JP2001277730A - Image forming method and image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method and an image forming material, wherein coloring matter having absorption in a wavelength region of 360-700 nm only by irradiation with laser beams, a change in concentration of >=3.0 is generated to a specific absorption wavelength in the wavelength region by generation of the coloring matter, and the image is high sensitive and excellent in storage stability, and further a haze is low even by drawing with a high output laser, and a good face shape is given. SOLUTION: In an image forming method, a coloring matter having an absorption in a specific wavelength range within a range of 360-700 nm is generated only by applying laser beam of energy of 1-700 mJ/cm2 or less to an image forming material containing coloring matter absorbing the laser beam on a base material, and a change in concentration of >=3.0 is generated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming method for completing image formation only by laser irradiation. TECHNICAL FIELD The present invention relates to an image forming material utilizing a coloring (or decoloring) reaction with an acid. The present invention relates to an image forming material having an acid generator that generates an acid by the action of heat and a coloring layer containing a compound that undergoes an absorption change by a reaction with the acid, and having high sensitivity and good storage stability. is there.

[0002]

2. Description of the Related Art Numerous methods have been proposed for an image forming method. The outline of the method is described in "Organic Materials for Imaging" edited by Organic Electronics Materials Research Group (Bunshin Publishing).
(1997), the simplest system is a system that completes image formation only by light irradiation or heating, and in consideration of image quality, a system that completes image formation only by laser light irradiation. Is considered to be the ultimate form. However, image formation only by laser light irradiation requires the construction of an image formation reaction in a very short time, and requires extremely difficult technology because it is necessary to achieve compatibility with storage stability. No proposal has been made. Although U.S. Patent No. 5858583 has been proposed an image forming system in only the irradiated laser light, laser light irradiation power of 750 mJ / cm ^2, yet also only be achieved coloring density 1.9 in the reflection-sensitive material Not.

[0003] An image forming method using only a laser beam using a sulfonic acid ester as an acid generator is disclosed in European Patent No. 905,656, but from the viewpoint of color density and storage stability of the image forming material. However, this method is inadequate, and in particular, when using a high-power laser, the surface of the image recording medium is partially destroyed by heat (so-called ablation), the haze is increased, and background contamination is caused. However, there are restrictions on raising the reaction temperature.
As a result, the compatibility between the reaction activity and the storage stability, that is, the discriminability as a recording material is not sufficient even in a recording method using a laser beam, and the development of a practical compatible image recording method and material has been required. It is still an issue in the field of imaging technology.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above background, and a first object of the present invention is to produce a dye having an absorption in a wavelength range of 360 to 700 nm only by irradiation with a laser beam, An object of the present invention is to provide an image forming method capable of causing a density change of a density of 3.0 or more at a specific absorption wavelength in a wavelength range of 360 to 700 nm by generation of the dye. A second object of the present invention is to provide a novel image forming method and an image forming material having high sensitivity and excellent storage stability. A third object of the present invention is to provide an image forming method and an image forming material which have a low haze even when an image is formed by using a high-power laser and provide a good surface state.

[0005]

Means for Solving the Problems The present inventors can generate an acid sensitively by the action of heat, and form a dye by using the acid as a trigger. The inventor thought that a compound that does not decompose would be the key to solving the problem, and as a result of intensive studies, came to achieve the object of the invention. That is, the present invention has been achieved by the following items 1 to 9.

[0006] 1. In an image forming method in which a dye is formed in an irradiated portion by laser light irradiation, a laser having an energy of 1 to 700 mJ / cm ² is irradiated on an image forming material containing a dye that absorbs the laser light on a support. A dye having an absorption in the wavelength range of 360 to 700 nm is generated only by performing
An image forming method, wherein a density change of 3.0 or more occurs at a specific wavelength in a wavelength range of nm.

[0007] 2. 2. The image forming method according to the above item 1, wherein the dye that absorbs laser light is an infrared absorbing dye.

[0008] 3. An image forming material, on a support, an acid generator that generates an acid by the action of heat, and a density of 3.0 or more at a specific wavelength in a wavelength range of 360 to 700 nm by an intramolecular or intermolecular reaction by the action of the acid. 3. The image forming method according to the above item 1 or 2, further comprising a compound causing a change and an infrared absorbing dye.

4. 4. The image forming method according to the above item 3, wherein the acid generator is a compound represented by the following formula (I) or (II).

[0010]

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In the general formula (I), R ¹ represents an alkyl group, an aryl group or a heterocyclic group. R ² and R ³ each independently represent an alkyl group or an aryl group, but R ² and R ³ are not simultaneously an aryl group. R ² and R ³ may combine to form a ring.

[0012]

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In the general formula (II), R ³¹ represents an alkyl group, an aryl group or a heterocyclic group. R ³² represents a substituent. R ³³ and R ³⁴ independently represent a hydrogen atom or a substituent. X ¹ represents an atomic group necessary for forming a ring. R ³² , R ³³ or R ³⁴ is X ¹
To form a ring.

5. A compound that causes an intramolecular or intermolecular reaction by the action of an acid and causes a concentration change of 3.0 or more at a specific wavelength in a wavelength range of 360 to 700 nm is represented by any of the following general formulas (III) to (V). 5. The image forming method as described in 3 or 4 above, which is a compound represented by the formula:

[0015]

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In the above general formula (III), X ² is N
(R ⁵⁸ ), O or S; Y ¹ represents an atomic group necessary for forming a cyclic structure together with NC—X ² ;
¹ represents C (R ⁵⁹ ) or N; R ^{51 to} R ⁵⁹ represent a hydrogen atom or a substituent, which may be the same or different, and R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ are B ¹ may combine with each other to form a condensed ring, and B ¹ represents an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group, an arylamino group or a heterocyclic amino group.

[0017]

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In the above general formula (IV), Ar ¹ and A
r ² represents an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different; R ⁷¹ represents a hydrogen atom or a substituent; Y ² represents an aromatic hydrocarbon ring or a heterocyclic group; X ³ represents O, S or N (R ⁷² ), and R ⁷² represents a hydrogen atom or a substituent.

[0019]

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In the above general formula (V), Ar ³ and Ar
⁴ represents an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different,
Z ¹ represents an aromatic hydrocarbon ring or a hetero ring, A ² represents O, S or N (R ⁷³ ), and R ⁷³ represents a hydrogen atom or a substituent.

6. The image forming method according to any one of the above items 1 to 5, wherein the image forming material contains a polymer represented by the following general formula (VI). Formula (VI)-(A) _x- (B) _y- (C) _z -In the above formula (VI), A represents a repeating unit obtained by polymerization of an acid generator monomer, and B represents an acid Represents a repeating unit obtained by polymerization of at least one kind of vinyl monomer having a partial structure which causes a concentration change of 3.0 or more at a specific wavelength in a wavelength range of 360 to 700 nm by action, wherein C is A and B Represents a repeating unit obtained by polymerization of at least one or more copolymerizable vinyl monomers. x, y and z are mol%
And 1 ≦ x ≦ 100, 0 ≦ y ≦ 99, 0 ≦
It represents z ≦ 99, x + y + z = 100.

7. The image forming method according to claim 1, wherein a transmission type image is formed on a transmission support.

8. The image forming method according to claim 1, wherein the image forming layer does not contain a silver compound or a salt thereof.

