JP2001277731A - Image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new image forming material which is highly sensitive and excellent in storage stability, and also prode a sulfonate wherein fermentation performance coexists with storage stability, a discriminating property of an image area from a non-image area (a background area) is excellent, and can be applied to various uses. SOLUTION: The image forming material contains a specific structured sulfonate type generator which generates an acid by an action of heat on a base material, and a compound wherein a change is generated in an absorption area of 360-700 nm by ay reaction inside a molecule or between the molecules owing to an action of the acid. The sulfonate generator may be a polymer, and can double as a compound generating a change in absorption by the action of the acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 Sulfonates are widely used as various reactants in organic synthesis. Utilizing the property of decomposing to generate sulfonic acid, it is used as an acid generator in the field of image formation.
As the acid generator, those which generate an acid by the action of heat, light or the like are known, and they are used properly depending on the purpose of use. Among them, a thermal acid generator that generates an acid by heat needs to have both storage stability that does not decompose over time due to heat during storage and activity of an acid generation reaction due to heat, which is insufficient. If there is, the discriminability between the area that has received heat or light and the area that has not received heat is reduced. Investigations have been made to improve the compatibility between this kind of preservability and reaction activity of thermal acid generators, and the outline is described in “Organic Materials for Imaging” (1), edited by Organic Electronics Materials Research Group (Bunshin Publishing).
997), but this point is still extremely insufficient, and further improvement is desired.

In recent years, with the progress of high-power lasers, research on heat mode image recording media using these lasers has been actively conducted. A method of generating an acid by laser irradiation using a high-power laser and forming an image by a reaction between the acid and a dye precursor is disclosed in EP 905,656.
In this method, when a high-power laser is used, the surface of the image recording medium is partially destroyed by heat (so-called ablation), the haze is increased, and the background is stained. There are restrictions on raising 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]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel image-forming material having high sensitivity and excellent storage stability. A second object of the present invention is to provide a sulfonate ester which has both acid generating ability and storage stability, has good discrimination between an image area and a non-image area (background area), and is applicable to various uses. To provide.

[0005]

The present inventors have found that a sulfonic acid ester having a specific structure generates an acid sensitively by the action of heat, and is stable in a storage environment and does not thermally decompose. Based on this fact, as a result of further study, the object of the invention has been achieved. That is, the present invention has been achieved by the following items 1 to 6.

[0006] 1. An acid generator represented by the following general formula (I) which generates an acid by the action of heat on a support; and 360 to 700 n by an intramolecular or intermolecular reaction by the action of an acid.
An image forming material comprising: a compound which changes the absorption range of m.

[0007]

Embedded image

In the general formula (I), R ¹ represents an alkyl group, an aryl group or a heterocyclic group. R ² represents a substituent. R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. X represents an atomic group necessary for forming a ring. R ² , R ³ or R ⁴ may combine with X to form a ring.

[0009] 2. Wherein the acid generator represented by the general formula (I) has a polymerizable unsaturated group.
2. The image forming material according to item 1.

[0010] 3. A polymer having a partial structure composed of an acid generator represented by the above general formula (I) in a repeating unit and an intramolecular or intermolecular reaction caused by the action of an acid to form 3
An image forming material comprising: a compound which changes the absorption range of 60 to 700 nm. Further, obtained by polymerization of an acid generator represented by the general formula (I),
The polymer having a partial structure having an acid generating function in the repeating unit may also contain a functional group which causes a change in the absorption range of 360 to 700 nm by an intramolecular or intermolecular reaction caused by the action of an acid. Is also a compound in which this polymer causes a change in the absorption range from 360 to 700 nm by an intramolecular or intermolecular reaction caused by the action of the acid.

4. 4. The image forming material as described in 3 above, wherein the polymer as described in 3 above is a polymer represented by the following general formula (II). General formula (II)-(A) _x- (B) _y- (C) _z -In general formula (II), A represents a repeating unit obtained by polymerization of an acid generator represented by general formula (I). B represents a repeating unit obtained by polymerization of at least one or more kinds of vinyl monomers having a partial structure that causes a change in an absorption range of 360 to 700 nm by the action of an acid;
Represents a repeating unit obtained by polymerization of at least one or more vinyl monomers copolymerizable with A and B. x, y and z represent mol%, and 1 ≦ x ≦
100, 0 ≦ y ≦ 99, 0 ≦ z ≦ 99, x + y + z = 1
Represents 00. )

5. 5. The image forming material as described in any one of the above items 1 to 4, which contains an infrared absorbing dye and forms an image by irradiation with an infrared laser.

