Dye precursor, photosensitive material containing dye...

Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making

Reexamination Certificate

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C430S270150, C430S170000, C430S955000, C564S047000

Reexamination Certificate

active

06303269

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a dye precursor and a photosensitive material useful for a printing material for digital image information output and the like, and a method for forming a color image using the dye precursor.
BACKGROUND OF THE INVENTION
A dye precursor which forms a dye by heating is disclosed in WO 90/00978, and a dye precursor represented by the following formula is disclosed as one example:
wherein X represents —NR′R″ (wherein R′ and R″ each is selected from a hydrogen atom and an alkyl group having from 1 to 6 carbon atoms); Y′ represents a hydrogen atom, an alkyl group or a substituted alkyl group; and Z and Z′ each represents a protective group capable of being removed by heating or a dissociative group.
As examples of a dissociative group on a nitrogen atom or a protective group capable of being removed by heating on a nitrogen atom, an alkylsulfonyl group, an arylsulfonyl group and the groups represented by the following formulae (a) and (b):
wherein R
A1
represents an alkyl group generally having from 1 to 6 carbon atoms, a halomethyl group such as a methyl group substituted with 1, 2 or 3 halo groups (e.g., chloro or bromo), or a substituted or unsubstituted aryl group (generally a phenyl group);
wherein R
A2
and R
A3
each represents a hydrogen atom, an alkyl group or an aryl group (generally a phenyl group); R
A4
represents a hydrogen atom, an alkyl group, an aryl group (generally a phenyl group), or EW; and EW represents an electron attractive group.
However, the dye precursor represented by the above formula having a dissociative group or a protective group represented by Z cannot satisfy the conditions that the heat stability of the dye precursor under a neutral or basic condition should be sufficiently high and the color-forming capability under an acidic condition should be sufficiently high.
Dye precursors which form dyes by oxidizing agents such as silver salts are known and disclosed in WO 94/22052. As these dye precursors form dyes by an oxidation reaction, coupler components other than 4-equivalent couplers cannot be used. Further, these dye precursors did not substantially form dyes by the action of an acid.
That is, dye precursors which substantially do not form a dye by heating the dye precursor alone or by an oxidation reaction but rapidly form a dye by the action of an acid have not been known yet.
However, a photosensitive material containing a dye precursor represented by the above-described formula is not known.
Photosensitive materials containing dye precursors are disclosed in WO 94/22052. As these dye precursors form dyes by an oxidation reaction, coupler components other than 4-equivalent couplers cannot be used. Further, these techniques require to use an oxidizing agent such as a silver salt which is not desirable for a printing material for digital image information output.
That is, photosensitive materials containing dye precursors which do not necessitate oxidizing agents such as silver salts for color-forming have not been known yet.
Dye precursors which form azomethine dyes are disclosed in WO 90/00978 and WO 94/22052. Specific examples of coupler residues for use in the dye precursors disclosed in these publications are a pyrazolone type coupler, a phenol type coupler and a naphthol type coupler. However, magenta and cyan dyes formed from the dye precursors containing these coupler residues were inferior in absorption coefficient and absorption wavelength.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a dye precursor useful for a printing material for digital image information output which substantially does not form a dye by heating the dye precursor alone or by the action of an oxidizing agent but rapidly forms a dye by the action of an acid.
Another object of the present invention is to provide a photosensitive material containing a dye precursor useful for a printing material for digital image information output which does not necessitate an oxidizing agent such as a silver salt in color-forming.
A further object of the present invention is to provide a method for forming a color image using a dye precursor useful for a printing material for digital image information output, which shows high color density and forms a color having excellent absorption wavelength.
The above-described objects of the present invention have been attained by the following means:
(1) A dye precursor represented by the following formula (I):
wherein A
1
and A
2
each represent an atomic group to form a coupler residue together with —N(R
5
)(R
6
) and the carbon atom to which A
1
and A
2
are bonded; R
1
represents a substituent; n represents an integer of from 0 to 4; R
2
represents a hydroxyl group or a group represented by —N(R
7
l)R
8
; R
7
and R
8
each independently represents a hydrogen atom or a substituent; R
3
and R
4
each independently represents a hydrogen atom or an alkyl group; and R
5
and R
6
each independently represents a substituent.
(2) The dye precursor as described in the above item (1), which substantially does not form a dye by heating the dye precursor alone or by an oxidation reaction but forms a dye by the action of an acid.
(3) A photosensitive material which contains a dye precursor represented by formula (I).
(4) A photosensitive material which contains a dye precursor represented by formula (I) and a polymerizable electrophilic agent.
(5) A method for forming a color image which comprises using a dye precursor represented by the following formula (Ia), along with an oxidizing agent, an acid or a combination thereof, and effecting heat treatment:
wherein R
1a
represents a substituent; n
a
represents an integer of from 0 to 4; R
2a
represents a hydroxyl group or a group represented by —N(R
5a
)R
6a
; R
5a
and R
6a
each independently represents a hydrogen atom or a substituent; Q
1a
and Q
2a
each represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocyclic condensed type coupler residue together with the nitrogen atom, the carbon atom, and Y
a
; R
3a
and R
4a
each independently represents a hydrogen atom or an alkyl group; Y
a
represents a hydrogen atom or a group represented by —N(R
7a
)R
8a
bonded to the coupling position of the coupler mother nucleus; and R
7a
and R
8a
each independently represents a substituent.
DETAILED DESCRIPTION OF THE INVENTION
The dye precursors for use in the present invention will be described in detail below.
In the first place, examples of the coupler residues represented by (R
5
)(R
6
)N—C(A
1
)(A
2
)— in the dye precursor represented by formula (I) will be explained below.
The coupler residues preferably used in the present invention have the structures represented by the following formulae (1) to (12). These are the residues of the compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole.
Formulae (1) to (4) represent the residues of couplers called active methylene couplers, wherein R
14
represents an acyl group, a cyano group, a nitro group, an aryl group, a heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, each of which may have a substituent.
In formulae (1) to (3), R
15
represents an alkyl group, an aryl group, or a heterocyclic residue, each of which may have a substituent. In formula (4), R
16
represents an aryl group or a heterocyclic residue, each of which may have a substituent. As the substituents which R
14
, R
15
and R
16
may have, examples of R
1
described later can be exemplified.
In formulae (1) to (4), Y represents a group represented by —N(R
5
)(R
6
) in formula (I).
In formulae (1) to (4), R
14
and R
15
, and R
14
and R
16
may be bonded to each other to form a ring.
Formula (5) represents the residue of a coupler called a 5-pyrazolone coupler, wherein R
17
represents an alkyl group, an aryl group, an acyl group or a carbamoyl group; R
18
repres

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