9. An image forming material, on which an image is formed by the method according to claim 1.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, two types of dyes according to the present invention will be additionally described. In the following specification, `` a dye that absorbs laser light for image writing such as infrared light '',
"360 to 700 generated by laser light irradiation
Dyes having an absorption band in the wavelength range of nm are described.
In the following description of the present invention, these are distinguished from each other as “dye that absorbs laser light” and “dye having an absorption range in a wavelength range of 360 to 700 nm”. In such cases, each may be simply referred to as a “dye”. The image formation of the present invention achieves color development of 3.0 or more in a specific region in a wavelength range of 360 to 700 nm only by laser irradiation. The required color density varies depending on the target product, and the density is preferably 3.5 or more, more preferably 4.0 or more in applications such as plate making films. However, the color density need not be 20 or more for the purpose of image formation.

Various types of laser light can be used, and it is necessary that the image forming material irradiated with the laser light contains a dye that absorbs the laser light. Examples of the laser light source include an excimer laser, an argon laser, a helium neon laser, a semiconductor laser, a glass (YAG) laser, a carbon dioxide laser, and a dye laser. It is a laser light source. Among them, a semiconductor laser is particularly useful because the device is small and inexpensive. The oscillation wavelength of a semiconductor laser is usually 670 to 830 nm, and therefore, a dye having absorption in the near infrared is used for the photosensitive material used in the present invention. As near-infrared absorbing dyes, cyanine dyes,
Squarylium dyes, merocyanine dyes, oxonol dyes, phthalocyanine dyes and the like are used. Specific examples thereof include, for example, U.S. Pat. Nos. 4,973,572, 4,948,777, and 4,950,640.
Nos. 4,950,639 and 4,948,776
Nos. 4,948,778, 4,942,141, 4,952,552, 5,036,040 and 4,912,083. No.

In the image forming method of the present invention, the irradiation intensity of the laser beam used for writing on the image forming material is
Is 700 mJ / cm ² from 1, but is preferably 600 mJ / cm ² to 10, more preferably from 500 mJ / cm ² from 20. If the irradiation intensity is less than 1 mJ / cm ² , the image forming material may be covered with natural light and the storage stability may be deteriorated. Further, when the irradiation intensity of the laser light exceeds 700 mJ / cm ² , the writing speed of the laser is slow, the cost of the hard element accompanying the laser is high, and the haze is easily generated on the image surface.
There are adverse effects such as heat scattering of the image forming layer.

Next, the acid generator will be described. As the acid generator, those which generate a strong acid by laser irradiation are preferable, and among them, those which generate a sulfonic acid are preferable. Many acid generators that generate sulfonic acid are described in, for example, “Organic Materials for Imaging”, edited by Organic Electronics Materials Research Group, published by Bunshin Publishing Company (1997). Among them, secondary alkyl esters of sulfonic acid are among them. And more preferably those represented by the following general formula (I) or general formula (II). In the general formula (I), R ¹ is an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group,
n-octyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, [0,1,3] bicyclohexyl group, [1,2,2] bicycloheptyl group, [1,1,3] bicycloheptyl group Etc.), an aryl group (phenyl group, naphthyl group, etc.) or a heterocyclic group (furyl group, thienyl group, pyrimidinyl group, benzothiazolyl group, etc.). Of these, an alkyl group or an aryl group is preferred, and an aryl group is particularly preferred. These groups have 1 to 18 carbon atoms, and preferably 1 to 12 carbon atoms, excluding a substituent.

Further, these groups may further have a substituent, and any substituent may be used as long as it can be substituted, and a preferable substituent is a halogen atom. (Fluorine, chlorine, bromine and iodine),
Alkyl group (specific examples are the same as above, including cycloalkyl group and bicycloalkyl group), alkenyl group (vinyl group, allyl group, prenyl group, geranyl group, oleyl group, 2-cyclopenten-1-yl group, etc.) , Alkynyl group (ethynyl group, propargyl group, trimethylsilylethynyl group, etc.), aryl group (specific examples are as described above), heterocyclic group (specific examples are as described above), cyano group, hydroxyl group, nitro group, carboxyl group , An alkoxy group (methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, etc.), an aryloxy group (phenoxy group, naphthoxy group, etc.), a silyloxy group (trimethylsilyloxy group, t-butyldimethyl group) Silyloxy group, etc.), heterocyclic oxy group (pyridyloxy group, 2-tetrahydropyrani Oxy group, etc.), acyloxy group (formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, etc.), carbamoyloxy group (N, N-dimethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N -Di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group, etc., alkoxycarbonyloxy group (methoxycarbonyloxy group, ethoxycarbonyloxy group, t-butoxycarbonyloxy group, n-octylcarbonyloxy group etc),
An aryloxycarbonyloxy group (such as a phenoxycarbonyloxy group),

Further, an amino group (including an anilino group,
Amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, etc., acylamino group (acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group,
3,4,5-tri-n-octyloxyphenylcarbonylamino group, etc., carbamoylamino group (carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group Etc.), alkoxycarbonylamino group (methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino, n-
Octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino, etc.), aryloxycarbonylamino group (phenoxycarbonylamino group, etc.), sulfamoylamino group (sulfamoylamino group, N,
N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group, etc., alkyl and arylsulfonylamino groups (methylsulfonylamino group,
Butylsulfonylamino group, phenylsulfonylamino group, etc.),

Furthermore, mercapto groups, alkylthio groups (methylthio group, ethylthio group, n-hexadecylthio group, etc.), arylthio groups (phenylthio group, etc.), heterocyclic thio groups (2-benzothiazolylthio group, 1-phenyltetrazole- 5-ylthio group, etc.), sulfamoyl group (N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N
-Benzoylsulfamoyl group, N- (N "-phenylcarbamoyl) sulfamoyl group, etc., sulfo group, alkyl and arylsulfinyl group (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), alkyl and arylsulfonyl group ( Methylsulfonyl, ethylsulfonyl, phenylsulfonyl, etc.), acyl (acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, etc.), aryloxycarbonyl (phenoxycarbonyl, etc.), alkoxycarbonyl (Methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl,
N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group, etc., imide group (N-succinimide group, N-
Phthalimido group), phosphino group (dimethylphosphino group, diphenylphosphino group, etc.), phosphinyl group,
Examples include a phosphinyloxy group, a phosphinylamino group, and a silyl group (such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group). Most preferably, R ¹ is an alkyl group. Specific examples of R ¹ are shown below, but the present invention is not limited thereto.

[0032]

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[0033]

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[0034]

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The substituents R ² and R ³ each independently represent an alkyl group or an aryl group, but R ² and R ³ are not simultaneously an aryl group. Examples of the alkyl group and the aryl group are the same as those described for R ¹ , and may further have a substituent. Preferred substituents are those described for R ¹ . At least one of R ² and R ³ may have a polymerizable unsaturated group, and a vinyl group is preferable as the polymerizable unsaturated group. R ² and R ³ may combine to form a ring. Although various examples are given as such examples, preferred forms are those represented by the general formula (VII).

[0036]

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In the general formula (VII), R¹Is the general formula
It is synonymous with (I). X^FourForms a ring with C
Represents an atomic group required for X^FourForms a ring with C
And the ring size is preferably 3 to 8.
And more preferably 5 or 6, particularly preferably
6. X^FourIs preferably a non-metallic atomic group.
Is preferably -C (R^Four) (R^Five)-, -C (= Y^Three)
-, -N (R⁶)-, -O-, -S-, and particularly preferred.
Or -C (R^Four) (R^Five)-. Where R^Four, R^Five,
R ⁶Represents a hydrogen atom or a substituent, and
A preferred example of R is¹Is the same as that described in the description.
R^Four, R^FiveOr R⁶If there is more than one in the molecule,
They may be the same or different, and
Or two or more are linked to form a ring
Is also good. Y^ThreeIs = O, = S, or = N-R⁶Represents
Then R⁶Is the same as described above. The general formula (VII
 The compound represented by) is a polymer as described later.
By performing the conversion, more excellent performance is exhibited. Heavy for that
Preferably as a monomer having a compatible unsaturated group, the following
It is a compound represented by the general formula (VIII).