6. Any one of the above items 1 to 5, wherein the image forming layer does not contain a silver compound or a salt thereof.
Item.

7. A sulfonic acid ester derivative represented by the above general formula (I).

[8] A polymer containing a sulfonic acid ester group, which is represented by the general formula (II).

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the compound of the general formula (I) will be described. 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., aryl group (phenyl group, naphthyl group, etc.) ) Or a heterocyclic group (furyl, thienyl, pyrimidinyl, benzothiazolyl, 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),

Furthermore, 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.

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

In the general formula (I), the substituent R^TwoIs a substituent
And the substituent is R¹What was written in the description of
I can do it. R^TwoPreferably an alkyl group, halogen
Atom or alkoxy group, more preferably
Is a alkyl group. R^ThreeAnd R ^FourAre each independently hydrogen
Represents an atom or a substituent, and the substituent is R¹Theory of
Those mentioned in the clear. R^ThreeAnd R^FourGood as
Preferably a hydrogen atom, an alkyl group, a halogen atom or
An alkoxy group, more preferably a hydrogen atom or
Is an alkyl group. Also R^ThreeAnd R^FourAt least of
One is preferably a substituent. X forms a ring
Represents an atomic group required for Preferred as ring size
Is preferably a 3- to 9-membered ring, more preferably a 5-membered ring or
Is a 6-membered ring, particularly preferably a 6-membered ring. X is non
It is preferably a metal atom group, more preferably -C
(R^Five) (R⁶)-, -C (= Y)-, -N (R⁷)-,
—O— and —S—, and particularly preferably —C (R^Five)
(R⁶)-. Where R^Five, R⁶, R⁷Is a hydrogen atom
Or a substituent, and a preferred example of the substituent is R¹
Is the same as that described in the description. R^Five, R⁶Or
R⁷Are the same when there are multiple
Or different, and any two or
More than one may combine to form a ring. Y is =
O, = S, or = N-R⁷And R⁷Is
Same as the ones. R^Two, R^ThreeOr R^FourIs combined with X
To form a ring. Also R¹~ R^FourAt least
It is preferred that at least one has a polymerizable unsaturated group.
Preferably, the polymerizable unsaturated group is a vinyl group. Further
Are more preferred among the compounds represented by the general formula (I).
And a compound represented by the following general formula (III).

[0024]

Embedded image

In the formula, R ^{1 to} R ⁴ have the same meaning as in formula (I). R ⁸ and R ¹⁰ 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 ⁹ represents a hydrogen atom or a substituent (specific examples are those described in the description of R ¹ ), and preferably have a Hammett σm value of 0 or more, and more preferably a hydrogen atom or an acyloxy group. Further, the compound represented by the general formula (III) preferably has a polymerizable unsaturated group at any site, and a vinyl group is preferable as the polymerizable group.

Specific examples of the compounds represented by formulas (I) and (III) 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. In addition, as specifically described later in the synthesis examples, these compounds can be synthesized using a general sulfonic acid esterification method such as a dehydrochlorination reaction between a compound having a hydroxy group and a sulfonyl chloride. it can.

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

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 absorption region 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, compounds which cause an intramolecular or intermolecular reaction by the action of an acid to cause a change in the absorption 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 a retro Diels-Alder reaction (eg, 9, 10
An adduct of distyrylanthracene and maleic anhydride,
(C) a compound which expands a conjugated system by β-hydrogen elimination to form a color image in the region (for example, 1-acetoxy-1,2-diarylethane, 1-sulfoxy-1,
(D) a combination of an aldehyde and an active methylene compound which forms a color image in the area by dehydration condensation (for example, a photographic 4 equivalent magenta coupler (pyrazolone derivative) and p-methoxycinnamaldehyde) Or (e) a compound 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 whose absorption in the absorption region changes due to the removal of the substituent. No.

