. Furthermore, other suitable antifoggants are disclosed in
U.S. Pat. No. 5,028,523, and European Patent 600,587; 605,981 and
631,176.
[0182] In the thermally processable photosensitive material of the
present invention, employed can be sensitizing dyes described, for
example, in JP-A Nos. 63-159841, 60-140335, 63-231437, 63-259651,
63-304242, and 63-15245; U.S. Pat. Nos. 4,639,414, 4,740,455,
4,741,966, 4,751,175, and 4,835,096. Useful sensitizing dyes
employed in the present invention are described, for example, in
publications described in or cited in Research Disclosure Items
17643, Section IV-A (page 23, December 1978). Particularly,
selected can advantageously be sensitizing dyes having the spectral
sensitivity suitable for spectral characteristics of light sources
of various types of scanners. For example, compounds described in
JP-A Nos. 9-34078, 9-54409 and 9-80679 are preferably employed.
[0183] Various kinds of additives can be incorporated into a
photosensitive layer, a non-photosensitive layer or other
construction layers. Except for the compounds mentioned above,
surface active agents, antioxidants, stabilizers, plasticizers, UV
(ultra violet rays) absorbers, covering aids, etc. may be employed
in the thermally developable photosensitive material according to
the present invention. These additives along with the
above-mentioned additives are described in Research Disclosure Item
17029 (on page 9 to 15, June, 1978) and can be employed.
[0184] Supports employed in the present invention are preferably,
in order to minimize the deformation of images after development
processing, plastic films (for example, polyethylene terephthalate,
polycarbonate, polyimide, nylon, cellulose triacetate, polyethylene
naphthalate). The thickness of the support is between about 50 and
about 300 .mu.m, and is preferably between 70 and 180 .mu.m.
Furthermore, thermally processed plastic supports may be employed.
As acceptable plastics, those described above are listed. The
thermal processing of the support, as described herein, is that
after film casting and prior to the photosensitive layer coating,
these supports are heated to a temperature at least 30.degree. C.
higher than the glass transition point, preferably by not less than
35.degree. C. and more preferably by at least 40.degree. C.
However, when the supports are heated at a temperature higher than
the melting point, no advantages of the present invention are
obtained. Commonly known casting methods and subbing methods are
applicable to the support used in the invention, as described in
JP-A 9-50094, items [0030]-[0070].
[0185] To improve an electrification property, a conducting
compound such as a metal oxide and/or a conducting polymer can be
incorporated into a construction layer. These compounds can be
incorporated into any layer, preferably into a sublayer, a backing
layer and an intermediate layer between a photosensitive layer and
a sublayer, etc. In the present invention, the conducting compounds
described in U.S. Pat. No. 5,244,773, column 14 through 20, are
preferably used.
[0186] In cases where the thermally developable photosensitive
material is specifically employed for the output of a printing
image setter with an oscillation wavelength of 600 to 800 nm,
hydrazine derivatives are preferably incorporated into the
photosensitive material. Exemplary preferred hydrazine compounds
are described in RD23515 (November, 1983, page 346), U.S. Pat. Nos.
4,080,207, 4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347,
4,478,928, 4,560,638, 4,686,167, 4,912,016, 4,988,604, 4,994,365,
5,041,355, and 5,104,769; British Patent 2,011,391B; European
Patents 217,310, 301,799 and 356,898; JP-A 60-179734, 61-170733,
61-270744, 62-178246, 62-270948, 63-29751, 63-32538, 63-104047,
63-121838, 63-129337, 63-22374, 63-234244, 63-234245, 63-234246,
63-294552, 63-306438, 64-10233, 1-90439, 1-100530, 1-105041,
1-105943, 1-276128, 1-280747, 1-283548, 1-283549, 1-285940, 2-2541,
2-7057, 2-13958, 2-196234, 2-196235, 2-198440 , 2-198441,2-198442,
2-220042, 2-221953, 2-221954, 2-285342, 2-285343, 2-289843,
2-302750, 2-304550, 3-37642, 3-54549, 3-125134, 3-184039, 3-240036,
3-240037, 3-259240, 3-280038, 3-282536, 4-51143, 4-56842, 4-84134,
2-230233, 4-96053, 4-216544, 5-45761, 5-45762, 5-45763, 5-45764,
5-45765, 6-289524, and 9-160164.
[0187] Furthermore, other than those, employed can be compounds
described in (Ka 1) of Japanese Patent Publication (hereinafter,
denoted as JP-B) No. 6-77138, specifically, compounds described on
pages 3 and 4 of the Publication; compounds represented by general
formula (I) in JP-B No. 6-93082, specifically, compounds 1 through
38 described on pages 8 to 18 of the Publication; compounds
represented by general formula (4), general formula (5), and
general formula (6) in JP-A No. 6-230497, specifically, compounds
4-1 through 4-10 on pages 25 and 26, compounds 5-1 through 5-42 on
pages 28 to 36, and compounds 6-1 through 6-7 on pages 39 and 40 of
the Publication; compounds represented by general formula (I) and
general formula (2) in JP-A No. 6-289520, specifically, compounds
1-1) through 1-17) and 2-1) on pages 5 to 7 of the Publication;
compounds described in (Ka 2) and (Ka 3) of JP-A No. 6-313936,
specifically, compounds described on pages 6 to 19 of the
Publication; compounds described in (Ka 1) of JP-A No. 6-313951,
specifically, compounds described on pages 3 to 5 of the
Publication; compounds represented by general formula (I) in JP-A
No. 7-5610, specifically, compounds I-1 through I-38 described on
pages 5 to 10 of the Publication; compounds represented by general
formula (II) in JP-A No. 7-77783, specifically, compounds II-1
through II-102 described on pages 10 to 27 of the Publication; and
compounds represented by general formula (H) and general formula
(Ha) in JP-A No. 7-104426, specifically, compounds H-1 through H-44
described on pages 8 to 15 of the Publication.
[0188] In addition to these materials, a variety of adjuvants may
be incorporated into the photosensitive layer, non-photosensitive
layer or other layer(s). Exemplarily, a surfactant, an antioxidant,
a stabilizer, a plasticizer, a UV absorbent or a coating aid may be
incorporated. As these adjuvants and other additives can be used
compounds described in RD17029 (June, 1978, page 9-15).
[0189] Supports usable in the thermally developable photosensitive
materials include various kinds of polymeric materials, glass, wool
fabric, cotton fabric, paper, metal (e.g., aluminum) and those
which are convertible to flexible sheets or rolls are preferred in
terms of handling as information recording material. Preferred
supports usable in thermally developable photosensitive materials
are plastic resin films (e.g., cellulose acetate film, polyester
film, polyethylene terephthalate film, polyethylene naphthalate
film, polyamide film, polyimide film, cellulose triacetate film,
polycarbonate film) and biaxially stretched polyethylene
terephthalate film is specifically preferred. The thickness of the
support is preferably 50 to 300 .mu.m, and more preferably 70 to
180 .mu.m.
[0190] In the present invention, to improve an electrification
property, a conducting compound such as a metal oxide and/or a
conducting polymer can be incorporated into a construction layer.
