JP3515846B2 - Negative image recording material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material that can be used as an offset printing master, and more particularly to a lithographic printing plate for so-called direct plate making which can be made directly from digital signals of a computer or the like.

[0002]

2. Description of the Related Art Conventionally, as a system for directly making a plate from digital data of a computer, an electrophotographic method, a photopolymerization system by a combination of Ar laser exposure and post-heating, and a silver salt sensitive material laminated on a photosensitive resin , A silver master type, and a method in which the silicone rubber layer is destroyed by discharge or laser light have been proposed. The one that uses the electrophotographic method of
Processing such as charging, exposure, and development is complicated, and the apparatus becomes complicated and large-scale. This method requires a post-heating step and also requires a highly sensitive plate material, which makes it difficult to handle in a bright room. The methods (1) and (2) have the drawback that the processing becomes complicated and the cost becomes high because a silver salt is used. Further, although the method of (1) is a method with a relatively high degree of perfection, it has a problem in removing the silicone residue remaining on the plate surface. On the other hand, the development of lasers in recent years has been remarkable, and in particular, solid-state lasers and semiconductor lasers having a light emitting region from near infrared to infrared have high output and small size and are easily available. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like. However, many practically useful photosensitive image recording materials have a photosensitive wavelength of 450 nm or less, and thus cannot record images with these lasers. Therefore, an image recording material capable of recording without depending on the wavelength of the exposure light source is desired.

As a technique capable of recording without depending on the wavelength of the exposure light source, JP-A-52-113219 discloses a compound (for example, a diazonium compound) which decomposes with light and heat,
A positive image recording material is disclosed which comprises a substance particle capable of absorbing light and converting it into heat, and a binder. In this method, the diazonium compound is decomposed by heat to record an image. Further, JP-A-58-148792 discloses a positive type photosensitive heat-sensitive recording material containing thermoplastic resin particles, a light-heat converting substance and a photo-crosslinking substance (for example, a diazonium compound) as main components. There is. In this case, the durability of the image is improved by utilizing the fact that the thermoplastic resin particles form an image by heat and the photocrosslinking substance is directly decomposed by light. In direct plate making, writing is performed by scanning a beam of a laser light source, but a negative type material is preferable because writing time can be shortened. However, a negative image recording that can be thermally recorded by using a solid-state laser or semiconductor laser (thermal mode) having an emission region from near infrared to infrared as an exposure light source when directly making a plate from digital data of a computer or the like. No material having good recording properties has been known so far.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a negative image recording material capable of recording without depending on the emission wavelength of an exposure light source, and particularly from near infrared to infrared ( It is an object of the present invention to provide a negative image recording material capable of recording with light in the (heat ray) region. Further, an object of the present invention is to enable plate making directly from digital data of a computer or the like by recording using a solid-state laser or semiconductor laser (thermal mode) having a light emitting region from near infrared to infrared. It is an object of the present invention to provide a negative lithographic printing plate for heat mode writing type direct plate making which can directly use a processing device and a printing device.

[0005]

The above object can be achieved by the constitution of the present invention shown in the following (1). (1) A substance that absorbs light and generates heat, a water-insoluble and alkaline water-soluble resin, and 4 to 8 benzene nuclei in the molecule,
A negative image recording material containing a phenol derivative having at least one phenolic hydroxyl group and at least two groups represented by formula (I). —CH ₂ OR ¹ (I) (In the formula, R ¹ represents a hydrogen atom, an alkyl group or an acyl group) Further, preferred embodiments of the present invention include the following (2) to (12). (2) A substance that absorbs light and generates heat, a water-insoluble and alkaline water-soluble resin, and 4 to 8 benzene nuclei in the molecule,
A negative image recording material comprising a phenol derivative having at least one phenolic hydroxyl group and at least two groups represented by formula (I), wherein the water-insoluble and alkaline water-soluble resin is A negative image recording material comprising a resin having a phenolic hydroxyl group or an olefinically unsaturated bond.

(3) A substance which absorbs infrared light or near infrared light to generate heat on a support, a water-insoluble and alkali-water-soluble resin having a phenolic hydroxyl group or an olefinic unsaturated bond, and an intramolecular substance 4 to 8 benzene nuclei, at least one phenolic hydroxyl group and at least 2
A negative image recording material containing a phenol derivative having one group represented by formula (I). (4) The image recording material according to (3) above, wherein a dye is used as a substance that absorbs infrared light or near infrared light and generates heat. (5) The image recording material according to (3) above, wherein a pigment is used as a substance that absorbs infrared light or near infrared light and generates heat. (6) The image recording material according to the above (3), wherein carbon black is used as a substance that absorbs infrared light or near infrared light and generates heat.

(7) The image recording material according to the above (3), wherein a novolac resin is used as a resin which is water-insoluble and alkali-water-soluble and has a phenolic hydroxyl group or an olefinic unsaturated bond. (8) The image recording material according to (3) above, wherein an acrylic resin having an allyl group is used as a resin which is water-insoluble and alkali-water-soluble and has a phenolic hydroxyl group or an olefinic unsaturated bond. (9) The image recording material according to (3) above, wherein an acrylic resin having a phenolic hydroxyl group is used as the resin which is water-insoluble and alkali-water-soluble and has a phenolic hydroxyl group or an olefinic unsaturated bond. (10) The image recording material as described in (3) above, which uses a polyester film as a support. (11) Above (3) using an aluminum plate as the support
Image recording material. (12) A negative image recording method, which comprises exposing the negative image recording material of the above (3) using a laser emitting infrared light or near infrared light, and then developing with alkaline water. (13) A negative image recording method, wherein R ¹ in the formula (I) in the above (3) is an alkyl group. (14) A negative image recording method, wherein R ¹ in the formula (I) in the above (3) is a methyl group. (15) The negative image recording material according to the above (3) is exposed by using a laser emitting infrared light or near infrared light, further heat-treated, and then developed with alkaline water. Type image recording method.