[0038]

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In the formula, R ¹ has the same meaning as in formula (I).
R ⁷ represents a hydrogen atom or an alkyl group, and the alkyl group may further have a substituent. Specific examples of the alkyl group and the substituent are those described in the specific examples of R ¹ .
R ⁷ is preferably a hydrogen atom or a methyl group. Hereinafter, specific examples of the compound represented by Formula (I), Formula (VII) or Formula (VIII) are shown, but the present invention is not limited thereto. Some compounds have isomers such as cis- and trans-forms, and the case where these are used as a mixture is also included in the present invention.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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In the general formula (II), R³¹Is the general formula
R of (I)¹Is synonymous with Substitution in general formula (II)
Group R³²Represents a substituent, and the substituent is R¹In the description
Described. R³²Preferably as al
A kill group, a halogen atom or an alkoxy group;
More preferably, it is an alkyl group. R³³And R³⁴Is
Each independently represents a hydrogen atom or a substituent;
The group is R ¹Described in the description. R³³
And R³⁴Is preferably a hydrogen atom, an alkyl group,
A halogen atom or an alkoxy group, more preferably
Or a hydrogen atom or an alkyl group. Also R³³And R
³⁴Preferably, at least one of is a substituent
No. X¹Represents an atomic group necessary for forming a ring. ring
The size of is preferably 3 to 8, more preferably
It is preferably 5 or 6, particularly preferably 6.
You. X¹Is preferably a non-metallic atomic group, more preferably
Or -C (R³⁵) (R³⁶)-, -C (= Y^Four)-,-
N (R³⁷)-, -O-, -S-, and particularly preferably
-C (R³⁵) (R³⁶)-. Where R³⁵, R³⁶, R
³⁷Represents a hydrogen atom or a substituent;
A preferred example is R¹Is the same as that described in the description. R
³⁵, R³⁶Or R³⁷If there is more than one in the molecule,
They may be the same or different, and
Or two or more are linked to form a ring
Is also good. Y is = O, = S, or = N-R³⁷The table
I, R³⁷Is the same as described above. R³², R³³Also
Or R³⁴Is X¹To form a ring. Ma
R³¹~ R³⁴At least one of which is a polymerizable unsaturated group
It is preferable to have a polymerizable unsaturated group
Vinyl groups are preferred.

Further, among the compounds represented by the general formula (II), more preferred are the compounds represented by the following general formula (IX).

[0047]

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In the general formula (II), R ^{31 to} R ³⁴ have the same meaning as in the general formula (II). R ³⁸ and R ⁴⁰ represent a hydrogen atom or a substituent (specific examples are those described in the description of R ¹ ), preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R ³⁹ represents a hydrogen atom or a substituent (specific examples are those described in the description of R ¹ ), and preferably has a Hammett σm value of 0 or more, and more preferably a hydrogen atom or an acyloxy group. Further, the compound represented by the formula (IX) preferably has a polymerizable unsaturated group at any position, and a vinyl group is preferable as the polymerizable group.

Specific examples of the compounds represented by formulas (II) and (IX) are shown below, but the present invention is not limited thereto. In some compounds, cis-form and tr
There are some isomers such as ans-isomers, but the following description does not specify the structure of these isomers, and includes the case where the isomers are used as a mixture of isomers.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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The amount of these acid generators varies depending on the type of the compound having a change in absorption, but is generally 0.001 to the compound having a change in absorption in the wavelength range of 360 to 700 nm due to the action of an acid described later. The range is preferably from 20 to 20 equivalents, particularly preferably from 0.01 to 5 equivalents.

Next, a compound which causes an intramolecular or intermolecular reaction by the action of an acid and causes a concentration change of 3.0 or more at a specific wavelength in a wavelength range of 360 to 700 nm will be described. The compound having such an absorption change may be a single compound or may be composed of two or more components. For example, (a) a combination of compounds forming a decolored image in the area by the Diels-Alder reaction (for example, a combination of 9,10-distyrylanthracene and maleic anhydride, or a combination of tetraphenylcyclopentadiene and acrylate) ), (B) a compound that forms a color image in the region by the retro Diels-Alder reaction (for example, an adduct of 9,10-distyrylanthracene and maleic anhydride, an adduct of diphenylisobenzofuran and acrylamide, etc.), (c) a compound (for example, 1-acetoxy-1,2-diaryleethane, 1-sulfoxy-1,2-diaryleethane, etc.) that expands a conjugated system by β-hydrogen elimination to form a color image in the region, Aldehyde and Active Methyle That Form a Colored Image in the Area The compounds of the combination (e.g., photographic 4 equivalents magenta coupler (pyrazolone derivative) and p-methoxycarbonylpyrrolidine cinnamaldehyde, etc.) or
(e) Compounds having an amino group or a hydroxyl group substituted by a substituent whose decomposition or elimination is promoted by the action of an acid in the molecule, and a compound or the like in which the absorption in the absorption region changes due to the removal of the substituent. Can be

As the substituent of the amino group in the compound in which the absorption is changed by decomposition or elimination of the substituent of the amino group by the action of an acid, an alkoxycarbonyl group (for example, t-butoxycarbonyl group, cyclohexyloxycarbonyl group, 2- (2-methyl) butoxycarbonyl group, 2- (2-phenyl) propyloxycarbonyl group, 2-chloroethoxycarbonyl group, etc.), acyl group (for example, acetyl group, benzoyl group, 2-nitrobenzoyl group, 4-chlorobenzoyl group, Preferred examples thereof include a 1-naphthoyl group) and a formyl group. In the present invention, an alkoxycarbonyl group having a hydrogen atom at the β-position is particularly useful from the viewpoint of storage stability and heat sensitivity.

Examples of such a compound are described in, for example, US Pat. Nos. 4,602,263 and 4,826,976, and can be obtained by combining with a thermal acid generator and an acid multiplying agent of the present invention. Thus, a heat-sensitive material having higher sensitivity and excellent storage stability can be provided.

As the substituent of the hydroxyl group in the compound whose absorption changes when the substituent of the hydroxyl group is decomposed or eliminated by the action of an acid, the hydroxyl group has a hydrogen atom at the β-position.
Secondary or tertiary alkoxycarbonyl group (for example, t-butoxycarbonyl group, isopropyloxycarbonyl group, 1-phenylethoxycarbonyl group, 1,1-diphenylethoxycarbonyl group, 2-cyclohexeneoxycarbonyl group, etc.), silyl group (for example, Trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, phenyldimethylsilyl group, etc.), alkoxymethyl group (for example, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group,
-Phenoxyethyl group, 2- (2-methoxypropyl)
A secondary or tertiary alkyl group having a hydrogen atom at the β-position (eg, a tetrahydropyranyl group, a tetrahydrofuranyl group, a 4,5-dihydro-2-methylfuran-5-yl group, a t-butyl group, A 2-cyclohexenyl group) is a preferable example, but in the present invention, a secondary or tertiary alkoxycarbonyl group having a hydrogen atom at the β-position is particularly preferable. Compounds whose absorption is changed by decomposition of a hydroxyl group substituent are described in US Pat.
Examples are described in JP-A-3,052 or JP-A-9-25360.