These compounds can be incorporated into any layer, preferably into
a sublayer, a backing layer and an intermediate layer between a
photosensitive layer and a sublayer, etc. In the present invention,
the conducting compounds described in U.S. Pat. No. 5,244,773,
column 14 through 20, are preferably used.
[0191] The thermally developable photosensitive material according
to the invention comprises a support having thereon a
photosensitive layer, and preferably further on the photosensitive
layer having a non-photosensitive layer. For example, it is
preferred that a protective layer is provided on the photosensitive
layer to protect the photosensitive layer and that a back coating
layer is provided on the opposite side of the support to the
photosensitive layer to prevent adhesion between photosensitive
materials or sticking of the photosensitive material to a roller.
Further, there may be provided a filter layer on the same side or
opposite side to the photosensitive layer to control the amount or
wavelengths of light transmitting the thermally developable
photosensitive layer. Alternatively, a dye or pigment may be
incorporated into the photosensitive layer. In this case, dyes
described in JP-A 8-201959 are preferably used therein. The
photosensitive layer may be comprised of plural layers. To adjust
contrast, a high speed layer and low speed layer may be provided in
combination. Various adjuvants may be incorporated into the
photosensitive layer, non-photosensitive layer or other component
layer(s).
[0192] The coating method of the photosensitive layer, protective
layer and backing layer is not specifically limited. Coating can be
conducted by any method known in the art, including air knife,
dip-coating, bar coating, curtain coating, and hopper coating. Two
or more layers can be simultaneously coated. As a solvent for
coating solution are employed organic solvents such as methyl ethyl
ketone (also denoted as MEK), ethyl acetate and toluene.
[0193] The thermally developable photosensitive material, which is
stable at ordinary temperatures, is exposed and heated at a high
temperature (preferably 80 to 200.degree. C., and more preferably
100 to 150.degree. C.) to undergo development. In cases when heated
at a temperature of lower than 80.degree. C., sufficient image
density can be obtained within a short time. Further, in cases when
heated at a temperature of higher than 200.degree. C., a binder
melts and is transferred to a roller, adversely affecting not only
images but also transportability and a developing machine. The
organic silver salt (functioning as an oxidant) and the reducing
agent undergo oxidation-reduction reaction upon heating to form
silver images. The reaction process proceeds without supplying any
processing solution such as water.
[0194] Any light source within the infrared region is applicable to
exposure of the thermally developable photosensitive material and
infrared semiconductor lasers (780 nm, 820 nm) are preferred in
terms of high power and transmission capability through the
photosensitive material.
[0195] In the invention, exposure is preferably conducted by laser
scanning exposure. It is also preferred to use a laser exposure
apparatus, in which scanning laser light is not exposed at an angle
substantially vertical to the exposed surface of the photosensitive
material. The expression "laser light is not exposed at an angle
substantially vertical to the exposed surface" means that laser
light is exposed preferably at an angle of 55 to 88.degree., more
preferably 60 to 86.degree., still more preferably 65 to 84, and
optimally 70 to 82.degree.. When the photosensitive material is
scanned with laser light, the beam spot diameter on the surface of
the photosensitive material is preferably not more than 200 .mu.m,
and more preferably not more than 100 .mu.m. Thus, the less spot
diameter preferably reduces an angle displacing from verticality of
the laser incident angle. The lower limit of the beam spot diameter
is 10 .mu.m. The thus laser scanning exposure can reduce
deterioration in image quality due to reflection light, such as
occurrence of interference fringe-like unevenness.
[0196] Exposure applicable in the invention is conducted preferably
using a laser scanning exposure apparatus producing longitudinally
multiple scanning laser light, whereby deterioration in image
quality such as occurrence of interference fringe-like unevenness
is reduced, as compared to scanning laser light with longitudinally
single mode. Longitudinal multiplication can be achieved by a
technique of employing backing light with composing waves or a
technique of high frequency overlapping. The expression
"longitudinally multiple" means that the exposure wavelength is not
a single wavelength. The exposure wavelength distribution is
usually not less than 5 nm and not more than 10 nm. The upper limit
of the exposure wavelength distribution is not specifically limited
but usually about 60 nm.
[0197] It is preferred that when subjected to thermal development,
the thermally developable photosensitive material contains an
organic solvent. Examples of solvents include ketones such as
acetone, isophorone, ethyl amyl ketone, methyl ethyl ketone, methyl
isobutyl ketone; alcohols such as methyl alcohol, ethyl alcohol,
n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl
alcohol, diacetone alcohol, cyclohexanol, and benzyl alcohol;
glycols such as ethylene glycol, dimethylene glycol, triethylene
glycol, propylene glycol and hexylene glycol; ether alcohols such
as ethylene glycol monomethyl ether, and dimethylene glycol
monomethyl ether; ethers such as ethyl ether, dioxane, and
isopropyl ether; esters such as ethyl acetate, butyl acetate, amyl
acetate, and isopropyl acetate; hydrocarbons such as n-pentane,
n-hexane, n-heptane, cyclohexene, benzene, toluene, xylene;
chlorinated compounds such as chloromethyl, chloromethylene,
chloroform, and dichlorobenzene; amines such as monomethylamine,
dimethylamine, triethanol amine, ethylenediamine, and
triethylamine; and water, formaldehyde, dimethylformaldehyde,
nitromethane, pyridine, toluidine, tetrahydrofuran and acetic acid.
The solvents are not to be construed as limiting these examples.
These solvents may be used alone or in combination.
[0198] The solvent content in the photosensitive material can be
adjusted by varying conditions such as temperature conditions at
the drying stage after the coating stage. The solvent content can
be determined by means of gas chromatography under the conditions
suitable for detecting the solvent. The total solvent content
(based on weight) of the thermally developable photosensitive
material used in the invention is preferably adjusted to be 40 to
4500 ppm, and more preferably 100 to 4000 ppm (based on the weight
of constituting components of the photosensitive material, except
for a support). The solvent content within the range described
above leads to a thermally developable photosensitive material with
low fog density as well as high sensitivity.
[0199] The use of novel infrared sensitizing dyes relating to the
invention is not limited to silver halide light sensitive
photographic materials and thermally developable photosensitive
materials each of which contains silver halide as a photosensitive
material or photosensor. These novel infrared sensitizing dyes are
applicable to any photosensitive composition, in which these dye
are capable of functioning as a photoreceptor, including a
photosensitive composition containing a non-silver photosensitive
substance which is capable of being spectral-sensitized with this
novel infrared sensitizing dye and a photosensitive composition
containing the infrared sensitizing dye, light absorption of which
enable to form images. Exemplary examples of the photosensitive
composition include a quinoneazide containing photosensitive
material used for lithographic printing plate and a photosensitive
composition used for free radical photography. Photosensitive
materials to make a lithographic printing plate, for example, are
described in U.S. Pat. Nos. 5,430,699, and 3,799,778; JP-A
53-13342, 60-37549 and 9-171254.
EXAMPLES
[0200] The present invention will be explained based on examples,
but embodiments of the invention are not limited to these.
Example 1
[0201] Preparation of Photographic material Sample 101
[0202] On a subbed cellulose triacetate film were coated the
following compositions to prepare photographic material Sample 101.