As a result of intensive studies, the present inventors have found that the molecule has 4 to 8 benzene nuclei, at least one phenolic hydroxyl group and at least two groups represented by the formula (I). By using the characteristic phenol derivative in combination with a water-insoluble and alkaline water-soluble resin and a substance that absorbs light and generates heat, it does not depend on the wavelength of the exposure light source, especially recording from near infrared light to infrared light The present invention has been completed by finding that a possible negative recording material can be obtained. In the present invention, the energy of exposure is converted into heat energy, and the generated heat energy causes a condensation reaction with a phenol derivative to record an image.
In the present invention, by using a phenol derivative having 4 to 8 benzene nuclei in the molecule,
As compared with the case of using a phenol derivative having only to 3 benzene nuclei, it has the advantages of higher sensitivity and higher film strength in the exposed area. Further, the use of a phenol derivative having 9 or more benzene nuclei in the molecule is not preferable because it causes a problem that developability is lowered and stains easily occur.

In the present invention, the phenol derivative is 2
It is preferable to have at least 4 phenolic hydroxyl groups from the viewpoint of developability after exposure, and it is preferable that the group represented by the formula (I) be 4 or less.
It is preferable to have more than one because the film strength of the exposed part becomes higher. In the present invention, the substance that absorbs light and generates heat is a substance that absorbs infrared light or near infrared light and generates heat,
It is preferable because recording in the thermal mode can be made good. In the present invention, a substance that absorbs infrared light or near infrared light and generates heat is preferably a dye in terms of developability after exposure, and also absorbs infrared light or near infrared light to generate heat. When the substance that is generated is a pigment, the sensitivity is improved, which is preferable. Furthermore, when the substance that generates heat by absorbing infrared light or near infrared light is carbon black, the absorption wavelength range is wide and the sensitivity is high. preferable.

In the present invention, it is preferable to use a polyester film as the support because it is lightweight, and it is preferable to use an aluminum plate because the dimensional stability is good. The negative image recording material of the present invention is preferably used in a negative image recording method of exposing with a laser emitting infrared light or near infrared light and then developing with alkaline water. Preferred examples of the negative image recording material of the present invention are negative type heat-sensitive lithographic printing plates, and also heat mode writing type negative type lithographic printing plates for direct plate making. Heat mode writing uses an appropriate heat ray source,
This heat ray source is controlled based on digital data and recorded on the image recording material. As a heat ray source at this time,
There are thermal heads used in facsimiles and lasers that emit infrared light or near infrared light.However, when a thermal head is used, the resolution of the image is low. Lasers that emit infrared light are preferred.

The present invention is basically a photosensitive recording material because it converts light into heat by a light-heat converting substance and causes a crosslinking reaction by the generated heat. However, the preferred light used in the present invention is ultraviolet rays, visible rays, and infrared rays. Among them, infrared rays are generally called heat rays, and when recording on the recording material of the present invention with infrared rays, The recording material can be said to be a heat-sensitive recording material.
Hereinafter, the present invention will be described in detail. In R ¹ of the above formula (I), the alkyl group is a methyl group, an ethyl group, n
An alkyl group having 1 to 4 carbon atoms such as a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group, and an acyl group includes a formyl group, an acetyl group and a butyryl group. , Benzoyl group, cinnamoyl group and valeryl group are preferred. Further, a substituted alkyl group having 1 to 4 carbon atoms such as methoxyethyl group, methoxypropyl group, hydroxyethyl group and hydroxypropyl group can also be used.

The phenol derivative used in the present invention is a known phenol compound, for example, JP-A-1-289946,
JP-A-3-179353, JP-A-3-200252, JP-A-3-
128959, JP-A-3-200254, JP-A-5-158233,
The phenol compound described in JP-A-5-224409 and formaldehyde are mixed in a strongly alkaline medium to about 0.
By reacting at a temperature of 80 ° C., preferably 10 to 60 ° C. for 1 to 30 hours, R ¹ ═H can be obtained. Then, under acidic conditions, an alcohol having 1 to 4 carbon atoms, a substituted alcohol, an acid halide, or an acid anhydride, and 0 to 80.
By reacting at 1 ° C. for 1 to 30 hours, R ¹ = alkyl and acyl can be obtained. The temperature when reacting with an alcohol or a substituted alcohol is preferably 20 to 80 ° C., and the temperature when reacting with an acid halide or an acid anhydride is
0-30 degreeC is preferable.

Specific examples of the phenol derivative used in the present invention include, but are not limited to, compounds represented by the following general formulas (II) to (IX).
These phenol derivatives may be used alone or in combination of two or more, and the amount used in that case is 0.2 to 60% by weight in the photosensitive composition, preferably 0. 5-2
It is 0% by weight. Further, a compound having 1 to 3 benzene nuclei and having a phenolic hydroxyl group and a group represented by the formula (I) causes a decrease in inking property and development acceptability.
It is desirable that the photosensitive composition of the present invention be substantially free of these compounds. More specifically, it is preferably 5% by weight or less, more preferably 3% by weight or less, and most preferably 0% by weight, based on the photosensitive composition.

[0014]

[Chemical 1]

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

In the formula, R ^{2 to} R ⁴ , R ⁹ , R ¹⁷ , and R ¹⁸ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ⁵ , R ^{13 to} R ¹⁶ represent a hydrogen atom or an alkyl group. shown, R ⁶ to R ⁸ represents a hydrogen atom, a halogen atom or an alkyl group, R ¹⁰ to R ¹² represents a single bond, an optionally substituted alkylene group, an alkenylene group, a phenylene group, a naphthylene group, a carbonyl A group, an ether group, a thioether group, an amide bond, or a combination of two or more thereof, Y represents a group represented by formula (I), a, b,
c, d, x, and y are integers of 0 to 3, but a + b + c
+ D + x + y is an integer of 2 to 16, and k, l, m, n
Represents an integer of 0 to 3, but all are not 0, and e, f, g, h, p, q, r, s, t, and u are 0 to 3.
And the integer z is 0 or 1. The general formula (II)
Specific examples of the compounds represented by- (IX) include those having the following structures.

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

(In the formula, Y ^{1 to} Y ¹² represent a hydrogen atom or a group represented by the formula (I), and at least two of each compound have the group represented by the formula (I). , And preferably all are groups represented by formula (I).) In the present invention, various pigments or dyes can be used as the substance that absorbs light and generates heat. As the pigment, commercially available pigments and color indexes (C.I.
I. ) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association,
1977), "Latest pigment application technology" (CMC Publishing,
1986, "Printing Ink Technology" (CMC Publishing, 1
The pigments described in pp. 984) can be used. Examples of types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacrid pigments, dioxazine pigments, isoindolinone pigments. , Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.