Dye precursors such as basic leuco dyes which instantaneously develop color upon contact with an acid, and combinations thereof can also be used in the image forming material. Examples of such compounds include “Organic Materials for Imaging”, edited by the Society of Organic Electronics Materials, published by Bunshin Publishing Company (1
997), and the compounds described in the references cited therein. Hereinafter, specific examples of the compound which changes the absorption range of 360 to 700 nm by the action of an acid will be shown, but the present invention is not limited thereto.

Preferred compounds used in the present invention include:
They are represented by the general formulas (III) to (V). In the leuco dye represented by the general formula (III) of the present invention, R ⁵¹
To R ⁵⁷ represent a hydrogen atom or a substituent, which may be the same or different.

Examples of the substituent include R ^{1 of the} general formula (I)
Are shown. When R ⁵⁴ , R ⁵⁵ , R ⁵⁶ or R ⁵⁷ represents a substituent, two adjacent groups may be bonded to each other to form a condensed ring. Examples of the case where a condensed ring is formed include a naphthalene ring, an anthracene ring, a benzofuran ring and a benzothiophene ring.

In formula (III), R ⁵¹ and R ⁵² are preferably alkyl groups.

In the general formula (III), X ² represents N (R ⁵⁸ ), O
Or S, R ⁵⁸ represents a hydrogen atom or a substituent,
Examples in which ⁵⁸ represents a substituent include those described above as examples in which R ^{51 to} R ⁵⁷ represent a substituent. X ² is particularly preferably O.

In the general formula (III), Y ¹ represents an atomic group necessary for forming a cyclic structure together with NC—X ² , preferably an atomic group necessary for forming a 5- or 6-membered ring. It is. Examples of the constituent atoms of Y necessary to constitute the ring skeleton include a carbon atom, a nitrogen atom, a sulfur atom, a silicon atom and a phosphorus atom, and these atoms have a hydrogen atom or a necessary substituent. When a plurality of substitutions are possible, the respective substituents may be different or the same, and the substituents may be bonded to each other to further form a ring.

Examples of the substituent when the atom constituting Y ¹ has a substituent include 置換 O (forming a carbonyl group, a sulfonyl group and the like together with the skeleton atom of Y ¹ ), and 、 S (Y ¹
Forms a thiocarbonyl group with the skeletal atom of
= N-R ⁶⁰ (R ⁶⁰ is as an example of. Substituents represent a hydrogen atom or a substituent include those described above as examples of the case where R ⁵¹ to R ⁵⁷ represents a substituent), or, R ⁵¹ ~ Examples of the case where R ⁵⁷ represents a substituent include those described above.

A preferred form of Y is -C (R⁶¹) (R⁶²)-
Alternatively, a divalent group represented by —C (＝ O) — is an arbitrary group
It is a divalent linking group formed by combining
(R¹¹, R^{1 Two}Represents a hydrogen atom or a substituent, and is the same
Or different, R⁶¹And R ⁶²Or intramolecular
Multiple occurrences of R⁶¹And R⁶²Are linked together to form a ring
May be. R⁶¹, R⁶²An example of R⁵¹~ R⁵⁷Is a substituent
Examples of such a case include those described above. ). An example
For example -CH_Two CH_Two−, − CH_Two CH_Two CH_Two-, -CH (CH_Three) CH_Two
−, −CH_TwoC (= O)-, -C (= O) CH_Two-, -CH_Two CH
_TwoC (= O)-, -C (= O) CH_TwoCH_Two-, -CH = CH-, etc.
Is given as an example. Y among these¹Preferred form of
The state is-[C (R⁶¹) (R⁶²)]_Two-.

In the general formula (III), A ¹ represents C (R ⁵⁹ ) or N, and R ⁵⁹ represents a hydrogen atom or a substituent. When R ⁵⁹ represents a substituent, examples of the substituent include those described above as examples when R ^{51 to} R ⁵⁷ represent a substituent. A ¹
A particularly preferred form for is CH.

B ¹ represents an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group, an arylamino group or a heterocyclic amino group. Examples of these include those described above as examples where R ^{1 to} R ⁷ represent a substituent. These groups may have a substituent at a substitutable position,
Examples of the substituent include those described above as examples when R ^{51 to} R ⁵⁷ represent a substituent. These substituents may be bonded to form a condensed ring by combining two different groups each other and may form a ring with R ^59. Preferred forms for B ¹ are an aryl group or a heterocyclic group.

Among the compounds represented by the general formula (III) of the present invention, a particularly preferred embodiment is the one represented by the general formula (X).

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In the general formula (X), R ^{51 to} R ⁵⁷ have the same meaning as in the general formula (III), and D ¹ represents an aryl group or a heterocyclic group. Examples of the aryl group or heterocyclic group represented by D ¹ include those described above in the example of the case where R ⁵¹ to R ⁵⁷ represents a substituent. The compound represented by the general formula (III) or (X) has a polymerizable group (acrylic group, methacrylic group, 4-vinylphenyl group, etc.) introduced into a substitutable position of R ^{51 to} R ^62. It may be a polymer formed by linking a plurality. Hereinafter, specific examples of the compound represented by formula (III) or (X) useful in the present invention are shown, but the present invention is not limited thereto. These compounds are described in JP-A-51-34885, JP-A-51-44127,
According to the method described in JP-A-56-149489, for example, dehydration condensation of an aldehyde group of an aromatic or heterocyclic aldehyde compound, a nitroso group of a nitroso compound with an active methyl group or methylene group at the 2-position of the indolenine nucleus It can be synthesized by a reaction. Hereinafter, in the polymer material of the present invention, the value represented by n or m indicates the mole percentage of the polymer composition.

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In the leuco dye represented by formula (IV) of the present invention, R ⁷¹ represents a hydrogen atom or a substituent.

Examples of the substituent include R ^{1 of the} general formula (I)
Are shown. Among the substituents, preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group,
Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group, heterocycle A thio group or a silyl group, particularly preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group (including an anilino group), an acylamino group, an aminocarbonylamino group, An alkoxycarbonylamino group and an aryloxycarbonylamino group. Among the above functional groups, those having a hydrogen atom may be removed, and further substituted with the above group.

In the general formula (IV), Ar ¹ and Ar ²
Represents an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different, and examples thereof include those described above in the description of the substituent R ⁷¹ ; Further, these groups may further have a substituent at a substitutable position, and examples of the substituent include those described above when R ⁷¹ represents a substituent.

Ar¹And Ar^TwoHas multiple substituents
In these cases, these may be combined with each other to form a condensed ring.
Ar¹And Ar^TwoMay be linked to form a ring
No. Ar¹Substituents introduced into each other or Ar^TwoIntroduced in
Where the substituted substituents combine with each other to form a fused ring
Examples of the case include a julolidine ring, a naphthalene ring,
Toracene ring, benzofuran ring, benzothiophene ring, etc.
Ar¹And Ar ^TwoLink to form a ring
Examples of the case include a 9H-xanthene ring and a 10-alkyl
Rou 9,10-dihydroacridine ring, 9H-thioxa
Ring, 1-alkyl-4H-chromeno [2,3-
C] pyrazole ring, 11H-benzo [b] thieno [2,
3-b] Chromene ring, 6-alkyl-5-oxo-5,
6-dihydro-12H-chromeno [2,3-C] isoki
Norin ring, 4H-chromene ring, 2H-chromene ring or
And a fluorene ring.