Unless otherwise noted, the addition amount of each compound was
represented in term of g/m.sup.2, provided that the amount of
silver halide or colloidal silver was converted to the silver
amount and the amount of a sensitizing dye was represented in
mol/Ag mol.
5 1st Layer: Anti-Halation Layer Black colloidal silver 0.18 UV
absorbent (UV-1) 0.30 High boiling solvent (Oil-2) 0.17 Gelatin
1.59 2nd Layer: Intermediate Layer High boiling solvent (Oil-2)
0.01 Gelatin 1.27 3rd Layer: Infrared-sensitive Layer Silver
iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.70
Sensitizing dye (as shown in Table 1) 5.0 .times. 10.sup.-5 Magenta
coupler (M-1) 0.20 High boiling solvent (Oil-1) 0.34 Gelatin 0.90
4th Layer: First Protective Layer Silver iodobromide emulsion 0.30
(av. 0.04 .mu.m, I:4.0 mol %) UV absorbent (UV-2) 0.03 UV absorbent
(UV-3) 0.015 UV absorbent (UV-4) 0.015 UV absorbent (UV-5) 0.015 UV
absorbent (UV-6) 0.10 High boiling solvent (Oil-1) 0.44 High
boiling solvent (Oil-3) 0.07 Gelatin 1.35 5th Layer: Second
protective Layer Alkali-soluble matting agent 0.15 (Av. Particle
size of 2 .mu.m) Polymethyl methacrylate 0.04 (av. Particle size of
3 .mu.m) Lubricant (WAX-1) 0.02 Gelatin 0.54
[0203] In addition to the above compositions, compounds Su-1, Su-2,
SU-3 and SU-4; viscosity-adjusting agent V-1; hardeners H-1 and
H-2; stabilizer ST-1; antifoggant AF-1 and AF-2, and AF-3 having a
weight-averaged molecular weight of 10,000 and 100,000; dyes AI-1,
AI-2 and AI-3; compounds FS-1 and Fs-2; and antiseptic agent DI-1
were optimally added to each layer. 12
[0204] Characteristics of silver iodobromide emulsions described
above are shown below, in which the average grain size refers to an
edge length of a cube having the same volume as that of the grain.
Each emulsion was subjected to gold, sulfur and selenium
sensitization.
6 Emul- Av. AgI Con- Av. Grain Crystal Diameter/ sion tent (mol %)
Size (.mu.m) Habit Thickness A 6.0 0.60 Twinned 4.0 Tabular B 8.0
0.90 Twinned 3.0 Tabular
[0205] Preparation of Photographic material Samples 102 to 115
[0206] Samples 102 to 115 were prepared in a manner similar to
Sample 101, except that sensitizing dye Dye-A (comparative dye)
used in the 3rd layer was replaced by an equimolar amount of a dye
as shown in Table 1.
[0207] Evaluation of Sensitivity and Fog
[0208] Samples 1-1 to 115 were cut to a size according to the
135-standard and allowed to stand under the following
conditions:
[0209] Condition A: 23.degree. C., 55% RH, 4 days
[0210] Condition B: 40.degree. C., 80% RH, 4 days.
[0211] Each sample was exposed to infrared light for 1/100 sec.,
using Kodak Wratten filter 89B, subjected to color processing
(CNK-4, available from Konica Corp.) and evaluated with respect to
sensitivity and fogging.
[0212] Fog Density
[0213] The fog density was represented by a green light
transmission density value measured by using PD transmission type
densitometer (available from Konica Corp.), as shown in Table
1.
[0214] Sensitivity
[0215] Sensitivity was represented by a relative value of
reciprocal of exposure necessary to give a density of a fog density
plus 0.15, based the sensitivity of Sample 101 being 100.
[0216] Evaluation of Standing and Storage Stability
[0217] Coating solution stability was evaluated as follows. A
coating solution used for the 3rd layer of each sample was allowed
to stand at 40.degree. C. for 30 min. and then coated to prepare a
photographic material sample. The photographic material was further
aged under the condition A and obtained sensitivity was denoted as
SiA. Another coating solution was allowed to stand at 40.degree. C.
for 8 hrs., the prepared photographic material sample was similarly
aged under the condition A and obtained sensitivity was denoted as
SCA. A value of variation in sensitivity, .DELTA.Sp (.dbd.SiA/SCA)
was regarded as a measure of coating solution stability.
[0218] Further, photographic material samples coated after allowing
the coating solution to stand at 40.degree. C. for 8 hrs. were each
aged under the condition B and obtained sensitivity was denoted as
SCB. Similarly, the photographic material samples each were aged
under the condition A and obtained sensitivity was denoted as SCA.
A value of variation in sensitivity, .DELTA.Ss (.dbd.SCA/SCB) was
regarded as a measure of storage stability of the photographic
material. Furthermore, a fog density of the photographic material
aged under the condition A was determined and denoted as FCA.
Similarly, a fog density of the photographic material aged under
the condition B was determined and denoted as FCB. A value of
difference in fog density, AFs (=FCB-FCA) was regarded as a measure
of storage stability with respect to fogging. The value of
.DELTA.Sp is the closer to 1, production stability (or coating
solution stability) was superior. The value of .DELTA.Ss or
.DELTA.Fs is the closer to 1, storage stability of the photographic
material was superior. Results are shown in Table 1.
7 TABLE 1 Sensitizing Fog Sensitivity Standing Aging Sample Dye
(FCA) (SCA) (.DELTA.Sp) .DELTA.Ss .DELTA.Fs Remark 101 Dye-A 0.08
100 1.29 1.23 0.05 Comp. 102 Dye-B 0.09 97 1.26 1.21 0.10 Comp. 103
Dye-C 0.07 102 1.15 1.28 0.05 Comp. 104 Dye-D 0.08 100 1.20 1.19
0.09 Comp. 105 No. S-3 0.06 106 1.12 1.14 0.05 Inv. 106 No. S-7
0.06 110 1.12 1.13 0.04 Inv. 107 No. S-9 0.07 112 1.09 1.12 0.03
Inv. 108 No. S-15 0.06 108 1.11 1.14 0.04 Inv. 109 No. S-21 0.06
106 1.13 1.15 0.07 Inv. 110 No. S-24 0.06 105 1.13 1.16 0.07 Inv.
111 No. S-41 0.06 109 1.08 1.11 0.04 Inv. 112 No. S-61 0.06 110
1.09 1.10 0.05 Inv. 113 No. S-63 0.07 109 1.12 1.13 0.06 Inv. 114
No. S-63 & 0.07 114 1.13 1.14 0.06 Inv. No. 10 (20:1) 115 No.
10 0.06 82 1.20 1.17 0.05 Comp. Dye-A 13 Dye-B 14 Dye-C 15 Dye-D
16
[0219] As apparent from Table 1, silver halide photographic
materials obtained according to the invention exhibited high
sensitivity, low fog, reduced variation in sensitivity due to
standing of coating solution and superior storage stability of raw
films.