In a compound in which the absorption is changed by the decomposition or elimination of the amino group by the action of an acid, the amino group is substituted with an alkoxycarbonyl group (for example, a t-butoxycarbonyl group, a cyclohexyloxycarbonyl group, (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 the compound with the thermal acid generator and the 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 in which the absorption is changed by the decomposition or elimination of the hydroxyl group 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.

A basic leuco dye or the like which develops color instantly upon contact with an acid can also be used in the image forming material. An example of such a compound is “Organic Materials for Imaging”, edited by Organic Electronics Materials Research Group.
Compounds described in Bunshin Publishing Co., Ltd. (1997) and compounds described in the cited references described therein. Below 360-700nm by the action of acid
Specific examples of the compound which causes a change in the absorption range are shown below, but the present invention is not limited thereto. When the compound is a polymer, the molecular weight of the polymer is 1,000 to 10
It is preferably in the range of 100,000, particularly preferably in the range of 2,000 to 100,000. In the following specific examples, examples of the polymer are LD3, 5, 23, 24, 25, 30, and 34, and n in each structural formula can be selected from any molecular weight in the above range.

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

The image forming material of the present invention is generally prepared by coating a support with a compound capable of changing the absorption range from 360 to 700 nm by the action of the acid generator and the acid. At this time, when any of these is a polymer,
Or, unless it is amorphous with good coatability,
Usually, a binder coexists. When the binder does not need to be used, there is an advantage that the film thickness can be easily reduced and an image with good resolution can be obtained.

When a binder is used, water-soluble binders such as gelatin, casein, starches, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide, ethylene-maleic anhydride copolymer, and polyvinyl butyral, triacetyl cellulose, Any of water-insoluble binders such as polystyrene, methyl acrylate-butadiene copolymer, and acrylonitrile-butadiene copolymer can be used.

On the other hand, by the action of an acid generator or an acid, 3
When one or both of the compounds (including copolymerization) that cause a change in the absorption range of 60 to 700 nm are polymers, it is not necessary to separately add a binder, and an acid is generated in the immediate vicinity of the compound whose hue changes. In that sense, higher sensitivity can be expected. In addition, by controlling the diffusion of molecules by polymerization, there is a possibility that the cut-off and preservation of images can be improved. These characteristics are particularly preferable for applications requiring high image quality, such as graphic arts films. A preferred form of such a compound is represented by the general formula (I
It is represented by I).

The general formula (II) will be described. In the general formula (II), A is a compound represented by the general formula (I) or (III) with a polymerizable group, and specific examples thereof include a polymerizable group in the above compound examples. Are equivalent. In the general formula (II), B is 3 due to the action of an acid.
It represents a repeating unit obtained by polymerization of at least one kind of vinyl monomer having a partial structure that causes a change in an absorption range of 60 to 700 nm. This monomer is obtained by introducing a polymerizable group at a substitutable position in the structure of a compound which causes an absorption change by the action of an acid described above. Specific examples are shown below, but the present invention is not limited to these.

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

C in the general formula (II) represents a repeating unit obtained by polymerization of at least one kind of vinyl monomer capable of forming a copolymer with A and B, and represents a polarity, a glass transition temperature, and the like. The storage stability, the color-forming activity and the like can be controlled by adjusting. 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.

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

In the general formula (II), 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 (II) 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 is preferably a homopolymer or a random copolymer which is easily synthesized.

The monomers forming A, B, C in the polymer represented by the general formula (II) and x, y, z
Are shown, but the present invention is not limited to these.

[0063]

[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.

Among 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 (II), monomers forming A, B and C may be mixed and placed in a reaction vessel first, and an initiator may be charged, or these monomers may be polymerized. The polymerization may be carried out through a process of dropping in a solvent.

The polymer represented by the general formula (II) 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 partial structure having a change in the absorption range of 360 to 700 nm by the action of an acid. It is a polymer having both As such a polymer, there may be a polymer of a single monomer having both functions, but from a synthetic point of view, the polymer represented by the general formula (II) is advantageous because the selection range of the monomer is wide. . The image forming material of the present invention is generally prepared by coating a polymer represented by the general formula (II) on a support. When the polymer of the present invention also has a function of generating an acid by heat, since the absorption region alone changes due to the action of heat alone, when used as a heat-sensitive material, sensitivity and image resolution Is better. Further, in the image forming material of the present invention, since the material itself has a binder function, it is not necessary to use the above-mentioned binder, so that the film thickness can be reduced and an image with good resolution can be obtained. In addition, there is an advantage that thermal destruction, that is, ablation hardly occurs. However, when using the polymer represented by the general formula (II), if necessary, a binder may be used in combination, and specific examples thereof include those described above.

