JP2002052855A - Laser direct drawing-type lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly sensitive direct drawing-type lithographic printing plate which can be made up based on digital data such as of a computer using a laser and uses an application solution, for the printing plate, whose manufacture is easy without the necessity of using a dispersion step during the manufacture of the solution. SOLUTION: The laser direct drawing-type lithographic printing plate contains a chemical compound represented by the formula (1) as an infrared absorber (in the formula (1), R1 and R2 are each a substituting group; R3 and R4 are each an unsaturated alkyl group with a total number of carbon atoms of 12 or less; and X- is an anion which is present, if necessary).

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 which can be used as a plate material for a lithographic printing plate, and more particularly to a solid-state laser or a semiconductor which emits infrared rays, particularly a wavelength of 760 to 1200 nm, from a digital signal from a computer or the like. The present invention relates to a so-called direct plate making lithographic printing plate which can be made directly using a laser.

[0002]

2. Description of the Related Art Direct plate making, in which a plate is made directly from digital data of a computer without using a film for plate making, is so-called simplicity that does not require skill, quickness of obtaining a plate in a short time, and quality from various systems. It has features such as rationality that can be selected according to cost, and has begun to widely enter the printing industry such as general offset printing and graphic printing. These lithographic printing plates can be classified according to the plate-making method, such as a method of irradiating a laser beam, a method of writing with a thermal head, a method of partially applying a voltage with a pin electrode, and forming an ink repellent layer and an ink-coated layer by inkjet. There are methods. Above all, the method using laser light is superior to other methods in terms of resolution and plate making speed, and there are many types. Further, the development of lasers in recent years has been remarkable, and in particular, wavelengths of 760 nm to 1
As for solid-state lasers and semiconductor lasers that emit infrared light of 200 nm, high-output and small-sized lasers are easily available. These lasers are very useful as a recording light source when making a plate directly from digital data from a computer or the like, and plate making machines using a semiconductor laser emitting mainly at around 830 nm as a recording light source are on the market.

[0003] The method using laser light includes a photon mode (a high-sensitivity PS plate using a photopolymer,
Electrophotography dragon flat plate using organic semiconductors or zinc oxide, silver salt flat plate, etc.) and thermal mode in which photo-thermal conversion is performed to cause a thermal reaction. And high sensitivity to green light, making it difficult to handle in a bright room. On the other hand, the biggest feature of the thermal mode is that an infrared laser is used for image formation of a plate material, and handling in a bright room becomes easy.

As a recording material recordable by such an infrared laser, a recording material composed of a resin such as a phenol resin, a resol resin, a novolak resin, and an acrylic resin and a photothermal conversion material is often proposed. However, among the photothermal conversion materials used in these recording materials, most of the practically useful ones have a photosensitive wavelength in the visible light range of 760 nm or less, and are generally used as infrared dyes having absorption in the region of 800 to 1200 nm. Many of them were unstable and were difficult to use. Although carbon black has no stability problem, it does not dissolve in a coating solvent, so a dispersion step is required when introducing it to a printing plate, which is disadvantageous in cost, such as complicating the production process. Also, it was not always easy to form a uniform coating. In order to provide a highly sensitive lithographic printing plate that can be directly made from a digital signal from a computer or the like using a semiconductor laser that emits light at around 830 nm, it must have a large absorption near the recording light source and a solvent solubility. It is necessary to use an infrared-absorbing dye having a good quality as a light-to-heat conversion material, but an infrared-absorbing dye that sufficiently satisfies the requirements has not been provided.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to make plate making directly from digital data of a computer or the like using a laser, mainly a semiconductor laser emitting around 830 nm, and to carry out a dispersion step in the production of a printing plate coating solution. It is an object of the present invention to provide a laser direct-writing type printing plate which can be easily manufactured without requiring a laser beam and has high sensitivity.

[0006]

Means for Solving the Problems The present invention provides: [1] an infrared absorbent for a laser direct-drawing lithographic printing plate represented by the following general formula (1):

[0007]