Example 2
[0220] Preparation of a Subbed PET Photographic Support
[0221] Both surfaces of a biaxially stretched thermally fixed 175
.mu.m PET film, available on the market, was subjected to corona
discharging at 8 w/m.sup.2.multidot.min. Onto the surface of one
side , the subbing coating composition a-1 descried below was
applied so as to form a dried layer thickness of 0.8 .mu.m, which
was then dried. The resulting coating was designated Subbing Layer
A-1. Onto the opposite surface, the subbing coating composition b-1
described below was applied to form a dried layer thickness of 0.8
.mu.m. The resulting coating was designated Subbing Layer B-1.
8 Subbing Coating Composition a-1 Latex solution (solid 30%) of 270
g a copolymer consisting of butyl acrylate (30 weight %), t-butyl
acrylate (20 weight %) styrene (25 weight %) and 2-hydroxyethyl-
acrylate (25 weight %) (C-1) 0.6 g
Hexamethylene-1,6-bis(ethyleneurea) 0.8 g Water to make 1 liter
Subbing Coating Composition b-1 Latex liquid (solid portion of 30%)
270 g of a copolymer consisting of butyl acrylate (40 weight %)
styrene (20 weight %) glycidyl acrylate (25 weight %) (C-1) 0.6 g
Hexamethylene-1,6-bis(ethyleneurea) 0.8 g Water to make 1 liter
[0222] Subsequently, the surfaces of Subbing Layers A-1 and B-1
were subjected to corona discharging with 8
w/m.sup.2.multidot.minute. Onto the Subbing Layer A-1, the upper
subbing layer coating composition a-2 described below was applied
so as to form a dried layer thickness of 0.8 .mu.m, which was
designated Subbing Layer A-2, while onto the Subbing Layer B-1, the
upper subbing layer coating composition b-2 was applied so at to
form a dried layer thickness of 0.8 .mu.m, having a static
preventing function, which was designated Subbing Upper Layer
B-2.
9 Upper Subbing Layer Coating Composition a-2 Gelatin in an amount
(weight) to make 0.4 g/m.sup.2 (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g
Silica particles (av. size 3 .mu.m) 0.1 g Water to make 1 liter
Upper Subbing Layer Coating Composition b-2 (C-4) 60 g Latex
solution (solid 20% comprising) 80 g (C-5) as a substituent
Ammonium sulfate 0.5 g (C-6) 12 g Polyethylene glycol (average 6 g
molecular weight of 600) Water to make 1 liter (C-1) 17 (C-2) 18
(C-3) 19 (C-4) 20 ({overscore (M)}n is a number average molecular
weight) x:y = 75:25 (weight ratio) (C-5) 21 22 23 24 25 p:g:r:s:t =
40:5:10:5:40 (weight ratio) (C-6) 26 27 28 Mixture consisting of
the three compounds illustrated above
[0223] Thermal Treatment of Support
[0224] The subbed support was dried at 140.degree. C. in the
process of subbing and drying a support.
[0225] Preparation of Silver Halide Emulsion
[0226] In 900 ml of deionized water were dissolved 7.5 g of gelatin
and 10 mg of potassium bromide. After adjusting the temperature and
the pH to 35.degree. C. and 3.0, respectively, 370 ml of an aqueous
solution containing 74 g silver nitrate and an equimolar aqueous
solution containing potassium bromide, potassium iodide (in a molar
ratio of 98 to 2) and 1.times.10.sup.-6 mol/mol Ag of
Ir(NO)Cl.sub.5 and 1.times.10.sup.-6 of rhodium chloride were added
over a period of 10 minutes by the controlled double-jet method,
while the pAg was maintained at 7.7. Thereafter,
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added and the pH was
adjusted to 5 using NaOH. There was obtained cubic silver
iodobromide grains having an average grain size of 0.06 .mu.m, a
variation coefficient of the projection area equivalent diameter of
11 percent, and the proportion of the {100} face of 87 percent. The
resulting emulsion was flocculated to remove soluble salts,
employing a flocculating agent and after desalting, 0.1 g of
phenoxyethanol was added and the pH and pAg were adjusted to 5.9
and 7.5, respectively to obtain silver halide emulsion.
[0227] Preparation of Sodium Behenate
[0228] In 945 ml water at 90.degree. C. were dissolved 32.4 g of
behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid.
Aqueous 1.5 M sodium hydroxide solution of 98 ml was added thereto,
while stirring at high speed. Then, after adding 0.93 ml of
concentrated nitric acid, the reaction mixture was cooled to
55.degree. C. and stirred for 30 min. to obtain a sodium behenate
aqueous solution.
[0229] Preparation of Pre-formed emulsion of silver Behenate and
Silver Halide Emulsion
[0230] To the sodium behenate solution was added 15.1 g of the
silver halide emulsion. After adjusting the pH at 8.1 with aqueous
sodium hydroxide solution, 147 ml of aqueous 1 M silver nitrate
solution was added in 7 min. After stirring for 20 min., the
reaction mixture was subjected ultrafiltration to remove soluble
salts. Thus prepared silver behenate dispersion was comprised of
monodisperse particles having an average size of 0.8 .mu.m. The
dispersion was flocculated and water was removed and washing and
removal of water were further repeated six times and dried.
[0231] Preparation of Photosensitive Emulsion
[0232] To the pre-formed emulsion, 544 g of a methyl ethyl ketone
(MEK) solution of polyvinyl butyral (average molecular weight of
3,000 and 17 wt %) and 107 g toluene was gradually added with
mixing and dispersed at a rate of 280 kgf/cm.sup.2.
[0233] Backing-side Coating
[0234] A coating solution for a backing layer of the following
composition was coated by an extrusion coater on the side of B-2
layer of the support so as to have a wet thickness of 30 .mu.m and
dried at 60.degree. C. for 3 min.
10 Cellulose acetate (10% methyl ethyl ketone solution) 15
ml/m.sup.2 Dye-B 7 mg/m.sup.2 Dye-C 7 mg/m.sup.2 Matting agent,
monodispersed silica having mono- 30 mg/m.sup.2 dispersity of 15%
and a mean size of 10 .mu.m
C.sub.9H.sub.19--C.sub.6H.sub.4--SO.sub.3Na 10 mg/m.sup.2 Dye-B 29
Dye-C 30
[0235] Emulsion side coating Photosensitive layer 1
[0236] On the sub-layer A-2 side of the support, a photosensitive
layer having the following composition and, further thereon, a
protective layer were coated so as to have silver coverage of 2.4
g/m.sup.2, and thereafter dried at 55.degree. C. in 15 min.