In the present invention, a small amount of a base is added for the purpose of enhancing the storage stability of the image forming medium, and a compound capable of generating an acid by the action of light or heat is separately 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 preferable. For example, a guanidine derivative (for example, 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 (II).
1%, particularly preferably 5 to 20%.
mol% is added.

For the purpose of further increasing the sensitivity of the image forming material of the present invention, another acid generator different from that of the present invention may be added. 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 compounds described in cited references. No. Many of the photoacid generators described in these documents also function as thermal acid generators. When a pigment is added, preferred examples include diatomaceous earth, talc, kaolin, calcined kaolin, titanium oxide, silicon oxide, magnesium carbonate, calcium carbonate, aluminum hydroxide, and urea-formalin resin. 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 they can be added as needed.

As the support used in the image forming material 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 image, for example, a film for an OHP (overhead projector) or a film for plate making, a transparent support is used among the above supports. . 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.

In the image-forming material of the present invention, the means for image formation is heating or photothermal energy conversion from light to heat, that is, light irradiation in a heat mode. When performed by heating, as a heating method, a method of contacting with a heated block or plate,
A method of contacting with a heat roller or a heat drum, or a method of imagewise heating with a thermal head of a thermal printer is used.In the case of light irradiation, laser light is used in addition to the method of irradiating a halogen lamp or infrared or far infrared lamp heater. And the like. When the image forming material of the present invention is used for a material requiring a high resolution, such as a plate making material, a method of scanning and exposing with a laser beam is preferable.
In order to form an image with less heat energy, the heat-sensitive material of the present invention may be heated to an appropriate temperature in advance. In the present invention, after imagewise heating is performed by these methods, a temperature of 60 to 150 ° C. (preferably 60 to 150 ° C.) is used.
By heating the entire surface at 20 ° C.), the image can be amplified.

When an image is formed by irradiating a laser beam, in order to convert the laser beam into thermal energy, it is necessary that a dye absorbing light having the wavelength of the laser beam be present in the image forming material. 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. Therefore, dyes having absorption in the near-infrared spectral region are used in the image forming material of the present invention in which recording is performed by these laser beams. As the near-infrared absorbing dye, a cyanine dye, a squarylium dye, a merocyanine dye, an oxonol dye, a phthalocyanine dye, and the like are used. Specific examples thereof include, for example, U.S. Pat.
No. 73,572, No. 4,948,777, No. 4,
Nos. 950,640, 4,950,639, 4,948,776, 4948,778, and 4,9
No. 42,141, No. 4,952,552, No. 5,
Nos. 3,036,040 and 4,912,083. Hereinafter, a method for synthesizing the compound of the present invention will be described, but the present invention is not limited thereto. (Synthesis Example 1) Synthesis of Exemplified Compound (1)

[0074]

Embedded image

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

(Synthesis Example 2) Synthesis of Exemplified Compound (2) Except that the above-mentioned raw material compound 1a was replaced with the same amount of medityl sulfonyl chloride, the same operation as in the synthesis of Exemplified Compound (1) was performed. ) Was synthesized. The decomposition temperature of the compound was 156 ° C.

(Synthesis Example 3) Synthesis of Exemplified Compound (6) Exemplified Compound (1) except that the above-mentioned starting compound 1a was replaced with the same mole of 2,5-xylylsulfonyl chloride.
Exemplified compound (6) was synthesized by the same operation as in the synthesis of. The decomposition temperature of the compound was 142 ° C.

(Synthesis Example 4) Synthesis of Exemplified Compound (7) Except that the above-mentioned starting compound 1a was replaced with the same mole of 4-styrylsulfonyl chloride, the same operation as in the synthesis of Exemplified Compound (1) was carried out. 7) was synthesized.
The decomposition temperature of the compound was 173 ° C.