These pigments may be used without being surface-treated, or may be used after being surface-treated. The surface treatment method includes a method of coating a surface of resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface. Conceivable. The above-mentioned surface treatment method is described in "Characteristics and Applications of Metal Soap" (Koushobo), "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 198).
6 years). The particle size of the pigment is 0.01 μm
It is preferably in the range of from 10 μm to 0.05 μm
More preferably, it is in the range of 1 μm. As a method of dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill and a pressure kneader. Detail is,
It is described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

As the dye, commercially available dyes and literatures (for example, "Handbook of Dyes" edited by the Society of Synthetic Organic Chemistry, Showa 4)
The publicly known thing described in the 5-year publication can be used. Specific examples include dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes. Among these pigments or dyes, those absorbing infrared light or near infrared light are particularly preferable. Carbon black is preferably used as a pigment that absorbs infrared light or near infrared light.

Examples of dyes which absorb infrared light or near infrared light include those disclosed in JP-A-58-125246 and 59-59.
84356, 59-202829, 60-78.
Cyanine dyes described in Japanese Patent No. 787, etc., JP-A-58
-173696, 58-181690, 58-
Methine dyes described in 194595 and the like, JP-A-58-112793, JP-A-58-224793, and JP-A-58-224793.
9-48187, 59-73996, 60-5
2940, 60-63744 and the like, naphthoquinone dyes, JP-A-58-112792 and the like, squarylium dyes, British Patent 434,87.
Examples thereof include cyanine dyes described in No. 5. Further, the near infrared absorber described in US Pat. No. 5,156,938 is also preferably used. Further, substituted arylbenzo (thio) pyrylium salts described in US Pat. No. 3,881,924, trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-1810.
No. 51, No. 58-220143, No. 59-41363.
Nos. 59-84248, 59-84249, 59-146063, and 59-146061, and the pyrylium compounds described in JP-A-59-2161.
No. 46, cyanine dyes, pentamethine thiopyrylium salts described in US Pat. No. 4,283,475, and Japanese Patent Publication No. 5-1
The pyrylium compounds disclosed in Japanese Patent Nos. 3514 and 5-19702 are particularly preferably used. Another particularly preferable example is the near-infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993.

These pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1, based on the total solid content of the image recording material.
-20% by weight, more preferably 0.5-15% by weight, can be added to the image recording material. Addition amount is 0.
If the amount is less than 01% by weight, an image cannot be obtained, and if the amount is more than 50% by weight, stains occur on the non-image portion during printing. These dyes or pigments may be added to the same layer as the phenol derivative, or may be added to another layer provided separately. When it is provided as a separate layer, it is preferably added to the layer adjacent to the layer containing the phenol derivative. Next, the water-insoluble and alkaline water-soluble resin used in combination with the phenol derivative of the present invention will be described. Although various resins can be used as the water-insoluble and alkali-water-soluble resin, those having a phenolic hydroxyl group or an olefinic unsaturated bond are particularly preferable. Examples of preferable resins include the following novolac resins.

For example, phenol formaldehyde resin,
m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, o- or m- / p-, m- / Included are cresol formaldehyde resins such as mixed formaldehyde resins. Other resol type phenolic resins are also preferably used, and phenol / cresol (m-, p-, o- or m- / p-, m- /
Mixed formaldehyde resins are preferred, and any of o- and o- / p-mixtures are preferred, and especially JP-A-61-2170.
Phenolic resins described in Japanese Patent No. 34 are preferred. Further, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, JP-A-50-55406, JP-A-51-34711, JP-A-51-36129, JP-A-52-28401,
JP-A-62-38454, West German patent 3528390
, West German Patent 3528929, US Patent 472419
5, JP-A-5-230139, JP-A-5-2301
No. 40, Japanese Patent Application No. 6-123895, or the acrylic resin having a phenolic hydroxyl group described in the specification can also be used.

Olefinicity preferably used in the present invention
As an example of a resin having an unsaturated bond, Japanese Patent Publication No. 3-63
740, US Patent 3,376,138, US Patent 355.
6793, JP-A-52-988, JP-B-60-37.
What is described in each publication or specification of No. 123
Can be mentioned. In addition, olefinic unsaturated bond
For resins that have
In order to improve
It is preferably contained as a copolymerization component. Arca
An acidic group having a pKa of 14 or less is used as the re-soluble group.
, For example, -SO ₃H, -OP (O) (OH)₂, -P (O) (OH)₂,-
COOH, −CONHCO−, −CONHSO₂−, −SO₂NH-, Feno
OH and the like. These alkaline water soluble
The resin has a weight average molecular weight of 500 to 400,000,
It is preferable that the average molecular weight is 200 to 150,000. Or
One or more kinds of alkalescent water-soluble resin
May be used in combination, and the total solid content of the photosensitive composition
5 to 99% by weight, preferably 30 to 95% by weight
Used in weight.

If desired, various additives may be added to the image recording material of the present invention. For example, a polyfunctional monomer having two or more radically polymerizable ethylenic double bonds in the molecule can be added. Examples of such compounds include ethylene glycol di (meth) acrylate, cyethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, and triethyl ethane tri (meth) acrylate. Examples thereof include methylolpropane tri (meth) acrylate, pentaerythritol, and dipentaerythritol tri-, tetra-, or hexa (meth) acrylate. The addition amount of these polyfunctional monomers is 30% by weight or less in the image recording material. Also, alkyl ethers (eg, ethyl cellulose, methyl cellulose) for improving coating properties, surfactants (eg, fluorine-based surfactants), plasticizers for imparting film flexibility and abrasion resistance (eg, triacetate). Cresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added. The amount of these additives to be added varies depending on the purpose of use, but generally it is based on the total solid content of the image recording material.
It is 0.5 to 30% by weight.

As a printout agent for obtaining a visible image immediately after heat generation by exposure, a combination of a compound which releases an acid by heat generation by exposure and an organic dye capable of forming a salt can be mentioned as a representative example. Specifically, JP-A-50-
36209 and JP-A-53-8128, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye, and JP-A-53-
The combination of a trihalomethyl compound and a salt-forming organic dye described in JP-A-36223 and JP-A-54-74728 can be mentioned. As the image colorant, dyes other than the above-mentioned salt-forming organic dyes can be used. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101 and Oil Yellow # 13
0, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-50
5 (above, manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI425
55), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI5201).
5) etc. can be mentioned. These print-out agents and dyes are used in an amount of 0 to 30% by weight in the image recording material.