11 Photosensitive layer coating solution Photosensitive emulsion
240 g Sensitizing dye (as shown in Table 2) 1.7 ml (0.1% methanol
solution) Pyridinium bromide perbromide 3 ml (6% methanol solution)
Calcium bromide (0.1% methanol solution) 1.7 ml Antifoggant-2 (10%
methanol solution) 1.2 ml 2-(4-Chlorobenzoyl)-benzoic acid 9.2 ml
(12% methanol solution) 2-Mercaptobenzimidazole (1% methanol
solution) 11 ml Tribromethylsulfoquinoline (5% methanol solution)
17 ml Reducing agent A-3 (20% methanol solution) 29.5 ml
Phthalazinone 0.6 g 4-Methylphthalic acid 0.25 g
Tetrachlorophthalic acid 0.2 g Antifoggant-2 31 Surface protective
layer coating solution Acetone 5 ml/m.sup.2 Methyl ethyl ketone 21
ml/m.sup.2 Cellulose acetate 2.3 g/m.sup.2 Methanol 7 ml/m.sup.2
Phthalazinone 250 mg/m.sup.2 Matting agent, monodisperse silica
having mono 70 mg/m.sup.2 dispersity of 10% and a mean size of 4
.mu.m
CH.sub.2.dbd.CHSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2SO.sub.2CH.dbd.CH-
.sub.2 35 mg/m.sup.2 C.sub.9H.sub.19--C.sub.6H.sub.4--SO.sub.3Na 10
mg/m.sup.2
[0237] Exposure and Processing
[0238] The thus prepared thermally developable photosensitive
material samples were each exposed to laser light using an imager
having a semiconductor laser of 810 nm; and the exposed
photosensitive material samples were subjected to thermal
development at 110.degree. C. for 15 sec. Exposure and development
were conducted in an environment maintained at 23.degree. C. and
50% RH.
[0239] Sensitometric Evaluation
[0240] Unexposed areas of the developed samples were measured with
respect to a fog density. The less the value thereof, the better.
Sensitivity (also denoted as "S") was represented by relative value
of reciprocal of exposure necessary to a density of a fog density
plus 1.0, based on the sensitivity of Sample 2-1 being 100.
[0241] Thermostatic Aging Test
[0242] The thermally developable photosensitive material samples
were allowed to stand in a thermostatic chamber maintained at
40.degree. C. and 50% RH for 5 days. The aged samples were measured
with respect to sensitivity and fog density.
[0243] Evaluation results are shown in Table 2.
12 TABLE 2 Fresh Sample Aged Sample Sample Sensitizing Dye Fog S
Fog S Remark 2-1 Dye-E 0.18 100 0.22 111 Comp. 2-2 Dye-F 0.23 106
0.34 118 Comp. 2-3 Dye-G 0.12 40 0.15 44 Comp. 2-4 No. S-4 0.13 114
0.17 118 mv. 2-5 No. S-6 0.14 118 0.17 124 mv. 2-6 No. S-11 0.13
119 0.17 125 mv. 2-7 No. S-13 0.14 118 0.16 125 mv. 2-8 No. S-16
0.14 114 0.19 117 mv. 2-9 No. S-27 0.15 121 0.20 124 mv. 2-10 No.
S-30 0.16 111 0.21 117 mv. 2-11 No. S-43 0.13 122 0.19 125 mv. 2-12
No. S-43 & No. 3* 0.13 129 0.18 132 mv. 2-13 No. 3 0.12 58 0.16
70 Comp. 2-14 No. S-49 0.13 124 0.16 127 mv. 2-15 No. S-64 0.15 113
0.18 119 mv. 2-16 No. S-68 0.15 113 0.20 120 mv. 2-17 No. S-68
& No. 9* 0.15 122 0.18 128 mv. 2-18 No. 9 0.14 51 0.19 60 Comp.
Dye-E 32 Dye-F 33 Dye-G 34 *Mixture of the dyes in a molar ration
of 20:1
[0244] As apparent from Table 2, thermally developable
photosensitive materials according to the invention exhibited
superior sensitivity and reduced fogging, being little variation in
sensitivity and fog density even when subjected to accelerated
aging test and exhibiting superior storage stability of raw
films.
Example 3
[0245] Preparation of Presensitized Plate for Lithographic
Printing
[0246] A JIS-1050 aluminum plate of 0.24 mm thick was subjected to
a degreasing treatment by immersing it in aqueous 10% sodium
hydroxide solution maintained at 10.degree. C. for 1 min and
washed. The degreased aluminum plate was further subjected to a
death-matting treatment by immersion into aqueous 10% sulfuric acid
solution at 25.degree. C. and washed. The surface of the aluminum
plate was electrochemically roughened in aqueous 1.0% nitric acid
solution at 30.degree. C., a current density of 50 A/dm.sup.2 and
an electrolicity quantity of 400 c/dm.sup.2. Thereafter, the plate
was subjected to chemical etching at an aluminum-dissolution rate
of 3 g/m2 in aqueous 10% sodium hydroxide solution at 50.degree. C.
Subsequently, the plate was subjected to a death-matting treatment
by immersing in aqueous 10% nitric acid solution at 25.degree. C.
for 10 sec. and washed. The plate was then subjected to anodic
oxidation treatment in aqueous 20% sulfuric acid solution at
35.degree. C. and a current density of 2 A/dm.sup.2 for 1 min.
Thereafter, the plate was subjected to sealing treatment by
immersing into aqueous 0.1% ammonium acetate solution at 80.degree.
C. for 30 sec. and dried at 80.degree. C. for 5 min. On one side
(back side) of the aluminum plate, an aqueous solution of JIS No. 3
sodium silicate (10 g/l) was coated by a wire-bar and dried at
80.degree. C. for 3 min. to obtain an aluminum plate for use as a
support having a covering layer on the back side. The coverage of
the covering layer was 10 mg/M.sup.2.
[0247] On the other side of the support, a coating solution for a
photosensitive layer having the following composition was coated
using a wire-bar and dried at 80.degree. C. for 2 min. to obtain a
photosensitized plate 310 for lithographic printing. The coverage
of the photosensitive layer was 2.0 g/m.sup.2. The term, part(s)
means part(s9 by weight.
13 Binder A; novolac resin comprised of co- 70 parts
polycondensation polymer of phenol/ m-and p- cresol/formaldehyde
(5/57/38, Mw = 4,000) Binder B; copolymer of methyl methacrylate/ 5
parts hydroxyphenylmethacrylamide/methacry- lamide/
methacryloitrile (20/20/30/30, Mw = 30,000) Acid-decomposable
compound (A) 20 parts Acid-generating agent (B) 3 parts Infrared
absorbing dye (Table 3) 1 part Crystal violet 0.3 part Fluorinated
surfactant S-381 (available 0.5 part From Asahi Chemical Co. ltd.)
Methyl lactate 700 parts Methyl ethyl ketone (MEK) 200 parts
[0248] As the acid-decomposable compound (A) was used Compound S-1
described in Synthesis Example of Japanese Patent Application No.
9-300540, col. 0047, forming a diol compound containing an ethylene
glycol component or propylene glycol component upon reaction with
acid generated by the acid-generating agent (B), as shown below:
35
[0249] Using the thus obtained lithographic printing plate, images
were formed according to the following procedure. Thus, the plate
was image wise exposed using an exposure apparatus Trend Setter
3244 (available from Kreo Product Corp., mounted with semiconductor
laser of 830 nm at an output of 10 W and 240 channels) and
processed using an automatic processor PSZ-910 and developer SDR-1
(both available from Konica Corp.). Using 25 lit. of a developing
solution, which was prepared by diluting SDR-1 to 6 times with
water, in a developing bath, development was conducted at a
temperature of 32.degree. C. for 1.2 sec. and thereafter washing
was undergone. The thus prepared printing plate was evaluated with
respect to sensitivity and storage stability:
[0250] Sensitivity; exposure energy necessary to remove exposed
areas of the photosensitive layer (mJ/cm.sup.2), and
[0251] Storage stability; sensitivity of the printing plate
obtained after aged at 50.degree. C. and 80% RH for 3 days
[0252] Results thereof are shown in Table 3.