Ar ¹ and Ar ² are preferably an aryl group or a heterocyclic group, and particularly preferably A
At least one of r ¹ and Ar ² has an electron donating aryl group (for example, a p-dimethylaminophenyl group, p
-Julolidyl group, p-methoxyphenyl group, etc.) or 1,2,3,4-tetrahydroquinolin-6-yl group,
3,3-dimethylindoline-5-yl group, 3,4-methylenedioxyphenyl group, 1,2-dimethyl-5-benzimidazolyl group, 10-ethylphenoxazine-3
-Yl group, 9-ethylcarbazol-3-yl group, dibenzofuran-3-yl group, dibenzothiophen-3-yl group, quinolin-8-yl group, 1,2-dimethylindol-3-yl group, ethylindazole -3-yl group,
Benzo [b] -furan-3-yl group, benzo [b] -thiophen-3-yl group, 1-ethylpyrrole-3-yl group, 3-furyl group, 3-thienyl group, 2-thiazolyl group, 2 -In the case of a heterocyclic group selected from a benzoxazolyl group, a 2-pyridyl group and a 4-quinolyl group, or at least one of Ar ¹ and Ar ² has an electron-donating group as a substituent, and Ar ¹ and Ar ^Two are linked to form the above fused ring.

Y ² represents an aromatic hydrocarbon ring (eg, benzene ring, naphthalene ring, anthracene ring, etc.) or a hetero ring (eg, pyridine ring, pyrimidine ring, indole ring, furan ring, thiazine ring, etc.). May be substituted at a substitutable position with a substituent,
Examples thereof include those described as examples in the case where R ¹ represents a substituent. A preferred form of Y ² is an aromatic hydrocarbon ring, particularly preferably a benzene ring.

X ³ represents O, S or N (R ⁷² );
⁷² represents a hydrogen atom or a substituent, and examples of the case where R ⁷² represents a substituent include those described as examples when R ⁷¹ represents a substituent. X ³ is preferably O or S.

The compounds represented by the general formula (IV) and the general formula (V) described below have a polymerizable group (acryl group, methacryl group, 4-vinylphenyl group, etc.) introduced at a substitutable position. May be a polymer formed by connecting a plurality of groups. In this case, the molecular weight of the polymer is preferably in the range of 1,000 to 1,000,000, and particularly preferably in the range of 2,000 to 300,000. In this case, it may be a homopolymer or a copolymer with another monomer.

The compound represented by the general formula (IV) can be used, for example, in the form of an acid halide or a triarylmethane derivative having an amino group at the ortho position synthesized from Michlerhydrols and arylamines. It can be synthesized by reacting isocyanates and the like and then oxidizing with an oxidizing agent such as lead dioxide, manganese dioxide or chloranil.
And Nos. 63-251278.

Specific examples of the compound represented by formula (IV) useful in the present invention are shown below, but the present invention is not limited to these. Hereinafter, in the polymer material of the present invention, the value represented by n or m indicates the mole percentage of the polymer composition.

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Next, the general formula (V) will be described. A
r ³ and Ar ⁴ represent an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different, and are the same as those of the above-mentioned general formula (IV).
It has the same meaning as r ¹ and Ar ² .

Z ¹ represents an aromatic hydrocarbon ring or a hetero ring, which has the same meaning as Y ² in the aforementioned general formula (IV). A ² represents O, S or N (R ⁷³ );
⁷³ represents a hydrogen atom or a substituent, as an example of a case in which R ^{7 3} represents a substituent include those described as examples in the case where R ⁷¹ represents a substituent. A ² is preferably S. The compound represented by formula (V) of the present invention is disclosed in
The compound can be synthesized by the method described in -17036. Hereinafter, specific examples of the compound represented by formula (V) useful in the present invention will be shown, but the present invention is not limited thereto.

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It is prepared by applying a compound which changes the area on a support. At this time, a binder is usually coexisted, unless one of these is a polymer or an amorphous having good coatability. When the binder does not need to be used, there is an advantage that the film thickness can be easily reduced and a sharp image can be obtained. When a binder is used, gelatin, casein, starches, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide, a water-soluble binder such as ethylene-maleic anhydride copolymer, and polyvinyl butyral, triacetyl cellulose, polystyrene, acrylic Any water-insoluble binder such as a methyl acid-butadiene copolymer and an acrylonitrile-butadiene copolymer can be used. On the other hand, by the action of an acid generator or an acid,
When one or both of the compounds (including copolymerization) that cause a change in the wavelength region of 700 nm are polymers, it is not particularly necessary to add a binder. In that case, high sensitivity can be expected in the sense that an acid is generated very near the compound whose hue changes. Controlling the diffusion of molecules by polymerization may improve the resolution and storage of images. These characteristics are particularly preferable for applications requiring high image quality, such as graphic arts films. A preferred form as such a compound is represented by the general formula (VI).

The general formula (VI) will be described. In the general formula (VI), A represents a repeating unit obtained by polymerization of an acid generator monomer, and preferred examples thereof include compounds represented by the general formulas (I), (II), or (VII) to (IX). And those having a polymerizable unsaturated group. Specific examples thereof include those having a polymerizable unsaturated group among the compound examples of the general formula (I), (II) or (VII) to (IX). In the general formula (VI), B is a repetition obtained by polymerization of at least one or more vinyl monomers having a partial structure that causes a concentration change of 3.0 or more at a specific wavelength in a wavelength range of 360 to 700 nm by the action of an acid. A preferred example is a compound having a polymerizable unsaturated group among the compounds represented by formulas (III) to (V) and (X). Specific examples thereof include those having a polymerizable unsaturated group among the compound examples of the general formulas (III) to (V) and (X). In addition, the density change of the density of 3.0 or more at a specific wavelength in the wavelength range of 360 to 700 nm may be achieved by one type of dye or by generation of a plurality of dyes. Further, the formation of a plurality of dyes with B, which is a color former in the polymer, and another color former separately added to the image forming material, has a density of 3.0.
The above coloring may be achieved. C in the general formula (VI) represents a repeating unit obtained by polymerization of at least one kind of vinyl monomer capable of forming a copolymer together with A and B, and controls polarity, glass transition temperature and the like. Thus, storage stability, coloring activity and the like can be controlled. Such vinyl monomers may be used in combination of two or more. Preferred examples include acrylate, methacrylate, acrylamide, styrene, vinyl ether and the like. Specific examples of the monomer forming C are shown below, but the present invention is not limited thereto.

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In the general formula (VI), x, y, and z represent mol% of each composition. x, y, z are each 1 ≦ x ≦ 10
0, 0 ≦ y ≦ 99, 0 ≦ z ≦ 99, and x + y + z = 1
00. The molecular weight of the polymer represented by the general formula (VI) is preferably in the range of 1,000 to 1,000,000, and particularly preferably in the range of 2,000 to 100,000. The polymer may be in any form such as a homopolymer, a random copolymer, an alternating copolymer, and a block copolymer, but a homopolymer and a random copolymer, which are synthetically easy, are generally used. . Preferred combinations of monomers forming A, B, and C and x, y, and z in the polymer represented by the general formula (VI) are shown below, but the invention is not limited thereto.

[0122]

[Table 1]

The polymer of the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization,
It can be carried out by emulsion polymerization. The method of initiating polymerization includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and the method of initiating the polymerization are described in, for example, T. Tsuruta, “Polymer Synthesis Method” Revised Edition (Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masayoshi Kinoshita, “Experimental Method of Polymer Synthesis” Published in 1972,
It is described on pages 124-154.

Of the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferred. Solvents used in the solution polymerization method include, for example, ethyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, Various organic solvents such as methylene chloride, chloroform and dichloroethane may be used alone or as a mixture of two or more thereof, or may be used as a mixed solvent with water. The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, and the like. Polymerization can be performed at various temperatures, but usually the polymerization is carried out in the range of 30 to 100 ° C. In the present invention, it is preferable to carry out the polymerization in a temperature range of 30 to 90C.