Embedded image

(In the formula (1), R1 and R2 each independently represent a substituted or unsubstituted hydrocarbon group.
R4 each independently represents an unsubstituted alkyl group having up to 12 carbon atoms. X- represents an anion present as required. [2] In the formula (1), R1 and R2 are each independently
An infrared absorbent for a laser direct-drawing lithographic printing plate according to [1], which is a substituted or unsubstituted alkyl group, aryl group, or alkenyl group having up to 12 carbon atoms; [3] R1 in the formula (1); R2 is each independently an alkyl group having up to 12 carbon atoms, a cycloalkyl group, an alkoxy-substituted alkyl group, an alkoxyalkoxy-substituted alkyl group, a sulfonyl-substituted alkyl group, a cyano-substituted alkyl group, an aryl-substituted alkyl group, an acyl-substituted alkyl group, an alkenyl An oxy-substituted alkyl or alkenyl group, R3, R4
Each independently represents a methyl group or an ethyl group [2]
Infrared absorbent for laser direct-drawing lithographic printing plate described in
[4] A negative laser direct drawing type flat plate having a heat-sensitive layer containing the compounds described in (a), (b), (c) and [1] to [3] below on a support. Printing plate, (a) an alkali-soluble binder (b) a compound that generates an acid by heat (c) a compound that polymerizes or crosslinks (a) with an acid to make it insoluble in an aqueous alkali solution (hereinafter referred to as an acid crosslinkable compound) [5] (A) a positive laser direct-drawing lithographic printing plate comprising a support having thereon a photosensitive layer containing the compound described in (a), (d) and [1] to [3]; Binder (d) When it is thermally decomposable and does not decompose (a)
[6] A laser direct-drawing lithographic printing plate having a photosensitive layer containing the compound according to [1] to [3] on a support, wherein the hydrophilic layer is a silicone rubber layer or the like. Direct-printing lithographic printing plate, characterized by having on a photosensitive layer, [7]
A laser direct-drawing lithographic printing plate having a photosensitive layer containing the compound according to any one of [1] to [3] on a support, which is a non-processing type which does not require a development process. It relates to a laser direct drawing type lithographic printing plate.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the infrared absorbent used in the present invention is a compound represented by the following general formula (1), and this compound will be described.

[0010]

Embedded image

(In the formula (1), R1 and R2 each independently represent a substituted or unsubstituted hydrocarbon group.
R4 each independently represents an unsubstituted alkyl group having up to 12 carbon atoms. X- represents an anion present as required. In the general formula (1), R1 and R2 each independently represent a substituted or unsubstituted hydrocarbon group, and can be selected from a wide range. Specific examples thereof include a methyl group, an ethyl group, and an iso-propyl group. Linear or branched such as n-propyl, n-butyl, iso-butyl, t-butyl, n-amyl, t-amyl, n-hexyl, n-octyl; Alkyl group; cycloalkyl group such as cyclohexyl group, cyclopentyl group and cyclooctyl group; methoxy group, ethoxy group, propoxy group,
Alkoxy group such as butoxy group; alkoxy-substituted alkyl group such as ethoxymethyl group, methoxyethyl group, propoxymethyl group, butoxyethyl group, methoxymethoxyethyl group, ethoxyethoxyethyl group; 2-hydroxyethyl group, 3-hydroxy Hydroxy-substituted alkyl groups such as propyl group and 4-hydroxybutyl group; carboxy-substituted alkyl groups such as carboxymethyl group, 2-carboxyethyl group and 4-carboxybutyl group; 3-sulfopropyl group and 4-sulfobutyl group Such as sulfo-substituted alkyl group; cyano-substituted alkyl group such as 3-cyanopropyl group and 2-cyanoethyl group; acyl group such as formyl group, acetyl group and cinnamoyl group; 3-formylpropyl group and 4-acetylbutyl group Acyl-substituted alkyl group such as Alkenyloxy-substituted alkyl groups such as methyl group and vinyloxymethyl group; alkenyl groups such as allyl group, vinyl group, pentenyl group and octenyl group; phenyl group, xylyl group, ethylphenyl group, methoxyphenyl group and nitrophenyl group Aryl groups such as benzyl, chlorophenyl, dimethylaminophenyl, and naphthyl; aryl-substituted alkyl groups such as benzyl, p-chlorobenzyl, 2-phenylethyl, and 3-phenylpropyl; propargyl and hexynyl And the like. Other examples include a substituted or unsubstituted heterocyclic ring. Specifically, a thiophene ring, a pyrrolidine ring, a piperidine ring,
Examples include a morpholine ring, a tetrahydropyridine ring, a cyclohexylamine ring and the like. In the general formula (1), R
3, R4 each independently represents an unsubstituted alkyl group having up to 12 carbon atoms, and preferred are a methyl group, an ethyl group, a propyl group and the like.