14 TABLE 3 Sensitivity (mj/cm.sup.2) Sample IR Dye Fresh Aged
Remark 3-1 Dye-H 200 35 Comp. 3-2 Dye-I 160 200 Comp. 3-3 No. S-2
240 260 Inv. 3-4 No. S-18 250 265 Inv. 3-5 No. S-32 240 260 Inv.
3-6 No. S-47 255 265 Inv. 3-7 No. S-54 235 245 Inv. 3-8 No. S-66
205 230 Inv. Dye-H 36 Dye-1 37
[0253] As apparent from Table 3, image forming materials according
to the invention exhibited superior sensitivity upon exposure to
infrared light, being little variation in sensitivity even after
subjected to accelerated aging and superior in storage
stability.
Example 4
[0254] Preparation of a Subbed PET Photographic Support
[0255] Both surfaces of a biaxially stretched thermally fixed 100
.mu.m PET film, available on the market, was subjected to corona
discharging at 8 w/m.sup.2.multidot.min. Onto the surface of one
side , the subbing coating composition a-1 descried below was
applied so as to form a dried layer thickness of 0.8 .mu.m, which
was then dried. The resulting coating was designated Subbing Layer
A-1. Onto the opposite surface, the subbing coating composition b-1
described below was applied to form a dried layer thickness of 0.8
.mu.m. The resulting coating was designated Subbing Layer B-1.
15 Subbing Coating Composition a-1 Latex solution (solid 30%) of
270 g a copolymer consisting of butyl acrylate (30 weight %),
t-butyl acrylate (20 weight %) styrene (25 weight %) and 2-hydroxy
ethyl acrylate (25 weight %) (C-1) 0.6 g
Hexamethylene-1,6-bis(ethyleneurea) 0.8 g Water to make 1 liter
Subbing Coating Composition b-1 Latex liquid (solid portion of 30%)
270 g of a copolymer consisting of butyl acrylate (40 weight %)
styrene (20 weight %) glycidyl acrylate (25 weight %) (C-1) 0.6 g
Hexamethylene-1,6-bis(ethyleneurea) 0.8 g Water to make 1 liter
[0256] Subsequently, the surfaces of Subbing Layers A-1 and B-1
were subjected to corona discharging with 8
w/m.sup.2.multidot.minute. Onto the Subbing Layer A-1, the upper
subbing layer coating composition a-2 described below was applied
so as to form a dried layer thickness of 0.8 .mu.m, which was
designated Subbing Layer A-2, while onto the Subbing Layer B-1, the
upper subbing layer coating composition b-2 was applied so at to
form a dried layer thickness of 0.8 .mu.m, having a static
preventing function, which was designated Subbing Upper Layer
B-2.
16 Upper Subbing Layer Coating Composition a-2 Gelatin in an amount
(weight) to make 0.4 g/m.sup.2 (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g
Silica particles (av. size 3 .mu.m) 0.1 g Water to make 1 liter
Upper Subbing Layer Coating Composition b-2 (C-4) 60 g Latex
solution (solid 20% comprising) 80 g (C-5) as a substituent
Ammonium sulfate 0.5 g (C-6) 12 g Polyethylene glycol (average 6 g
molecular weight of 600) Water to make 1 liter (C-1) 38 (C-2) 39
(C-3) 40 (C-4) 41 ({overscore (M)}n is a number average molecular
weight) x:y = 75:25 (weight ratio) (C-5) 42 p:g:r:s:t =
40:5:10:5:40 (weight ratio) (C-6) 43 44 Mixture consisting of the
three compounds illustrated above
[0257] Thermal Treatment of Support
[0258] The subbed support was dried at 140.degree. C. in the
process of subbing and drying a support.
[0259] Preparation of Backing Coat Composition
[0260] To 830 g of methyl ethyl ketone, 84.2 g of cellulose
acetate-butylate (CAB381-20, available from Eastman Chemical Co.)
and 4.5 g of polyester resin (Vitel PE2200B, available from Bostic
Corp.) was added with stirring and dissolved therein. To the
resulting solution was added 0.30 g of infrared dye 1 (which was
the same as used in the photosensitive layer described later) and
4.5 g fluorinated surfactant (Surflon KH40, available from ASAHI
Glass Co. Ltd.) and 2.3 g fluorinated surfactant (Megafag F120K,
available from DAINIPPON INK Co. Ltd.) which were dissolved in 43.2
g methanol, were added thereto and sirred until being dissolved.
Then, 75 g of silica (Siloid 64X6000, available from W. R. Grace
Corp.), which was dispersed in methyl ethyl ketone in a
concentration of 1 wt % using a dissolver type homogenizer, was
further added thereto with stirring to obtain a coating composition
for backing layer.
[0261] Coating of Backing Layer
[0262] The thus prepared coating composition for a backing layer
was coated by an extrusion coater and dried so as to have dry
thickness of 3.5 .mu.m and dried at a dry-bulb temperature of
100.degree. C. and a wet-bulb temperature of 10.degree. C. over a
period of 5 min.
[0263] Preparation of Photosensitive Silver Halide Emulsion a
[0264] In 900 ml of deionized water were dissolved 7.5 g of gelatin
and 10 mg of potassium bromide. After adjusting the temperature and
the pH to 35.degree. C. and 3.0, respectively, 370 ml of an aqueous
solution containing 74 g silver nitrate and an equimolar aqueous
solution containing potassium bromide, potassium iodide (in a molar
ratio of 98 to 2) and 1.times.10.sup.-4 mol/mol Ag of iridium
chloride were added over a period of 10 minutes by the controlled
double-jet method, while the pAg was maintained at 7.7. Thereafter,
4-hydroxy-6-methyl-1,3,3a,7-tetraazain- dene was added and the pH
was adjusted to 5 using NaOH. There was obtained cubic silver
iodobromide grains having an average grain size of 0.06 .mu.m, a
variation coefficient of the projection area equivalent diameter of
11 percent, and the proportion of the {100} face of 87 percent. The
resulting emulsion was flocculated to remove soluble salts,
employing a flocculating agent and after desalting, 0.1 g of
phenoxyethanol was added and the pH and pAg were adjusted to 5.9
and 7.5, respectively to obtain silver halide emulsion a. The thus
obtained photosensitive emulsion grains were measured with respect
to the average iodide content in the vicinity of the grain surface
and it was proved to be 4.0 mol %.
[0265] Preparation of Powdery Organic Silver Salt
[0266] In 4720 ml water were dissolved 111.4 g of behenic acid,
83.8 g of arachidic acid and 54.9 g of stearic acid at 80.degree.
C. The, after adding 540.2 ml of 1.5 M aqueous sodium hydroxide
solution with stirring and further adding 6.9 ml of concentrated
nitric acid, the solution was cooled to a temperature of 55.degree.