Examples of the radical initiator used in the polymerization include 2,2′-azobisisobutyronitrile,
Such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, and 4,4'-azobis (4-cyanopentanoic acid) Preferred are azo-based initiators and peroxide-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, and potassium persulfate (for example, redox initiators may be used in combination with sodium bisulfite). In the present invention, the initiator (for example, 2,2'-azobis (2,4-dimethylvaleronitrile)) or 2,2'-azobis (4-methoxy-2,
4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (3,4,5,6-tetrahydropropane)
Dihydrochloride] and the like are particularly preferred. The amount of the polymerization initiator used can be adjusted according to the polymerizability of the monomer and the required molecular weight of the polymer, but is preferably in the range of 0.01 to 5.0 mol% based on the monomer.

In the synthesis of the polymer represented by the general formula (VI), monomers forming A, B and C are mixed and put into a reaction vessel first, and then an initiator may be added. The polymerization may be performed through a process of dropping the monomer into the polymerization solvent.

The polymer represented by the general formula (VI) of the present invention has a partial structure having a function of generating an acid by the action of heat or an acid, and a polymer having a function of 360 to 700 nm by the action of an acid.
It is a polymer having a partial structure that causes a change in the wavelength range. As such a polymer, a polymer of a single monomer having both functions can be used, but the structure represented by the general formula (VI) is generally used from a synthetic viewpoint. The image forming material of the present invention generally has the general formula (VI)
It is prepared by coating a polymer represented by the formula (1) on a support.
When the polymer of the present invention also has a function of generating an acid by heat, the absorption alone changes due to the action of heat alone, so that when the polymer is used as a heat-sensitive material, the sensitivity and the sharpness of the image are excellent. I have. Further, the image forming material of the present invention does not require the use of a so-called binder, and thus has the advantages that the film thickness can be reduced, a sharp image can be obtained, and abrasion hardly occurs. However, when the polymer represented by the general formula (VI) is used, a binder may be used together if necessary, and specific examples thereof include those described above.

In the present invention, a small amount of a base may be added for the purpose of enhancing the storage stability of the image forming material, or a compound capable of generating an acid by the action of light or heat may be added for the purpose of enhancing the sensitivity. Various additives such as a pigment, an antioxidant, and an anti-sticking agent can be added according to the requirements. Further, an overcoat layer may be provided to protect the image forming layer, or a backcoat layer may be provided on the back surface of the support. Various known techniques for heat-sensitive materials can be used, such as providing a single layer or a plurality of layers of an undercoat layer made of pigment or resin between the image forming layer and the support.

When a base is added, an organic base is preferred. For example, a guanidine derivative (eg, 1,3-diphenylguanidine, 1,3-dimethylguanidine, 1,3-
Dibutylguanidine, 1-benzylguanidine, 1,
1,3,3-tetramethylguanidine, etc.), aniline derivatives (eg, aniline, pt-butylaniline, N,
N-dimethylaniline, N, N-dibutylaniline, triphenylamine, etc.), alkylamine derivatives (for example, tributylamine, octylamine, laurylamine,
Benzylamine, dibenzylamine and the like, and heterocyclic compounds (eg, N, N′-dimethylaminopyridine,
Preferred examples include 1,8-diazabicyclo [5.4.0] -7-undecene, triphenylimidazole, lutidine, and 2-picoline. These bases are 1 to 50 mo with respect to the composition represented by A in the general formula (1).
1%, particularly preferably 5 to 20%.
mol% is added.

When the image forming material of the present invention is used as a photon mode type image forming material, it is essential to add a compound which generates an acid by the action of light. On the other hand, when using as a heat mode type image forming material,
An acid generator may be separately added for the purpose of further increasing the sensitivity. Examples of known acid generators include compounds described in “Organic Materials for Imaging” edited by Organic Electronics Materials Research Society, published by Bunshin Publishing Company (1997), pp. 37-91, and references cited therein. And the like. Many of the photoacid generators described herein also function as thermal acid generators. When adding a pigment, diatomaceous earth, talc, kaolin, calcined kaolin, titanium oxide, silicon oxide, magnesium carbonate, calcium carbonate, aluminum hydroxide,
Urea-formalin resin and the like are exemplified. Other additives include benzophenone-based, benzotriazole-based ultraviolet absorbers, zinc stearate, head abrasion and sticking inhibitors composed of higher fatty acid metal salts such as calcium stearate, paraffin, paraffin oxide, polyethylene, polyethylene oxide, Waxes such as caster wax and the like can be mentioned, and can be added as needed.

As the support used in the image forming agent of the present invention, papers such as high quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,
6-naphthylenedicarboxylate, polyarylene,
Examples thereof include polymer films such as polyimide, polycarbonate, and triacetyl cellulose, glass, metal foil, and nonwoven fabric. When the image forming material of the present invention is used for a transmission type image such as a film for OHP or a film for plate making, a transparent support is used. For a plate making film, a support having a small coefficient of thermal expansion and good dimensional stability and having no absorption in the photosensitive region of the PS plate is selected.

The method for synthesizing the compound of the present invention is shown below.
The present invention is not limited to these. (Synthesis Example 1) Synthesis of Exemplified Compound (A-1)

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Starting compound 1b (100 mmol) was converted to N, N-
Dissolved in dimethylacetamide (50 ml) and cooled the reactor to 7 ° C. The raw material compound 1a (100
mmol) was added dropwise over 10 minutes, followed by a reaction for 6 hours. After adding ethyl acetate (200 ml) and water (200 ml) and stirring, the mixture was allowed to stand and an aqueous layer was separated. Further, the organic layer was washed three times with 1 mol / l hydrochloric acid aqueous solution (100 ml), dried over magnesium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 → 1/1) to obtain Intermediate 1c in a yield of 61%. Next, the starting compound 1d (5
0 mmol) was dissolved in pyridine (30 ml) and cooled to 7 ° C. Intermediate 1c (50 mmol) was added to the solution, and the mixture was stirred for 8 hours. Then, water (3 ml) was added, and the mixture was stirred for 30 minutes. Ethyl acetate (100 ml) and water (200 ml) were added, and the mixture was stirred and left still to separate an aqueous layer. Further, the organic layer was washed three times with 1 mol / l hydrochloric acid aqueous solution (100 ml), dried over magnesium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 → 1/1) to give Exemplified Compound (A-1) as a mixture of cis- and trans-forms at 72%. In a yield of The cis-form and trans-form are obtained by silica gel column chromatography (eluent: ethyl acetate /
Hexane = 1/4 → 1/1), and when they were separated and their decomposition temperatures were examined, the cis form was found to be 1
The temperature was 92 ° C and the trans form was 184 ° C.

(Synthesis Example 2) Synthesis of Exemplified Compound (A-2)

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The starting compound 2a (100 mmol) was dissolved in pyridine (40 ml), and the reactor was cooled to 7 ° C. Thereto, the starting compound 2b (100 mmol) was added dropwise over 10 minutes, and then reacted for 2 hours, and then reacted at room temperature for another 5 hours. Thereafter, water (4 ml) was added, and the mixture was stirred for 30 minutes. Ethyl acetate (150 ml) and water (200 ml) were added, and the mixture was stirred and left still to separate an aqueous layer. The organic layer was further washed with 1 mol / l aqueous hydrochloric acid (100 ml) three times, and then concentrated by drying over magnesium sulfate. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate / chloroform = 1/8 → 1 /
Purification was performed in 1) to obtain an intermediate 2c in a yield of 76%. Then intermediate 2c (50 mmol) was dissolved in N, N-dimethylacetamide (60 ml) and the reactor was cooled to 7 ° C. Thereto, 2d (50 mmol) of the starting compound was added dropwise over 10 minutes, and then reacted at room temperature for 8 hours. After adding ethyl acetate (200 ml) and water (200 ml) and stirring, the mixture was allowed to stand and an aqueous layer was separated. 1 mol / l of organic layer
Was washed three times with aqueous hydrochloric acid (100 ml), dried over magnesium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 → 1/1) to give the exemplified compound (A-
2) was obtained in a 78% yield as a mixture of cis and trans forms. The decomposition temperature of the trans form of the compound was 189 ° C.