(Synthesis Example 5) Synthesis of Exemplified Compound (12) Except that the above-mentioned raw material compound 1a was replaced with the same mole of propylsulfonyl methacrylate chloride, the same operation as in the synthesis of Exemplified Compound (1) was carried out. 12) was synthesized. The decomposition temperature of the compound was 123 ° C.

(Synthesis Example 6) Synthesis of Exemplified Compound (P-1) Exemplified Compound (7) (50 mmol) was dissolved in toluene (22 ml).
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 solution was poured into hexane (1000 ml), and the precipitate was collected by filtration and dried to obtain Exemplified Compound (P-1) at a yield of 65%. The weight average molecular weight was 72,000, and the decomposition temperature was 120 ° C.

(Synthesis Example 7) Synthesis of Exemplified Compound (P-8) Exemplified Compound 7 (7.5 mmol) and B-3 (2.5 mmol) were mixed with toluene (4.4 ml) and methyl ethyl ketone (2 m).
l) 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) (0.025 g) in methyl ethyl ketone (0.6 ml), and the mixture was reacted for 2 hours. -Azobis (4-methoxy-2,4
-Dimethylvaleronitrile) (0.025 g) in methyl ethyl ketone (0.6 ml) was added. After reacting for 2 hours, the reaction solution was poured into hexane (400 ml),
The precipitate was collected by filtration and dried to give Exemplified Compound (P-8) in 59
% Yield. The weight average molecular weight was 48,000.

[0082]

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 recording film> Compound (7) of the present invention,
(2), (P-1), (P-4) and comparative compounds R-1 and R-2 having similar structures were dissolved in chloroform as shown in Table 2, and the solution was applied on a 175 μm-thick polyethylene terephthalate film. (The coating amount is also shown in Table 2
Described). The coating solution for the protective layer shown below was applied onto this film to prepare image forming materials 1 to 6. As the polystyrene used for the coating solution, polystyrene beads (particle diameter: about 3.2 mm) manufactured by Wako Pure Chemical Industries, Ltd. were used.

<Preparation of Coating Solution for Protective Layer> An aqueous solution containing 4% by weight of Kuraray Poval PVA-110 manufactured by Kuraray Co., Ltd. and 0.1% by weight 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 Conditions> A laser device (Spectra Diode Labs N) was used as a laser light source for writing images.
o.SDL-2430, wavelength range: 800 to 830 nm)
The two lasers were combined to obtain an output of 140 mW to obtain an image writing laser beam. Using this laser light, the beam diameter was 20 μm, and the laser energy density on the sample was 4.
It was set to 5 mJ / mm ² . Scanning exposure was performed on the formed image forming material from the protective layer side of the forming material under the above laser exposure conditions. Measurement of image forming ability: prepared image forming material samples 1 to 6
(Table 2) was subjected to laser exposure, and the resulting image was measured for color density at 410 nm (Table 3). Storage test: each of the prepared image forming materials 1 to 6 was subjected to humidity control at 45 ° C. without any humidity control (expressed as dry) and 4
Each sample was allowed to stand for 7 days under conditions of 5 ° C. and 70% RH, and the increase in the fog density at 410 nm of each sample over time was determined (Table 4). Test results: Samples 1 to 4 of the present invention showed little increase in fog concentration during the time-lapse test (Table 4), excellent storage stability, and Table 3 as compared with Comparative Samples 5 and 6.
Indicates that the sample has a high color density, and the sample of the present invention satisfies the object of the invention as an image forming material.

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

Embedded image

[0089]

Embedded image

(Example 2) The following shows that excellent performance can be exhibited even when the acid generator of the present invention is copolymerized with a leuco dye. Compound P-8 of the general formula (II) shown in Table 5,
P-15 and a comparative compound RP- having a similar structure
3 and RP-4 were dissolved in chloroform as shown in Table 5, and applied on a 175 μm-thick polyethylene terephthalate film (the coating amounts are also described in Table 5, respectively, and the structure of the comparative compound is described in Table 6). On this film, the protective layer coating solution shown in Example 1 was applied with a solid content of the protective layer of 1.0.
g / m2, and image forming materials 7 to 10 were prepared. Test of image forming ability: The formed image forming materials 7 to 10 were exposed to laser by the same exposure method as in Example 1 to measure the color density at 410 nm (Table 7). Storage test: Further, each of the prepared image forming materials 7 to 10 was subjected to the same method as in Example 1 at 45 ° C.
The samples were aged for 7 days at 70 ° C. and a humidity of 70% RH, and the increase in the fog density at 410 nm of each sample was examined (Table 8). Test results: Samples 7 and 8 using the compound of the present invention both exhibited a low increase in fog density during the time-lapse test, excellent storage stability, and a high coloring density in the exposed area. Is a useful image forming material that satisfies the objects of the invention.