If a visible image having a sufficient density can be obtained by the substance which absorbs light and generates heat according to the present invention, it is not necessary to add such a dye, but the dye is used for the purpose of promoting the crosslinking reaction. It is also possible to add only the releasing agent (acid generator). The image recording material of the present invention is coated on a support using a solvent that dissolves or disperses the above components. As the solvent used here, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-
2-Propyl acetate, N, N-dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, ethyl acetate, methyl lactate, ethyl lactate and the like are used, and these solvents may be used alone or as a mixture.
Further, a mixed solvent obtained by adding a small amount of water or a solvent which does not dissolve the phenol derivative such as toluene or the polymer compound to these solvents or the mixed solvent is also suitable. The concentration (solid content) of the above components in the solvent is 1 to 50% by weight.

When a solution dissolved or dispersed in these solvents is applied and dried, it is desirable to dry at 50 ° C to 120 ° C. The drying method may be such that the temperature is first lowered and pre-dried and then dried at a high temperature, but it may be directly dried at a high temperature by selecting an appropriate solvent and concentration, but since it is a thermosensitive recording material, it is 150 ° C or higher. It is not preferable to dry at high temperature. Although the coating amount varies depending on the use, for example, in the case of a photosensitive lithographic printing plate (heat-sensitive lithographic printing plate), generally, the solid content is preferably 0.5 to 3.0 g / m ² . As the coating amount decreases, the photosensitivity increases,
The physical properties of the photosensitive film deteriorate. Further, if necessary, a mat or a mat layer may be provided on the photosensitive film, and an undercoat layer may be provided.

The support to which the image recording material of the present invention is applied is, for example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), for example, aluminum (including aluminum alloy), zinc, Plates of metal such as copper, for example, plastics such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Film of
It includes paper or plastic film on which the above metal is laminated or vapor deposited. Among these supports, it is preferable to use a polyester film or an aluminum plate, and an aluminum plate is particularly preferable because it is extremely dimensionally stable. In addition, Japanese Examined Patent Publication
A composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in Japanese Patent No. 327 is also preferable.

Further, in the case of a support having a surface of metal, especially aluminum, it is desirable to carry out an appropriate hydrophilic treatment. Examples of such a hydrophilic treatment include a mechanical method such as wire brush graining, brush graining in which a surface of an aluminum surface is roughened with a nylon brush while pouring a slurry of abrasive particles, ball graining, HF or AlCl ₃ , Graining the surface by chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or complex graining performed by combining these surface roughening methods, and then acidifying as necessary. It is possible to form a strong passivation film on the aluminum surface by etching treatment with alkali, and subsequently by anodizing with sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulphamic acid or mixed acid of these with direct current or alternating current power supply. preferable.

The aluminum surface is hydrophilized by such a passivation film itself, and if necessary, US Pat.
714,066 and U.S. Pat. No. 3,181,461, silicate treatment (sodium silicate, potassium silicate), U.S. Pat. No. 2,946,638, potassium fluorozirconate treatment, U.S. Pat. 3,201,24
Phosphomolybdate treatment described in No. 7,
Alkyl titanate treatment described in British Patent No. 1,108,559, polyacrylic acid treatment described in German Patent No. 1,091,433, described in German Patent Nos. 1,134,093 and British Patent No. 1,230,447 Polyvinylphosphonic acid treatment described in JP-B-44-6409, U.S. Patent No. 3,307,
Phytic acid treatment described in Japanese Patent No. 951 and a composite of a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-16893 and JP-A-58-18291. Those treated with a hydrophilizing treatment by undercoating a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651 are particularly preferable.
Other hydrophilic treatment methods include U.S. Pat. No. 3,658,662.
The silicate electrodeposition described in the specification can be mentioned.

Examples of the light source of actinic rays used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp and the like.
Radiation includes electron beams, X-rays, ion beams, far infrared rays, and the like. Also, g-line, i-line, Deep-UV light, high-density energy beam (laser beam) can be used. Examples of the laser beam include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, and KrF excimer laser. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser and a semiconductor laser are particularly preferable.

As the developer and replenisher for the negative image recording material of the present invention, conventionally known aqueous alkali solutions can be used. For example, sodium silicate, potassium, sodium triphosphate, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, Inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium are mentioned. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkaline agents such as ethyleneimine, ethylenediamine and pyridine are also used. These alkaline agents may be used alone or in combination of two or more.

Various surfactants and organic solvents may be added to the developing solution and the replenishing solution, if necessary, for the purpose of promoting or suppressing the developing property, dispersing the developing gas and enhancing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. If necessary, the developer and replenisher
It is also possible to add a reducing agent such as sodium salt or potassium salt of an inorganic acid such as hydroquinone, resorcin, sulfurous acid or bisulfite, and further an organic carboxylic acid, an antifoaming agent or a water softener. Among these developers, particularly preferable ones are, for example, JP-A-54-62004 and JP-B-57-7.
Those described in Japanese Patent No. 427, and JP-A-51
No. 77401, a developer composition comprising benzyl alcohol, an anionic surfactant, an alkali agent and water, and benzyl alcohol, an anionic surfactant described in JP-A-53-44202. A developer composition comprising an aqueous solution containing a water-soluble sulfite, an organic solvent having a solubility in water of 10% by weight or less at room temperature, an alkaline agent and water, which are described in JP-A-55-155355. The developer composition etc. which are contained are mentioned.

When the image recording material of the present invention is used as a printing plate, it is developed using the above-mentioned developing solution and replenishing solution, and then rinsed with water, a rinse solution containing a surfactant, gum arabic and a starch derivative. It is preferably post-treated with a desensitizing solution. Various combinations of these treatments can be used for the post-treatment. In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate, each processing liquid tank and a spraying device, which conveys an exposed printing plate horizontally while pumping it up with each pump. The processing liquid is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid for processing. In such automatic processing, it is possible to perform processing while supplementing each processing solution with a replenishing solution according to the processing amount, operating time, and the like. Further, a so-called disposable processing method of processing with a substantially unused processing liquid can be applied.