(Synthesis Example 3) Synthesis of Exemplified Compound (A-3) Exemplified compound (2) except that equimolar amount of 2,4-xylylsulfonyl chloride was used in place of starting compound 2a.
By the same operation as in the synthesis of Compound (A-3),
Obtained as a mixture of cis and trans forms. The decomposition temperature of the mixture was 181 ° C.

(Synthesis Example 4) Synthesis of Exemplified Compound (A-22) Except that raw material compound 2a was replaced with equimolar p-tolylsulfonyl chloride and raw material compound 2d was replaced with equimolar acryl chloride. By the same operation as in the synthesis of Exemplified Compound (2), Exemplified Compound (A-2)
2) was obtained as a mixture of a cis form and a trans form. The decomposition temperature of the cis form was 182 ° C, and the decomposition temperature of the trans form was 173 ° C.

(Synthesis Example 5) Synthesis of Exemplified Compound (A-13) An equimolar p-tolylsulfonyl chloride was used in place of the starting compound 2a, and an equimolar 4- {2- (4) was used in place of the starting compound 2b. -Hydroxy-cyclohexyl) propyl @ cyclohexanol was used, and the compound (A-1) was prepared in the same manner as in the synthesis of the compound (2).
3) was obtained as a mixture of a cis form and a trans form. The decomposition temperature of the mixture was measured, but no clean decomposition peak was obtained.

Synthesis Example 6 Synthesis of Exemplified Compound (A-29)

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The starting compound 29a (100 mmol) was dissolved in pyridine (50 ml), and the reactor was cooled to 7 ° C.
To this solution, the starting compound 29b (100 mmol) was added over 10 minutes, and further reacted at room temperature for 6 hours. afterwards,
After adding water (3 ml) and stirring for 30 minutes, ethyl acetate (1 ml) was added.
(00 ml) and water (200 ml), and the mixture was stirred and allowed to stand to separate an aqueous layer. Further, the organic layer was washed three times with 1 mol / l hydrochloric acid aqueous solution (100 ml), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate / hexane =
1/5) to give Exemplified Compound (A-29) as a mixture of isomers in a yield of 78%. Its decomposition temperature was 145 ° C.

(Synthesis Example 7) Synthesis of Exemplified Compound (A-35) Except that the starting compound 29a was replaced with an equimolar amount of 4-vinylsulfonyl chloride, the exemplified compound (A-29)
Compound (A-35) was synthesized by the same reaction as in the synthesis of Compound (A). The decomposition temperature of the compound was 142 ° C.

(Synthesis Example 8) Synthesis of Exemplified Compound (P-1) Exemplified Compound (A-1) (50 mmol) was added to toluene (22 m
1) and heated to 40 ° C. under a nitrogen atmosphere. To this solution was added a solution of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (0.125 g) in methyl ethyl ketone (3 ml), and the mixture was reacted for 2 hours. A solution of (4-methoxy-2,4-dimethylvaleronitrile) (0.125 g) in methyl ethyl ketone (3 ml) was added. After reacting for 2 hours,
The reaction mixture was poured into hexane (1200 ml), and the precipitate was collected by filtration and dried to give Exemplified Compound (P-1).
Was obtained in 89% yield. The weight average molecular weight was 85,000 and the decomposition temperature was 172 ° C.

(Synthesis Example 9) Synthesis of Exemplified Compound (P-2) An equimolar amount of (A-2)
Except having replaced with, Exemplified compound (P-2) was synthesized by the same reaction as the synthesis of Exemplified compound (P-1). The weight average molecular weight was 120,000 and the decomposition temperature was 187 ° C.

(Synthesis Example 10) Synthesis of Exemplified Compound (P-3) The starting compound, Exemplified Compound (A-1) was equimolar to (A-3)
Except having replaced with, Exemplified compound (P-3) was synthesized by the same reaction as the synthesis of Exemplified compound (P-1). The weight average molecular weight was 100,000, and the decomposition temperature was 174 ° C.

(Synthesis Example 11) Synthesis of Exemplified Compound (P-6) Exemplified Compound A-2 (7.5 mmol) and Exemplified Compound B-41
(2.5 mmol) was dissolved in toluene (4.4 ml), methyl ethyl ketone (2 ml) and methylene chloride (4 ml) and heated to 40 ° C. under a nitrogen atmosphere. There, 2,2'-
Azobis (4-methoxy-2,4-dimethylvaleronitrile) (0.025 g) in methyl ethyl ketone (0.6
ml) and react for 2 hours.
A solution of 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (0.025 g) in methyl ethyl ketone (0.6 ml) and methylene chloride (2 ml) were added. After reacting for 2 hours, hexane (400 m
1), the precipitate was collected by filtration and dried to give Exemplified Compound (P-6) in a yield of 53%. The weight average molecular weight was 45,000. The decomposition temperature was 188 ° C.

[0149]

The following examples illustrate the usefulness of the compounds of the present invention in more detail, but the present invention is not limited thereto. (Example 1) <Preparation of image forming material sample> As shown in Table 2, the compound composition according to the present invention (samples 1 to 6) and the compound composition for comparison (samples 7 and 8) were each dissolved in chloroform. A coating solution was prepared and coated on a 175 μm-thick polyethylene terephthalate film (the coating amount is described in Table 2). The protective layer coating solution having the following composition was applied on this film to prepare image forming materials 1 to 8.

<Preparation of Coating Solution for Protective Layer> An aqueous solution containing 4% by weight of Kuraray Povar PVA-110 manufactured by Kuraray Co., Ltd. and 0.1% by mass of Emarex 710 manufactured by Nippon Emulsion Co., Ltd. was prepared. The solid content is 1.0 g / m
2 was applied.

<Image Forming Processing and Evaluation Test> Exposure for Writing Image: Laser Light Apparatus (Spectra Diod)
e Labs No.SDL-2430, wavelength range: 800 to 830 nm)
Were combined to give an output of 140 mW to obtain an image writing laser beam. Using this laser light, a beam system of 20 μm and a laser energy density on the sample of 48
It was set to 0 mJ / cm2. Scanning exposure was performed on the produced image forming material from the protective layer side under the above laser exposure conditions. Test of image forming ability: The produced image forming materials 1 to 8 (Table 2) were subjected to laser exposure, and the color density at 360 to 700 nm, which is the maximum absorption wavelength of the formed dye, was measured (Table 3). The concentration was measured using a UV manufactured by Shimadzu Corporation.
Performed with -2500PC (same below). Storage stability: Each sample of the image forming materials 1 to 8 was left for 7 days at 45 ° C. in a non-humidity condition (referred to as dry) and a condition of 45 ° C. and a humidity of 70% RH, and then each sample was measured. The increase in fog density at a wavelength of 410 nm (the same wavelength as the color density measurement) was examined.