C. to obtain an aqueous organic acid sodium salt solution. To the
solution were added the silver halide emulsion obtained above
(equivalent to 0.038 mol silver) and 450 ml water and stirring
further continued for 5 min., while maintained at a temperature of
55.degree. C. Subsequently, 760 ml of 1 M aqueous silver nitrate
solution was added in 2 min. and stirring continued further for 20
min., then, the reaction mixture was filtered to remove aqueous
soluble salts. Thereafter, washing with deionized water and
filtration were repeated until the filtrate reached a conductivity
of 2 .mu.S/cm, and after subjecting to centrifugal dehydration, the
reaction product was dried with heated air at 37.degree. C. until
no reduction in weight was detected to obtain powdery organic
silver salt a.
[0267] Preparation of Photosensitive Emulsion dispersing Solution
1
[0268] In 1457 g methyl ethyl ketone was dissolved 14.57 g of
polyvinyl butyral powder (Butvar B-79, available from Monsanto
Corp.) and further thereto was gradually added 500 g of the powdery
organic silver salt with stirring by a dissolver type homogenizer.
Thereafter, the mixture was dispersed using a media type dispersion
machine (available from Gettzmann Corp.), which was packed 1 mm Zr
beads (available from Toray Co. Ltd.) by 80%, at a circumferential
speed of 13 m and for 0.5 min. of a retention time with a mill to
obtain photosensitive emulsion dispersing solution 1.
[0269] Preparation of Infrared Sensitizing Dye Solution
[0270] In 73.4 ml methanol were dissolved 350 mg of infrared
sensitizing dye 1 (IR Dye 1) or an equimolar amount of an infrared
sensitizing dye as shown in Table 1, 4.65 g of 2-chlorobenzoic
acid, 9.30 g of benzoic acid 1 (o-tolylsulfonyloxybenzoic acid) and
2.14 g of 5-methyl-2-mercaptobenzi- midazole in a dark room to
obtain an infrared sensitizing dye solution.
[0271] Preparation of Photosensitive Layer Coating Composition
[0272] The photosensitive emulsion dispersing solution 1 of 500 g
and 100 g MEK were maintained at 21.degree. C. with stirring.
[0273] Then, 0.45 g antifoggant 1 was added and stirred for 1 hr.
and calcium bromide (3.25 ml of 10% methanol solution) was added
and further stirred for 20 min. Subsequently, a compound
represented by CR-19 (1.00 ml of 15% methanol solution containing
5% potassium acetate) was added thereto, and stirred for 10 min.
Then, the sensitizing dye solution prepared above was added,
stirred for 1 hr. and after cooling to a temperature of 13.degree.
C., stirring further continued for 30 min. Further, 48 g of
polyvinyl butyral was added thereto and sufficiently dissolved,
while maintaining the temperature at 13.degree. C.; then, the
following additives were added:
17 Macrocyclic compound (CR-19) 0.20 g Developer (exemplified A-3)
15 g Antifoggant 2 0.5 g Desmodu N3300 (aliphatic isocyanate,
available from Movey Corp.) 1.10 g Phthalazinone 1.5 g
Tetrachlorophthalic acid 0.5 g 4-Methylphthalic acid 0.5 g Infrared
dye 1 0.30 g
[0274] Surface protective Layer Preparation of Dispersion
[0275] In 42.5 g methyl ethyl ketone was dissolved 15 g of
cellulose acetate-butylate (CAB171-15, available from Eastman
Chemical Co.) and then 5 g of calcium carbonate (Super-Pflex 200,
available from Speciality Mineral Corp.) was added thereto and
dispersed using a dissolver type homogenizer at a speed of 800 rpm
over a period of 30 min. to obtain calcium carbonate
dispersion.
[0276] Preparation of Coating solution for Protective Layer
[0277] To 865 g of methyl ethyl ketone were added with stirring 96
g of cellulose acetate-butylate (CAB171-15, available from Eastman
Chemical Co.) and 4.5 g of polymethyl methacrylate (Paraloid A-21,
available from Rohm & Haas Corp.). Further thereto were added
and dissolved 1.5 g of vinylsulfon compound HD-1, 1.0 g of
benzotriazole and 1.0 g of fluorinated surfactant (Surflon KH40,
available from ASAHI Glass Co. Ltd.). Finally, 30 g of calcium
carbonate dispersion was added and stirred to obtain a coating
composition for the surface protective layer.
[0278] Coating of Photosensitive Layer and Protective Layer
[0279] The prepared coating composition for the photosensitive
layer was allowed to stand for a period of time as shown in Table 4
with maintaining a temperature of 13.degree. C. and then coated
according to the following procedure to prepare coating Samples 1
to 3. Further, coating Samples 4 to 24 were similarly prepared,
except that the infrared sensitizing dye 1 (also denoted as IR Dye
1) was replaced by a dye according to the invention and the layer
to be added with phthalazine, tetrachlorophthalic acid or
4-methylphthalic acid or the standing time after addition thereof
was varied as shown in Table 4. The amount of these compounds to be
added to the protective layer was 1.25 times the amount to be added
to the photosensitive layer. The photosensitive layer coating
composition and the protective layer coating composition described
above were simultaneously coated by means of an extrusion coater at
a coating speed of 20 m/min so that the silver coverage of the
photosensitive layer was 2.0 g/m.sup.2 and dry thickness of the
protective layer was 2.5 .mu.m. Thereafter, drying was conducted
using hot-air at a dry-bulb temperature of 750 C and a wet-bulb
temperature of 10.degree. C. over a period of 10 min. 45
[0280] HD-1
CH.sub.2.dbd.CHSO.sub.2CH.sub.2
CH.sub.2OCH.sub.2CH.sub.2SO.sub.2CH.dbd.CH- .sub.2
[0281] Thus obtained coating Sample Nos. were shown in Table 4.
18TABLE 4 Sensi- Benzenepolycarbox- Standing Time tizing
Phthalazine ylic Acid (Sample No.) 30 Dye Compd. Layer Compd. Layer
sec 2 hr. 24 hr. IR Dye 1 Ph.sup.*1 Phot.sup.*2 Tp.sup.*1 +
Mp.sup.*1 Phot 1 2 3 IR Dye 1 Ph Pro.sup.*2 Tp + Mp Phot 4 5 6
No.S-43 Ph Phot Tp + Mp Phot 7 8 9 No.S-43 Ph Pro Tp + Mp Phot 10
11 12 No.S-49 Ph Phot Tp + Mp Phot 13 14 15 No.S-49 Ph Pro Tp + Mp
Phot 16 17 18 No.S-6 Ph Phot Tp + Mp Phot 19 20 21 No.S-6 Ph Pro Tp
+ Mp Phot 22 23 24 .sup.*1Ph; Phthalazine, Tp;
Tetrachlorophthalazine, and Mp; 4-Methylphthalic acid .sup.*2Phot;
Photosensitive layer, Pro; Protective layer
[0282] Measurement of Solvent Content of Film
[0283] Film samples were each measured with respect to the solvent
content. Thus, sample films each were cut to an area of 46.3
cm.sup.2, further finely cut to about 5 mm, contained into a
specified Bayern bottle, which was closely packed with septum and
aluminum cap, and set to head space sampler HP769 (available
Hewlett Pachard Co.), which was connected to gas chromatography
(GC) Hewlett Packard type 5971 provided with a hydrogen flame ion
detector (FID). Chromatograms were obtained under the measurement
conditions including a head space sampler heating temperature of
120.degree. C. for 20 min., a GC-introducing temperature of
150.degree. C., column of DB-624 (available from J & W co.) and
temperature-increasing of 45.degree. C. (3 min.) to 100.degree. C.
at a rate of 8.degree./min. Solvents to be measure were methyl
ethyl ketone and methanol. A given amount of each solvent, which
was further diluted with butanol was contained into a Bayern bottle
and subjected to the chromatographic measurement in a manner
similar to above. Using a calibration curve prepared from the
obtained chromatogram peak area, the solvent content of each film
sample was determined. Unless otherwise noted, the solvent content
in the film was set to be 50 ppm by adjusting the drying time of
coated samples.