[0044]

The present invention will be described in detail below with reference to examples.
However, the present invention is not limited to these.(Synthesis example 1-1) (Synthesis a of Compound (X) a) 1- [α-methyl-α- (4-hydroxyphenyl) e
Cyl] -4- [α, α-bis (4-hydroxyphenyl)
Lu) ethyl] benzene (in the general formula (X), Y ¹~ Y
⁶Is a compound in which all are hydrogen atoms) 20 g of potassium hydroxide
It was dissolved in 100 ml of an aqueous solution of um (10%). This reaction
While stirring 60 ml of formalin (37%) in the liquid at room temperature
It dripped over 1 hour. Allow the reaction solution to continue for 6 hours at room temperature
After stirring, the mixture was poured into a sulfuric acid aqueous solution for crystallization. Got
After thoroughly washing the pasty precipitate formed with water, methanol 30
A white powder was obtained by recrystallization using ml. Income
20g quantity. The obtained compound was analyzed by 1- [α-
Methyl-α- (4-hydroxyphenyl) ethyl] -4
-[Α, α-bis (4-hydroxyphenyl) ethyl]
Benzene hexamethylol compound (smell of general formula (X)
Y¹~ Y⁶Is a compound in which all are methylol groups)
I found out that Reversed-phase HPLC (column: Shimapac CL
C-ODS (manufactured by Shimadzu Corporation), solvent: methanol / water = 60
/ 40 → 90/10) pure hexamethylol compound
The degree was 92%.

(Synthesis Example 1-2) (Synthesis b of Compound (X)) The hexamethylol compound of Synthesis Example 1-1 (a compound in which Y ^{1 to} Y ⁶ in the general formula (X) are all methylol groups)
20 g was dissolved in 1000 ml of methanol under heating, 1 ml of concentrated sulfuric acid was added, and the mixture was heated under reflux for 12 hours. After cooling the reaction solution, 2 g of potassium carbonate was added, further stirred and concentrated, 300 ml of ethyl acetate was added, washed with water and dried, and then the solvent was distilled off to obtain a white solid. Yield 22g. The obtained compound is NMR
Thus, a hexamethoxymethylated product of 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene (in the general formula (X), Y ¹ To Y ⁶ are all methoxymethyl groups). Reversed phase HP
The purity of hexamethoxymethylated product by LC (column: Shimapac CLC-ODS (manufactured by Shimadzu Corporation), solvent: methanol / water = 60/40 → 90/10) was 90%.

(Synthesis Example 1-3) (Synthesis c of Compound (X)) The hexamethylol compound of Synthesis Example 1-1 (a compound in which all of Y ^{1 to} Y ⁶ in the general formula (X) are methylol groups)
20 g was dissolved in 1000 ml of ethanol under heating, 1 ml of concentrated sulfuric acid was added, and the mixture was heated under reflux for 12 hours. After cooling the reaction solution, 2 g of potassium carbonate was added, the mixture was further stirred and concentrated, 300 ml of ethyl acetate was added, washed with water, dried and the solvent was distilled off to obtain a colorless oily substance. Yield 22g. Reversed phase HPLC (column:
Shimpac CLC-ODS (manufactured by Shimadzu Corporation), solvent: methanol / water = 60/40 → 90/10) hexaethoxymethylated compound (a compound of the general formula (X) in which Y ^{1 to} Y ⁶ are all ethoxymethyl groups) Was 70%.

(Synthesis Example 1-4) (Synthesis d of Compound (X)) The hexamethylol compound of Synthesis Example 1-1 (a compound in which Y ^{1 to} Y ⁶ in the general formula (X) are all methylol groups)
20 g was dissolved in 200 ml of 1-methoxy-2-propanol with heating, 1 ml of concentrated sulfuric acid was added, and the mixture was heated under reflux for 12 hours.
After cooling the reaction solution, 2 g of potassium carbonate was added, the mixture was further stirred and concentrated, 300 ml of ethyl acetate was added, washed with water, dried and the solvent was distilled off to obtain a colorless oily substance. Yield 23g. Reversed phase HPLC (column: Shimapac CLC-ODS (manufactured by Shimadzu Corp.), solvent: methanol / water = 60/40 → 90/1
The content of the hexaether compound according to 0) (a compound in which all of Y ^{1 to} Y ⁶ in the general formula (X) are 2-methoxy-1-methylethoxymethyl groups) was 55%.

(Synthesis Example 1-5) (Synthesis e of Compound (X)) A hexamethylol compound of Synthesis Example 1-1 (a compound in which all of Y ^{1 to} Y ⁶ in the general formula (X) are methylol groups)
20 g was dissolved in 100 ml of methylene chloride, 10 ml of acetyl chloride was added, and the mixture was stirred at 25 ° C for 12 hours. The reaction solution was washed with water and dried, and then the solvent was distilled off to obtain a colorless oily substance. Yield 2
1 g. The obtained compound was analyzed by 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4-
It was found to be a hexakisacetoxymethylated product of [α, α-bis (4-hydroxyphenyl) ethyl] benzene (a compound in which all Y ^{1 to} Y ⁶ in the general formula (X) are acetoxymethyl groups). Reversed phase HPLC
(Column: Shimapac CLC-ODS (Shimadzu), Solvent:
The purity of the hexakisacetoxymethylated product according to methanol / water = 60/40 → 90/10) was 85%.

(Synthesis Example 2-1) (Synthesis of Compound (XI) a) α, α ′, α ″ -tris (4-hydroxyphenyl)-
1,3,5-triisopropylbenzene (general formula (XI)
In which Y ^{1 to} Y ⁶ are all hydrogen atoms) 1.
7.3 g was dissolved in 60 g of sodium hydroxide aqueous solution (10%). After adding 15 g of methanol to this reaction liquid, 30 g of formalin (37%) was added dropwise. After completion of the dropping, the reaction solution was heated to 40 ° C. and further reacted for 12 hours, and then the reaction solution was crystallized in an aqueous acetic acid solution to obtain a white solid. The obtained white solid was thoroughly washed with water and then dried under reduced pressure at room temperature. Yield 20g. The resulting compound was analyzed by NMR for α, α ′, α ″ -tris (4-hydroxyphenyl)-
It was found to be a hexamethylol compound of 1,3,5-triisopropylbenzene (a compound in which all of Y ^{1 to} Y ⁶ in the general formula (XI) are methylol groups). Reversed phase HPLC (column: Shimapac CLC-ODS (manufactured by Shimadzu Corp.), solvent: methanol / water = 60/40 → 90/1
The purity of the hexamethylol compound according to 0) was 90%.