X-, which is an anion, is not present when R1 and R2 are each independently dissociated like a sulfo-substituted alkyl group and can take a negative charge,
Necessary for other non-charged substituents,
A wide selection of monovalent organic or inorganic ions can be selected. Specific examples include fluoride ions,
Chloride, bromide, iodine, perchlorate, nitrate, benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, propylsulfate, tetrafluoro Borate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propion acetate ion, benzoate ion,
Oxalate ion, succinate ion, malonate ion, oleate ion, stearate ion, citrate ion, dihydrogen phosphate ion, pentachlorostannate ion, chlorosulfonate ion, Fluorosulfonate ion, trifluoromethanesulfonate ion, hexafluoroarsenate ion, hexafluoroantimonate ion, molybdate ion, tungstate ion, titanate ion, zirconate ion and the like. Preferred are bromide ion, iodine ion, perchlorate ion, benzenesulfonate ion, p-toluenesulfonate ion, methyl sulfate ion, ethyl sulfate ion, tetrafluoroborate ion, and tetrafluoroborate ion. Phenyl borate ion, hexafluorophosphate ON, benzenesulfinate ion, propion acetate ion, benzoate ion, chlorosulfonate ion, hexafluoroantimonate ion and the like. Particularly preferred are perchlorate ion, p-toluene Sulfonate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluoroantimonate ion and the like can be mentioned.

Preferred examples of R1 and R2 in the general formula (1) of the present invention are each independently a substituted or unsubstituted alkyl group, aryl group or alkenyl group having up to 12 carbon atoms. Further preferred are each independently an alkyl group having up to 12 carbon atoms, a cycloalkyl group, an alkoxy-substituted alkyl group, an alkoxyalkoxy-substituted alkyl group, a sulfonyl-substituted alkyl group, a cyano-substituted alkyl group, an aryl-substituted alkyl group, an acyl-substituted group. It is an alkyl group, an alkenyloxy-substituted alkyl group or an alkenyl group, and R3 and R4 are each independently a methyl group or an ethyl group. Note that in the general formula (1), R
Specific examples of preferable examples of 1, R2 include a methyl group,
Ethyl group, iso-propyl group, n-propyl group, n-
Linear or branched alkyl groups such as butyl group, iso-butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group and n-octyl group; cyclohexyl group, cyclopentyl group A cycloalkyl group such as cyclooctyl group; an alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group; ethoxymethyl group, methoxyethyl group, propoxymethyl group, butoxyethyl group, methoxymethoxyethyl group, ethoxy group. Alkoxy-substituted alkyl groups such as ethoxyethyl group; hydroxy-substituted alkyl groups such as 2-hydroxyethyl group, 3-hydroxypropyl group and 4-hydroxybutyl group; carboxymethyl group, 2-carboxyethyl group, 4-carboxybutyl A carboxy-substituted alkyl group such as a group;
Sulfo-substituted alkyl groups such as sulfopropyl group and 4-sulfobutyl group; cyano-substituted alkyl groups such as 3-cyanopropyl group and 2-cyanoethyl group; acyl groups such as formyl group, acetyl group and cinnamoyl group; Acyl-substituted alkyl groups such as formylpropyl group and 4-acetylbutyl group; alkenyloxy-substituted alkyl groups such as allyloxymethyl group and vinyloxymethyl group; alkenyl groups such as allyl group, vinyl group, pentenyl group and octenyl group Groups; aryl groups such as phenyl, xylyl, ethylphenyl, methoxyphenyl, nitrophenyl, chlorophenyl, dimethylaminophenyl, and naphthyl; benzyl, p-chlorobenzyl,
Aryl-substituted alkyl groups such as -phenylethyl group and 3-phenylpropyl group; alkynyl groups such as propargyl group and hexynyl group. Other examples include a substituted or unsubstituted heterocyclic ring. Specific examples include a thiophene ring, a pyrrolidine ring, a piperidine ring, a morpholine ring, a tetrahydropyridine ring, and a cyclohexylamine ring. And the like. Preferred examples of the anion X- include p-toluenesulfonic acid ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion and the like.

In the general formula (1), R1, R2, R3,
Preferred combinations of R4 and X- include R1,
R2 is a methyl group or a methoxyethyl group; R3 and R4 are a methyl group or an ethyl group; and X- includes p-toluenesulfonate ion, hexafluoroantimonate ion, tetrafluoroborate ion and the like.

Tables 1 and 2 show specific examples of the infrared absorbing agent and the compound represented by the general formula (1) used in the present invention. However, the compounds used in the present invention are not limited to these. Ph represents a phenyl group.