[0284] Exposure and Development
[0285] Samples each were cut to a size of 3.5 cm.times.15 cm and
allowed to stand under the following condition (A) or (B):
[0286] (A) at 23.degree. C. and 55% RH, and for 24 hrs. and
[0287] (B) at 55.degree. C. and 55% RH, and for 72 hrs.
[0288] Thereafter, each of aged samples was subjected to laser
scanning exposure from the emulsion side using an exposure
apparatus having a light source of 800 to 820 nm semiconductor
laser of longitudinal multi-mode, which was made by means of high
frequency overlapping. In this case, exposure was conducted at an
angle between the exposed surface and exposing laser light was
75.degree. and in an atmosphere at a temperature of 23.degree. C.
and 50% RH (and as a result, images with superior sharpness were
unexpectedly obtained, as compared to exposure at an angle of
90.degree.). Using an automatic processor provided with a heated
drum, subsequently, exposed samples were subjected to thermal
development at 120.degree. C. for 15 sec., while bringing the
protective layer surface of the photosensitive material into
contact with the drum surface. The thermal development was
conducted in an atmosphere at 23.degree. C. and 50% RH.
[0289] Sensitometric Evaluation
[0290] Thermally developed samples each were subjected to
sensitometry using a densitometer and evaluated with respect to a
fog density (i.e., minimum density and denoted as Dmin) and
sensitivity. The sensitivity was represented by a relative value of
reciprocal of exposure necessary to give a density of Dmin plus
1.0, based on the sensitivity of Sample 1 being 100.
19 TABLE 5 Condition A Condition B Sample Fog Sensitivity Fog
Sensitivity 1 0.25 100 0.34 70 2 0.26 90 0.35 65 3 0.27 70 0.37 54
4 0.25 105 0.35 72 5 0.26 95 0.36 66 6 0.27 80 0.38 53 7 0.22 125
0.27 107 8 0.22 120 0.27 100 9 0.23 100 0.28 81 10 0.23 125 0.27
105 11 0.23 125 0.27 103 12 0.23 123 0.28 102 13 0.22 130 0.28 106
14 0.22 125 0.28 102 15 0.23 100 0.29 71 16 0.23 133 0.28 105 17
0.23 130 0.28 101 18 0.24 125 0.29 100 19 0.22 127 0.28 105 20 0.22
125 0.28 103 21 0.23 100 0.30 73 22 0.24 130 0.28 106 23 0.24 130
0.28 103 24 0.24 125 0.28 99
[0291] As apparent from Table 5, it was proved that samples
prepared according to the invention by the combined use of
inventive sensitizing dyes, and phthalazine/tetrachlorophthalic
acid/4-methylphthalic acid led to superiority in sensitivity and
fogging, irrespective of aging conditions.
Example 5
[0292] Samples 25 to 45 were prepared similarly to example 4,
provided that the infrared sensitizing dye used in Samples 7 to 12
was used, and additives and the standing time were varied as shown
in Table 6.
20TABLE 6 Benzenepoly- Standing Time Phthalazine carboxylic Acid
(Sample No.) Compd. Layer Compd. Layer 30 sec 2 hr. 24 hr.
Ph*.sup.1 Phot*.sup.2 Tp*.sup.1 + Mp*.sup.1 Phot 25 26 27 Ph
Pro*.sup.2 Tp + Mp Phot 28 29 30 Phn*.sup.1 Phot Tp + Mp Phot 31 32
33 Ph Pro Tp + Mp Phot 34 35 36 Ch*.sup.1 Pro Tp + Mp Phot 37 38 39
Ph Pro Np*.sup.1 + Mp Phot 40 41 42 Ph Pro Tp + Np Phot 43 44 45
*.sup.1Ph; Phthalazine, Phn; Phthalazinone, Ch;
6-Chlorophthalazine, Tp; Tetrachlorophthalazine, Mp;
4-Methylphthalic acid and Np; 4-Nitrophthalic acid *.sup.2Phot;
Photosensitive layer, Pro; Protective layer
[0293] Samples were evaluated in the same manner as Example 4.
Results thereof are shown in Table 7.
21 TABLE 7 Condition A Condition B Sample Fog Sensitivity Fog
Sensitivity 25 0.22 127 0.27 103 26 0.22 125 0.28 99 27 0.24 70
0.35 50 28 0.22 128 0.27 104 29 0.22 126 0.28 100 30 0.25 80 0.34
53 31 0.22 125 0.27 105 32 0.23 120 0.27 101 33 0.25 100 0.32 71 34
0.22 125 0.28 107 35 0.22 125 0.28 103 36 0.23 123 0.29 101 37 0.22
130 0.28 107 38 0.22 125 0.28 105 39 0.23 120 0.29 102 40 0.22 133
0.29 106 41 0.23 130 0.29 105 42 0.23 125 0.29 100 43 0.22 127 0.28
104 44 0.23 125 0.28 103 45 0.24 120 0.28 102
[0294] As apparent from Table 7, the use of phthalazines,
phthalazinones or benzenepolycarboxylic acids led to enhanced
sensitivity and little variation in photographic performance, even
when being allowed to stand for a long period of time. Even in
cases where the compounds described above are separately
incorporated into the photosensitive layer and protective layer,
similar effects were displayer.
Example 6
[0295] Remaining Solvent Dependence
[0296] Samples 46 to 49 were prepared in a manner similar to Sample
4 of Example 4, except that the drying time was varied, and Samples
50 to 53 were prepared in a manner similar to Sample 7 of Example
4, except that the drying time was varied, as shown in Table 8.
22TABLE 8 Remained Solvent Content (ppm) 10 50 500 4000 8000 46 4
47 48 49 50 7 51 52 53
[0297] Samples each were similarly exposed, processed and
evaluated. Results thereof are shown in Table 9.
23 TABLE 9 Condition A Sample Fog Sensitivity 46 0.23 72 4 0.25 105
47 0.29 108 48 0.36 112 49 0.51 110 50 0.22 97 7 0.22 125 51 0.23
132 52 0.26 130 53 0.37 129
[0298] As apparent from table 9, the organic solvent-remaining
content within the preferred range led to preferable results with
respect to relationship between fog and sensitivity. Further, it
was shown that the combination of the sensitizing dye according to
the invention, and phthalazine, phthalazinone and
benzenepolycarboxylic acid tended to reduce variation in
photographic performance, caused by the organic solvent remaining
content. Thus, it was proved that superior thermally developable
photosensitive materials could be stably supplied to the
market.
* * * * *