(Synthesis Example 2-2) (Synthesis b of Compound (XI)) The hexamethylol compound of Synthesis Example 2-1 (a compound in which Y ^{1 to} Y ⁶ in the general formula (XI) are all methylol groups)
20 g was dissolved in 1000 ml of methanol under heating, 1 ml of concentrated sulfuric acid was added, and the mixture was heated under reflux for 9 hours. After cooling the reaction solution, 2 g of potassium carbonate was added, the mixture was further stirred and concentrated, 300 ml of ethyl acetate was added, washed with water, dried and the solvent was distilled off to obtain a colorless oily substance. Yield 22g. Reversed-phase HPLC (column: Sh
impac CLC-ODS (Shimadzu), solvent: methanol /
The purity of the hexakis methoxymethylated product (a compound in which all of Y ^{1 to} Y ⁶ in the general formula (XI) are methoxymethyl groups) with water = 60/40 → 90/10 was 83%.

(Synthesis Example 3-1) (Synthesis a of Compound (XII)) α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene (in the general formula (XII), Y ¹ to Y
10 g of a compound in which all ⁸ are hydrogen atoms were dissolved in 25 ml of an aqueous sodium hydroxide solution (15%). After adding 15 ml of methanol to this reaction solution, formalin (37
%) 20 g was added dropwise. After the dropping was completed, the reaction solution was heated to 40 ° C., reacted for 12 hours, and then crystallized in an acetic acid aqueous solution. The solid obtained was thoroughly washed with water and then reslurried with 100 ml of ethyl acetate to obtain a white powder. Yield 11.4
g The resulting compound was analyzed by NMR for α, α, α ′, α ′
-Tetrakis (4-hydroxyphenyl) -1,4-dimethylbenzene octamethylol compound (general formula (XII)
In the above, it was found that Y ^{1 to} Y ⁸ are all methylol groups). Reversed-phase HPLC (column: Sh
impac CLC-ODS (Shimadzu), solvent: methanol /
The purity of the octamethylol compound by water = 60/40 → 90/10) was 95%.

(Synthesis Example 3-2) (Synthesis b of Compound (XII)) The octamethylol compound of Synthesis Example 3-1 (a compound in which all of Y ^{1 to} Y ⁸ in the general formula (XII) are methylol groups)
20 g was dissolved in 1000 ml of methanol under heating, 1 ml of concentrated sulfuric acid was added, and the mixture was heated under reflux for 10 hours. After cooling the reaction solution, 2 g of potassium carbonate was added, and the mixture was further stirred and concentrated, 300 ml of ethyl acetate was added, washed with water, dried and the solvent was distilled off to obtain a pale yellow oily substance. Yield 21g. Reverse phase HPLC (column: Shimapac CLC-ODS (manufactured by Shimadzu Corporation), solvent: methanol / water = 60/40 → 90/10) octakismethoxymethylated compound (Y ^{1 to} Y ⁸ in general formula (XVI))
Is a methoxymethyl group) purity is 87
%Met.

(Synthesis Example 3-3) (Synthesis c of Compound (XII)) The octamethylol compound of Synthesis Example 3-1 (a compound in which Y ^{1 to} Y ⁸ in the general formula (XII) are all methylol groups)
Dissolve 20 g in 800 ml of ethanol by heating and add concentrated sulfuric acid 1
ml was added and the mixture was heated under reflux for 12 hours. After cooling the reaction solution, 2 g of potassium carbonate was added, the mixture was further stirred and concentrated, 300 ml of ethyl acetate was added, washed with water, dried and the solvent was distilled off to obtain a colorless oily substance. Yield 23g. Reversed-phase HPLC (column: Sh
impac CLC-ODS (Shimadzu), solvent: methanol /
The purity of the octakisethoxymethylated product (compound in which all of Y ^{1 to} Y ⁸ in the general formula (XII) are ethoxymethyl groups) with water = 60/40 → 90/10 was 72%.

(Synthesis Example 3-4) (Synthesis d of Compound (XII)) The octamethylol compound of Synthesis Example 3-1 (a compound in which Y ^{1 to} Y ⁸ in the general formula (XII) are all methylol groups)
20 g was dissolved in 100 ml of methylene chloride, 10 ml of acetyl chloride was added, and the mixture was stirred at 25 ° C for 12 hours. The reaction solution was washed with water and dried, and then the solvent was distilled off to obtain a colorless oily substance. Yield 2
2 g. Reversed phase HPLC (column: Shimapac CLC-ODS (manufactured by Shimadzu Corporation), solvent: methanol / water = 60/40 → 90
/ 10), the purity of the octakisacetoxymethylated compound (a compound in which all Y ^{1 to} Y ⁸ in the general formula (XII) are acetoxymethyl groups) was 75%.

(Synthesis Example 4-1) (Synthesis a of Compound (XIII) a) 1,3,3,5-tetrakis (4-hydroxyphenyl) -pentane (in the general formula (XIII), Y ^{1 to} Y ⁸ are all 11 g of a compound that is a hydrogen atom was dissolved in 40 g of an aqueous sodium hydroxide solution (10%). After adding 10 g of methanol to this reaction solution, formalin (37%)
20 g was added dropwise. After the completion of the dropping, the reaction solution was heated to 40 ° C. and further reacted for 12 hours, and then crystallized in an acetic acid aqueous solution to obtain a white viscous solid. The obtained solid was washed well with water and then dried under reduced pressure at room temperature. Yield 13.6g. The obtained compound is an octamethylol compound of 1,3,3,5-tetrakis (4-hydroxyphenyl) -pentane by NMR (a compound in which Y ^{1 to} Y ⁸ in the general formula (XIII) are all methylol groups). I knew it was.
Reversed phase HPLC (column: Shimapac CLC-ODS (manufactured by Shimadzu Corp.), solvent: methanol / water = 60/40 → 90/1
The purity of the octamethylol compound according to 0) was 93%.