[0016]

[Table 1]

(Continuation of Table 1)

[Table 2]

Further, in the laser direct-drawing type lithographic printing plate of the present invention, the compound represented by the general formula (1) may be used alone as an infrared absorber, or an organic dye having a different absorption wavelength may be used in combination. May be used. Such organic dyes include:
For example, polymethine dyes, cyanine dyes, azurenium dyes, squarylium dyes, croconium dyes, azo dyes, bisazostilbene dyes, metal complex azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, metal thiolates Dyes and perylene dyes.

The infrared absorbing agent for a laser direct drawing type lithographic printing plate of the present invention can obtain a particularly useful printing plate in the following system. (a) an alkali-soluble binder, (b) an acid generator, (c)
Negative laser direct-drawing lithographic printing plate containing an acid-crosslinkable compound in the photosensitive layer. A positive laser direct-drawing lithographic printing plate comprising (a) an alkali-soluble binder, and (d) a substance which is thermally decomposable and substantially reduces the solubility of the alkali-soluble binder when not decomposed. Laser direct drawing type waterless lithographic printing plate with a silicone rubber layer on the photosensitive layer. A so-called non-processing type printing plate that can be attached to a printing machine without laser processing and then printed as it is. A positive or negative type lithographic printing plate which does not necessarily contain a thermally decomposable substance, but whose exposed part is solubilized or insolubilized by heating with a laser.

Next, the materials used in the above-mentioned examples will be described in detail.

Examples of (a) used in the above examples include novolak resins, polyhydrostyrenes, acrylic resins and the like. The novolak resin used in the present invention is a resin obtained by condensing phenols and aldehydes under acidic conditions. Preferred novolak resins include, for example, a novolak resin obtained from phenol and formaldehyde, a novolak resin obtained from m-cresol and formaldehyde, a novolak resin obtained from p-cresol and formaldehyde, a novolak resin obtained from o-cresol and formaldehyde, m
Novolak resin obtained from mixed cresol and formaldehyde, phenol / cresol (o-, p-
-, M-, m- / p-, o- / pm- / o-) and a novolak resin obtained from formaldehyde. These novolak resins preferably have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000.

Examples of the alkali-soluble binder other than the novolak resin used in the examples include polyhydrostyrenes, hydroxystyrene-N-substituted maleimide copolymers, acrylic polymers having an alkali-soluble group, and those having an alkali-soluble group. Urethane type polymers and the like can be mentioned. Here, examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphone group, and an imide group. When a hydroxystyrene-based polymer such as poly-p-hydrostyrene or p-hydroxystyrene-N-substituted maleimide copolymer is used, the weight average molecular weight is from 2,000 to 500,000.
0, and more preferably 4,000 to 300,000.

Examples of the acrylic polymer having an alkali-soluble group include methacrylic acid-benzyl methacrylate copolymer, poly (hydroxyphenyl methacrylamide), poly (hydroxyphenylcarbonyloxyethyl acrylate), and poly (2,4-dihydroxyphenylcarbonyl). Oxyethyl acrylate). These acrylic polymers have a weight average molecular weight of 2,000 to 500,000, preferably 4,000.
~ 300,000 are preferred.

Examples of urethane polymers having an alkali-soluble group include resins obtained by reacting diphenylmethane isocyanate with hexamethylene diisocyanate, tetraethylene glycol, and 2,2-bis (hydroxymethyl) propionic acid. Among these alkali-soluble polymers, a hydroxystyrene-based polymer and an acrylic copolymer having an alkali-soluble group are preferable from the viewpoint of developability.

In the example of (a), these (a) are 10 to 90% by weight, preferably 20 to 90% by weight in the total solid content of the lithographic printing plate material.
To 85% by weight, more preferably 30 to 80% by weight. If the amount of the alkali-soluble polymer compound is less than 10% by weight, the durability of the recording layer is deteriorated, and if it exceeds 90% by weight, it is not preferable in terms of both sensitivity and durability. Further, these (a) may be used alone or in combination of two or more. (B) used in the example is a substance that generates an acid by heat or light, and is generally a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, Examples of known light-generating substances used for photochromic agents, micro resists, and the like, which generate an acid by light, and mixtures thereof, and the like can be conveniently selected and used.