<Results of Test> Test results: Table 4 shows that each of the image forming material samples (samples 1 to 6) using the compounds according to the present invention were comparative samples 7 and 8.
In each case, it was shown that the fog concentration was low and the storage stability was excellent. Table 3 also shows that all of the samples 1 to 6 of the present invention have high color density. From these results, it was shown that the image forming material of the present invention is a useful image forming material having excellent color developability and storage stability, and having high discrimination ability between an image area and a non-image area. Looking further at the forming material after laser writing, 1-6
The sample No. showed almost no haze, while the comparative samples Nos. 7 and 8 had a high haze, and the usefulness of the present invention was apparent also in this regard. Furthermore, as exposure conditions,
Even when the beam diameter was set to 20 μm and the laser energy density on the sample was set to 700 mJ / cm 2, haze due to thermal destruction (ablation) of the image forming layer did not occur.

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[Table 2]

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[Table 3]

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[Table 4]

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(Example 2) It is shown below that excellent performance can be exhibited even when the acid generator of the present invention is copolymerized with a leuco dye. The compounds shown in Table 5 were dissolved in chloroform and coated on a 175 μm-thick polyethylene terephthalate film (the coating amount is also described in Table 5). The protective layer coating solution described in Example 1 was applied on this film so that the solid content of the protective layer was 1.0 g / m 2, and the image forming material 9 was obtained.
~ 12 were created. The image forming materials of the formed forming materials 9 to 12 were exposed to laser light, and the color density at the maximum absorption wavelength (360 to 700 nm) of the formed dye was measured (Table 6). Further prepared image forming materials 7-1
A fresh sample of No. 0 was allowed to stand for 7 days under conditions of 45 ° C., dry and 45 ° C., and humidity of 70% RH, and the increase in fog density (measured at the same wavelength as the color density measurement) of each sample was examined (Table 7). ). All of the image forming materials using the compound according to the present invention have low fog density, excellent storage stability, and high color density, indicating that the image forming material of the present invention has achieved the object of the invention. .

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[Table 5]

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[Table 6]

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[Table 7]

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According to the present invention, an image is formed by irradiating a laser light in the range of 1 to 700 mJ / cm <2> to an image forming material containing a dye absorbing laser light on a support to form a dye in an absorption light wavelength range of 360 to 700 nm. The forming method and the image forming material form an image having a high color density of 3 or more, and the increase in fog during storage is small. Provided are an excellent image forming material and an image forming method which have less haze due to thermal destruction.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08F 20/00 C08F 20/38 20/38 26/06 26/06 C08J 7/04 CERZ C08J 7/04 CER G03F 7 / 004 503Z G03F 7/004 503 507 507 511 511 C08L 101: 00 // C08L 101: 00 B41M 5/18 102Z (72) Inventor Yasuya Sakurai 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term ( 2H025 AA01 AA11 AB09 AC08 AD03 BE00 CC11 CC14 DA19 2H026 AA07 AA24 BB48 DD02 DD42 DD45 DD48 DD53 4F006 AA02 AA12 AA35 AA36 AA39 AB16 AB24 AB65 AB66 BA00 CA01 DA04 4J100 AB00R AB02R AB04R AB07 AM07 AL08A AQ15Q BA02P BA03Q BA03R BA04Q BA04R BA08Q BA15Q BA15R BA31Q BA34Q BA41Q BA56P BA58Q BB01P BB01Q BC04P BC04R BC12P BC26P BC43P BC43Q BC43R BC49Q BC49R BC53Q BC58Q BC65Q BC83Q CA01 CA04 CA05

Claims (9)

[Claims] 1. An image forming method in which a dye is formed on an irradiated portion by laser light irradiation, wherein an image forming material containing a dye absorbing the laser light on a support is used.
Irradiates a laser having an energy of 700 mJ / cm ² or less to generate a dye having an absorption in a wavelength range of 360 to 700 nm.
An image forming method, wherein a density change of 3.0 or more occurs at a specific wavelength in a wavelength range of nm. 2. The image forming method according to claim 1, wherein the dye that absorbs laser light is an infrared absorbing dye. 3. An image forming material comprising: an acid generator which generates an acid on a support by the action of heat; and a concentration of 3 at a specific wavelength in a wavelength range of 360 to 700 nm by an intramolecular or intermolecular reaction by the action of an acid. The image forming method according to claim 1, further comprising a compound that causes a change in density of 0.0 or more and an infrared absorbing dye. 4. The method according to claim 1, wherein the acid generator has the following general formula (I):
A compound represented by the general formula (II):
The image forming method according to claim 3. Embedded image(Where R¹ Is an alkyl group, an aryl group or a hetero group
Represents a ring group. R^TwoAnd R^ThreeAre each independently an alkyl group
Or an aryl group,^TwoAnd R^ThreeAre simultaneously
It is not reel-based. Also R^TwoAnd R^ThreeAre connected to each other
They may combine to form a ring. )(Where R³¹ Is an alkyl group, an aryl group or
Represents a ring group. R³²Represents a substituent. R³³And R
³⁴Each independently represents a hydrogen atom or a substituent.
X¹Represents an atomic group necessary for forming a ring. R³²,
R³³Or R ³⁴Is X¹May be combined with to form a ring
No. ) 5. A compound which causes a concentration change of 3.0 or more at a specific wavelength in a wavelength range of 360 to 700 nm by an intramolecular or intermolecular reaction by the action of an acid, has the following general formulas (III) to (V): The image forming method according to claim 3, wherein the compound is a compound represented by any of the following. Embedded image (Wherein, X ² represents N (R ⁵⁸ ), O, or S, Y ¹ represents an atomic group necessary for forming a cyclic structure together with N—C—X ² , and A ¹ represents C (R ⁵⁹⁾ or an N, R ⁵¹ ~
R ⁵⁹ represents a hydrogen atom or a substituent, which may be the same or different, and R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R
⁵⁷ may combine with each other to form a condensed ring, and B ¹ is an aryl group, a heterocyclic group, an alkenyl group, an alkynyl group,
Represents an arylamino group or a heterocyclic amino group. ) (Wherein, Ar ¹ and Ar ² are an aryl group, a heterocyclic group,
Represents an alkenyl group or an alkynyl group, which may be the same or different, R ⁷¹ represents a hydrogen atom or a substituent, Y ² represents an aromatic hydrocarbon ring or a hetero ring, and X ³ represents O, S Or N (R ⁷² ), wherein R ⁷² represents a hydrogen atom or a substituent. ) (Ar ³ and Ar ⁴ represent an aryl group, a heterocyclic group, an alkenyl group or an alkynyl group, which may be the same or different, Z ¹ represents an aromatic hydrocarbon ring or a hetero ring, and A ² represents Represents O, S or N (R ⁷³ );
R ⁷³ represents a hydrogen atom or a substituent. ) 6. The image forming material contains a polymer represented by the following general formula (VI).
The image forming method according to any one of the above items. Formula (VI)-(A) _x- (B) _y- (C) _z- (wherein A represents a repeating unit obtained by polymerization of an acid generator monomer, and B represents 360 to 360 due to the action of an acid. 7
Represents a repeating unit obtained by polymerization of at least one or more vinyl monomers having a partial structure that causes a concentration change of 3.0 or more at a specific wavelength in a wavelength range of 00 nm, and C is copolymerizable with A and B Represents a repeating unit obtained by polymerization of at least one or more vinyl monomers. x, y and z represent mol%, and 1 ≦ x ≦ 100, 0 ≦ y ≦ 99, 0 ≦ z ≦ 99, and x + y, respectively.
+ Z = 100. ) 7. The image forming method according to claim 1, wherein a transmission type image is formed on a transmission support. 8. The image forming method according to claim 1, wherein the image forming layer does not contain a silver compound or a salt thereof. 9. An image forming material on which an image is formed by the method according to claim 1.