(Synthesis Example 4-2) (Synthesis b of Compound (XIII)) The octamethylol compound of Synthesis Example 4-1 (general formula (XIII))
20 g of a compound in which Y ^{1 to} Y ⁸ are all methylol groups) were dissolved by heating in 1000 ml of methanol, 1 ml of concentrated sulfuric acid was added, and the mixture was heated under reflux for 10 hours. After cooling the reaction mixture, 2 g of potassium carbonate was added, and the mixture was further stirred and concentrated,
After adding 300 ml of ethyl acetate, washing with water and drying, the solvent was distilled off to obtain a pale yellow oily substance. Yield 21g. Reversed phase HPLC
(Column: Shimapac CLC-ODS (Shimadzu), Solvent:
Octakis methoxymethylated compound (methanol / water = 60/40 → 90/10) (Y in general formula (XIII))
The purity of the compound in which ^{1 to} Y ⁸ are all methoxymethyl groups was 85%.

(Synthesis Example 5-1) (Synthesis a of Compound (XVI) a) α, α, α ′, α ′, α ″, α ″ -hexakis (4-hydroxyphenyl) -1,3,5-tri 15 g of ethylbenzene (a compound in which all of Y ^{1 to} Y ¹² in the general formula (XVI) are hydrogen atoms) was added with an aqueous sodium hydroxide solution (15
%) 35 ml and methanol 25 ml.
33 g of formalin (37%) was added dropwise to this reaction solution.
After completion of the dropping, the reaction solution was heated to 40 ° C., reacted for 20 hours, and then poured into an acetic acid aqueous solution. From the water layer,
The viscous oily substance was separated by decantation, washed well with water, and then dried under reduced pressure at room temperature to obtain a pale yellow powder. Yield: 16.6 g The obtained compound was analyzed by NMR for α, α, α ', α',
α ", α" -hexakis (4-hydroxyphenyl)-
It was found to be a dodecamethylol compound of 1,3,5-triethylbenzene (a compound in which all of Y ^{1 to} Y ¹² in the general formula (XVI) are methylol groups). Reversed phase HPL
The purity of the dodecamethylol compound by C (column: Shimapac CLC-ODS (manufactured by Shimadzu Corporation), solvent: methanol / water = 60/40 → 90/10) was 80%.

(Synthesis Example 5-2) (Synthesis b of Compound (XVI)) Dodecamethylol compound of Synthesis Example 5-1 (a compound in which Y ^{1 to} Y ¹² in the general formula (XVI) are all methylol groups)
20 g was dissolved in 1000 ml of methanol under heating, 1 ml of concentrated sulfuric acid was added, and the mixture was heated under reflux for 13 hours. After cooling the reaction solution, 2 g of potassium carbonate was added, and the mixture was further stirred and concentrated, 300 ml of ethyl acetate was added, washed with water, dried and the solvent was distilled off to obtain a pale yellow oily substance. Yield 21g. Reversed-phase HPLC (column: Shimapac CLC-ODS (manufactured by Shimadzu Corporation), solvent: methanol / water = 60/40 → 90/10) by dodecakis methoxymethylated compound (Y ^{1 to} Y ¹² in the general formula (XVI)).
Is a methoxymethyl group), the purity is 75
%Met.

[Preparation of Substrate] An aluminum plate (material 1050) having a thickness of 0.3 mm was solvent-cleaned and degreased, and then a nylon brush and 400 mesh pumice-water suspension were used to grain the surface. After that, it was washed well with water. This plate was immersed in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds for etching, washed with water, and further immersed in 20% nitric acid for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Then this plate is 7%
A sulfuric acid electrolytic solution was used to form a direct current oxide film of 3 g / m ² at a current density of 15 A / dm ² and then washed with water and dried. Next, the following undercoat liquid was applied to this aluminum plate and dried at 80 ° C. for 30 seconds. The coating amount after drying was 10 mg / m ² . (Undercoating liquid) β-alanine 0.1 g Phenylphosphonic acid 0.05 g Methanol 40 g Pure water 60 g

[Preparation of Carbon Black Dispersion] A composition having the following weight ratio was dispersed with glass beads for 10 minutes to obtain a carbon black dispersion. Carbon black 1 part by weight Copolymer of benzyl methacrylate and methacrylic acid 1.6 parts by weight (molar ratio 71:29, weight average molecular weight 70,000) Cyclohexane 1.6 parts by weight Methoxypropyl acetate 3.8 parts by weight

[Preparation of negative lithographic printing plate] (Examples 1 to 13 and Comparative Examples 1 to 4) The aluminum plate obtained above was coated with the following photosensitive solution and dried at 100 ° C for 2 minutes to obtain a negative. A type photosensitive lithographic printing plate was obtained. The weight after drying was 2.0 g / m ² .

Photosensitive Solution 2.4 g Phenol derivative (as described in Table 1) Phenol-formaldehyde novolac (as described in Table 1) (Weight average molecular weight 12000) 4- (pN, N-) Bis (ethoxycarbonylmethyl) 0.02g ^{* 1} aminophenyl) -2,6-bis (trichloromethyl) -S-triazine Megafac F-176 (Dainippon Ink and Chemicals Co., Ltd. 0.06g, fluorine-based interface) Activator) Methyl ethyl ketone 15 g 2-Methoxy-1-propanol 12 g * 1: Not added in Examples 1 and 2.

[0063]

[Table 1] ─────────────────────────────────── Amount of novolak phenol derivative used ───── ─────────────── (g) General formula Synthesis amount Usage (g) Number of prints Example 1 2.10 (X) Compound of Synthesis Example 1-1 0.21 30,000 sheets Example 2 2.00 (X) Compound of Synthesis Example 1-2 0.21 25,000 sheets Example 3 2.10 (X) Compound of Synthesis Example 1-3 0.20 30,000 sheets Example 4 2.05 (X) Compound of Synthesis Example 1-4 0.21 20,000 sheets Example 5 2.00 (X) Synthesis example 1-5 compound 0.22 350,000 sheets Example 6 2.07 (XI) Synthesis example 2-1 compound 0.21 30,000 sheets Example 7 2.07 (XI) Synthesis example 2-2 Compound 0.21 30,000 sheets Example 8 2.11 (XII) Synthesis Example 3-1 compound 0.21 30,000 sheets Example 9 2.11 (XII) Synthesis Example 3-2 compound 0.21 25,000 sheets Example 10 2.10 (XII) Compound of Synthesis Example 3-3 0.21 30,000 sheets Example 11 2.08 (XII) I) Compound of Synthesis Example 4-1 0.21 25,000 sheets Example 12 2.08 (XIII) Compound of Synthesis Example 4-2 0.21 250,000 sheets Example 13 2.05 (XVI) Compound of Synthesis Example 5-1 0.20 30,000 sheets ─────────────────────────────────── Comparative Example 1 2.10 − − Image formation without addition No Comparative Example 2 2.09 (X) Raw material of Synthesis Example 1 0.20 No image formed Comparative Example 3 2.12 (XXI) − 0.22 No image formed Comparative Example 4 2.10 (XXII) − 0.22 10,000 sheets ─────── ────────────────────────────

The compound used in Comparative Example 2 is a compound in which Y ^{1 to} Y ⁶ are all hydrogen atoms in the general formula (X), and the compounds (XXI) and (XXII) used in Comparative Examples 3 and 4
Is a compound having the following structure each having one or two benzene nuclei and is a compound described in JP-B-1-49932.