The addition amount of (b) as described above is used in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 20% by weight, based on the total solid content of the lithographic printing plate material. It is used in the range of 0.1 to 5% by weight. (C) used in the example of refers to a compound that crosslinks (a) in the presence of an acid, for example, an aromatic compound poly-substituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group And heterocyclic compounds. Among them, preferred examples include compounds obtained by condensing phenols and aldehydes under basic conditions. Of the above compounds, preferred are, for example, compounds obtained by condensing phenol and formaldehyde under basic conditions as described above, compounds obtained from m-cresol and formaldehyde, compounds obtained from bisphenol A from formaldehyde, And compounds obtained from 4,4'-bisphenol and formaldehyde. These (c) have a weight average molecular weight of 500 to 100,000.
And a number average molecular weight of 200 to 50,000. These (c) may be used alone or in combination of two or more. The acid-crosslinkable compound used in the present invention is used in an amount of 5 to 80% by weight, preferably 10 to 75% by weight, more preferably 20 to 70% by weight, based on the total solid content of the lithographic printing plate material. If the amount of the acid-crosslinkable compound is less than 5% by weight, the durability of the photosensitive layer of the resulting lithographic printing plate will be deteriorated. If it exceeds 80% by weight, storage stability will be unfavorable.

The materials used in the example of (a)
And (d). As (a), the compounds described in the above examples can be used as they are.

As (d) in the example, various onium salts, quinonediazide compounds, etc. are excellent in lowering the solubility of (a) and are preferably used.

Examples of the onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like. Of these, diazonium salts are particularly preferred. Suitable quinonediazide compounds include o-
Quinone diad compounds can be mentioned. The o-quinone diad compound used in the present invention is a compound having at least one o-quinone diad group, which increases the alkali solubility by thermal decomposition, and can be a compound having various structures. The o-quinonediazide loses the ability to control the dissolution of the alkali-soluble binder due to thermal decomposition,
Quinonediazide itself changes the solubility of the plate material by becoming an alkali-soluble substance. As the o-quinonediazide compound used in the present invention, a sulfonate or a sulfonamide of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds is preferable. Also, U.S. Pat.
Nos. 46,120 and 3,188,210 disclose benzoquinone- (1,2) -diazidosulfonic acid chloride or naphthoquinone- (1,1).
2) -Diazide-5-sulfonic acid chloride and phenol-formaldehyde resin are also used separately. Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with a phenol-formaldehyde resin or a cresol-formaldehyde resin are also preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patent-related documents. For example, JP-A-47-5303, JP-B-41-11222, U.S. Pat. No. 2,797,2.
No. 13 Public Relations, No. 3,544,323, British Patent No. 1,
Publications such as 227, 602, 1,251, 345, and German Patent No. 854,890 can be cited.

The amount of the above-mentioned o-quinonediazide compound to be added is 1 to 50% by weight, more preferably 10 to 30% by weight, based on the total solid content of the lithographic printing plate material. These compounds can be used alone or as a mixture of several kinds. When the addition amount of the o-quinonediazide compound is 1% by weight or less, the image recording property is deteriorated and 5% by weight.
Exceeding the range causes deterioration of the durability of the image area.

The counter ions of the above onium salts include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5- Examples thereof include dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, dodecylbenzenesulfonic acid, and paratoluenesulfonic acid. . Among these, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 2,2
Alkyl aromatic sulfonic acids such as 5-dimethylbenzenesulfonic acid are preferred. The addition amount of the above compounds other than the o-quinonediazide compound is 1% of the solid content of all the lithographic printing plate materials.
-50% by weight, more preferably 10-30% by weight.

Regarding the example of JP-A-6-19906,
No. 4 public information, US-5339737 public information, JP-A-7-1
No. 64773, JP-A-11-59005, JP-A-11-157327, JP-A-11-1573
No. 26, JP-A-11-129938, 11-
In a negative printing plate similar to that disclosed in Japanese Patent Publication No. 348445, there is a so-called negative laser direct-drawing waterless lithographic printing plate having a silicone rubber layer provided on a light-sensitive material and requiring no immersion water.

With respect to the example of JP-A-10-2826,
No. 72 public information, Japanese Patent Application Laid-Open No. 10-230882, Japanese Patent Application Laid-Open No. 10-282624, Japanese Patent Application Laid-open No. 10-282644
JP-A-10-282646 discloses a system using a polymer compound having a sulfonic acid-generating functional group, which is described in WO-9635143, US-5.
A system using a carboxylic acid polymer protected with an acid-decomposable group, which is disclosed in JP-A-506090 and EP-652483, is exemplified.

With respect to the example of JP-B-46-2791,
A recording material described in PR No. 9 which contains a polymer compound or composition which is insoluble or slightly soluble before heating and which can be more soluble in a solvent under the influence of heat can be used. .