[0091]

[Table 5]

[0092]

[Table 6]

[0093]

[Table 7]

[0094]

[Table 8]

[Effect of the Invention] The compound of the present invention comprising a compound represented by the general formula (I) or a compound obtained by polymerization of the compound (for example, a compound of the general formula (II)) on a support as an acid generator. The image forming material has high sensitivity and excellent storage stability, and therefore, the discrimination between the image area and the fog area is also improved. It is also excellent as an image recording means by scanning with laser light.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 212/12 C08F 216/14 212/14 216/16 216/14 216/18 216/16 218/04 216 / 18 218/08 218/04 220/14 218/08 220/16 220/14 220/18 220/16 220/28 220/18 220/30 220/28 220/36 220/30 220/56 220/36 220/58 220/56 226/06 220/58 230/08 226/06 G03F 7/004 503Z 230/08 B41M 5/18 102Z G03F 7/004 503 5/26 SF term (reference) 2H025 AB20 AC01 AD01 BE00 CC14 2H026 AA07 BB01 BB48 DD02 DD42 DD45 DD48 2H111 HA00 HA14 HA24 HA31 4J100 AB00R AB02R AB04R AB07P AB07R AE02R AE09R AE10R AG04R AG08R AL03R BA04R AL08P AL08Q AL08R AL09R AL11R15A02A BA28Q BA31R BA40Q BA46Q BA55P BA76Q BA76R BB01Q BC04P BC 04R BC12P BC43P BC43Q BC43R BC48P BC48Q BC48R BC49Q BC49R BC53Q BC65Q BC73Q BC75Q BC79Q BC80Q BC83Q CA01 CA04 CA05 JA43

Claims (8)

[Claims] 1. An acid generator represented by the following general formula (I) which generates an acid on a support by the action of heat and 360 to 700 nm by an intramolecular or intermolecular reaction by the action of an acid.
An image forming material comprising: a compound which changes the absorption range of the compound. [Formula 1] (Wherein, R ¹ represents an alkyl group, an aryl group or a heterocyclic group; R ² represents a substituent; R ³ and R ⁴ each independently represent a hydrogen atom or a substituent; X forms a ring R ² , R ³ or R ⁴ may combine with X to form a ring.) 2. The method according to claim 1, wherein the acid generator represented by the general formula (I) has a polymerizable unsaturated group.
The image forming material as described in the above. 3. A polymer having a partial structure consisting of an acid generator represented by the general formula (I) in a repeating unit, and a polymer having a molecular weight of 360 to 7 by an intramolecular or intermolecular reaction caused by the action of an acid.
An image forming material comprising: a compound that changes the absorption range of 00 nm. 4. The image forming material according to claim 3, wherein the polymer according to claim 3 is a polymer represented by the following general formula (II). Formula (II)-(A) _x- (B) _y- (C) _z- (where A represents a repeating unit obtained by polymerization of an acid generator represented by Formula (I), Represents a repeating unit obtained by polymerization of at least one or more kinds of vinyl monomers having a partial structure in which the absorption range from 360 to 700 nm is changed by the action of an acid, and C represents A and B
And a repeating unit obtained by the polymerization of at least one or more vinyl monomers copolymerizable with. x, y and z represent mol%, and 1 ≦ x ≦ 100, 0 ≦
It represents y ≦ 99, 0 ≦ z ≦ 99, and x + y + z = 100. 5. The image forming material according to claim 1, further comprising an infrared absorbing dye, wherein an image is formed by irradiating an infrared laser beam. 6. The image forming material according to claim 1, wherein the image forming layer does not contain a silver compound or a salt thereof. 7. A sulfonic ester derivative represented by the above general formula (I). 8. A sulfonic ester group-containing polymer represented by the general formula (II).