[0065]

[Chemical 12]

The negative photosensitive lithographic printing plate thus obtained was exposed with a YAG laser adjusted to a plate surface output of 700 mW, and then developed by Fuji Photo Film Co., Ltd., DP-4 (1: 8),
When processed through an automatic processor equipped with rinse solution FR-3 (1: 7), a negative image was obtained. The results of printing the planographic printing plate with a Heidel SOR-KZ machine are shown in Table 1. Example 1 using the phenol derivative of the present invention
In No. 13, good printed matter was obtained. On the other hand, no image was formed in the comparative example in which the phenol derivative of the present invention was not used, and the number of printed sheets was also low in the comparative example 4 in which the image was formed.

Comparative Example 5 A negative photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the carbon black dispersion was not used in the photosensitive liquid composition of Example 1.
When this photosensitive lithographic printing plate was exposed and developed in the same manner as in Example 1, all the photosensitive film was dissolved in the developing solution, and no image was obtained. (Examples 14 to 19 and Comparative Examples 6 to 7) The aluminum plate used in Examples 1 to 13 was coated with the following photosensitive solution, and 100
It was dried at ℃ for 2 minutes to obtain a negative photosensitive lithographic printing plate. The weight after drying was 2.0 g / m ² . Photosensitive liquid 2.2 g of the carbon black dispersion liquid Phenol compound of Synthesis Example 1-2 0.25 g Alkali-soluble resin 2.05 g Megafac F-176 (Dainippon Ink 0.06 g Chemical Industry Co., Ltd., fluorine-based) Surfactant) Methyl ethyl ketone 15 g 2-Methoxy-1-propanol 12 g

[0068]

[Chemical 13]

[0069]

[Chemical 14]

The negative-working photosensitive lithographic printing plate thus obtained was exposed to a YAG laser adjusted to a plate surface output of 700 mW and then developed with an aqueous solution containing sodium carbonate and sodium hydrogen carbonate. As a result, an acrylic resin having a phenol ring or an allyl group was obtained. In each of Examples 14 to 19 using the resin, a negative image was obtained. On the other hand, in Comparative Examples 6 to 7 in which the acrylic resin having no phenol ring or allyl group was used, the photosensitive film was completely dissolved in the developing solution and no image was obtained.

(Examples 20 to 22, Comparative Examples 8 to 9) The carbon black dispersion used in Example 1 was replaced with a photosensitive solution containing the dyes shown in Table 2 by the same procedure as in Example 1. After coating and drying, a negative photosensitive lithographic printing plate was obtained. Photosensitive solution Dye described in Table 2 0.2 g Phenol compound of Synthesis Example 1-2 (as described in Table 2) Phenol-formaldehyde novolac 2.0 g (weight average molecular weight 12000) 4- (p-N, N-bis) (Ethoxycarbonylmethyl) 0.02 g ^{* 2} Aminophenyl) -2,6-bis (trichloromethyl) -S-triazine Megafac F-176 (Dainippon Ink 0.06 g Chemical Industry Co., Ltd., fluorine-based surfactant Agent) Methyl ethyl ketone 15 g 2-methoxy-1-propanol 12 g * 2 Not added in Example 21.

[0072]

[Table 2] ───────────────────────────────── Dyeing amount of phenolic compound (g) Number of printed sheets Example 20 0.35 25,000 sheets Example 21 0.34 20 thousand sheets Example 22 0.35 25,000 sheets Comparative Example 8 No addition 0.34 No image formation Comparative Example 9 No addition No image formation

[0073]

[Chemical 15]

The negative-working photosensitive lithographic printing plate thus obtained was applied to a semiconductor laser (wavelength 825 nm, spot diameter: 1 / e ² = 11.9).
μ) was used to adjust the plate surface output to 110 mW at a linear velocity of 8 m / sec for exposure. Next, when the same developing treatment as in Example 1 was carried out, in Examples 20 to 22, fine lines having a line width of 10 μ could be formed. The lithographic printing plate thus obtained was printed on high-quality paper with a commercially available ink using a SOR-KZ type printer manufactured by Heidelberg. The results are also shown in Table 2. Examples 20-using the phenol derivatives of the invention in combination with dyes
In No. 22, good printed matter was obtained. On the other hand, no image was formed in Comparative Example 8 in which no dye was added and Comparative Example 9 in which the phenol derivative of the present invention was not used.

[0075]

INDUSTRIAL APPLICABILITY The negative image recording material of the present invention can be recorded without depending on the emission wavelength of the exposure light source, and in particular, can be recorded with light in the near infrared to infrared (heat ray) region. Further, the recording material of the present invention can be directly plate-made from digital data of a computer or the like by recording using a solid-state laser / semiconductor laser (thermal mode) having an emission region from near infrared to infrared. It is possible to obtain a lithographic printing plate by the heat mode writing type direct plate making which can directly use the processing device and the printing device.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-245049 (JP, A) JP-A-52-46902 (JP, A) US Pat. No. 3628953 (US, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) B41C 1/05 G03F 7/00 G03F 7/038 G03F 7/20

Claims (2)

(57) [Claims] 1. A substance which absorbs infrared light or near infrared light to generate heat, a water-insoluble and alkali-water-soluble resin, 4 to 8 benzene nuclei in the molecule, at least one phenolic hydroxyl group, and A negative image recording material comprising a phenol derivative having at least two groups represented by formula (I). —CH ₂ OR ¹ (I) (in the formula, R ¹ represents a hydrogen atom, an alkyl group or an acyl group) 2. The negative image recording material according to claim 1,
Exposure using a laser that emits infrared light or near infrared light
Negative image recording by developing with alkaline water developer
Method.