In the lithographic printing plates described in Examples 1 to 3, various compounds other than the above may be added as necessary. For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, Victoria Blue (C.I. 42595), Crystal Violet (C.I. 42555), Methyl Bitelet (C.I.
I. 42535), Rhodamine B (C.I.
OB), malachite green (CI.42000),
Known dyes such as methylene blue (C.I. 52015) can be used. It is preferable to add these dyes after image formation in order to facilitate distinction between image areas and non-image areas. In addition, the amount of addition in the solid content of all lithographic printing plate materials,
Usually, the ratio is 0.01 to 10% by weight.

Various compounds can be added to the lithographic printing plates described in Examples 1 to 3 in order to improve stability under development conditions. Specifically, Japanese Patent Application Laid-Open No. Sho 62
-251740, JP-A-3-208514, JP-A-59-121044, JP-A-4-13149
Non-ionic, amphoteric surfactants and the like described in the bulletin can be added. Specific examples of these nonionic surfactants include sorbitan tristearate, sorbitan monopalmitate, stearic acid monoglyceride, etc. Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl Polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and the like can be mentioned. The amount of the surfactant to be added is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total solid content of the lithographic printing plate material.

Next, a method of preparing the lithographic printing plate described in the examples 1 to 3 will be described. That is, it can be produced by applying or laminating a composition for a photosensitive layer obtained by dissolving the above-mentioned components in a suitable solvent on a suitable support to form a photosensitive layer. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylacetamide, N, N-
Dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane,
Examples include, but are not limited to, γ-butyl lactone, toluene, water, and the like. These solvents are used alone or as a mixture. The concentration of the lithographic printing plate material (including additives) in the solvent is preferably 1
５０50% by weight. The coating amount (solid content) on the support obtained after coating and drying is preferably 0.5 to 5.0.
g / m ² . Various methods can be used as the method of coating, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating,
Examples include air knife coating, blade coating, roll coating, and the like.

In order to improve the coatability of the lithographic printing plates described in Examples 1 to 3, a surfactant is used, for example, a fluorine-based surfactant described in JP-A-62-170950. May be added. Further, a plasticizer or the like may be added as needed in order to improve various properties such as flexibility of the coating film.

Next, the support on which the materials used in the above-described examples are laminated or coated will be described. As the support used, various dimensionally stable plate-like materials are used. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene), metal plate (aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose propionate, polyethylene terephthalate, polyethylene, polypropylene, Polystyrene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited.

Among the above-mentioned supports, a polyester film or an aluminum plate is preferable. Among them, an aluminum plate having good dimensional stability and relatively low cost is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include:
Silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. The thickness of the aluminum plate used in the present invention is about 0.1 mm ~
About 0.6 mm, preferably 0.15 mm to 0.4 m
m, particularly preferably 0.2 mm to 0.8 mm.

Next, the pretreatment of aluminum used as a support will be described. The aluminum plate used in the present invention is roughened as necessary. At that time, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution for removing the rolling oil on the surface is performed. The surface roughening treatment of the aluminum plate
The method is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface.
Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in Japanese Patent Application Laid-Open No. 54-63902, a method in which both are combined can be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to an anodic oxidation treatment, if desired, in order to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes for forming a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The conditions of the anodizing treatment vary depending on the electrolyte used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm2, a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability becomes insufficient, the non-image portion of the lithographic printing plate is easily damaged, and the ink adheres to the scratched portion at the time of printing. "Scratch dirt" is likely to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. The hydrophilic treatment used in the present invention includes, for example, US Pat.
066 public information, the same 3,181,461 public information, the third
There is an alkali metal silicate (for example, an aqueous solution of sodium silicate) as disclosed in 280,734 and 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, Japanese Patent Publication No. 36-220
Potassium fluorozirconate disclosed in US Pat. No. 63,631 and US Pat. Nos. 3,276,868;
A method of treating with polyvinyl phosphonic acid as disclosed in 158,461 and 4,689,272 is used.

In addition, the lithographic printing plate according to the present invention includes:
If necessary, an undercoat layer can be provided on the support.
As the undercoat layer component, various organic compounds are used, for example, carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and phenylphosphonic acid optionally having a substituent Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphinic acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloric acid of triethanolamine Hydroxy such as salt -Alanine, and hydrochlorides of amines having a group may be used in combination of two or more. The coating amount of the organic undercoat layer is suitably from ² to 200 mg / m ² .

Also, when producing a waterless lithographic printing plate or the like.
In particular, in order to prevent heat diffusion to the substrate, between the substrate and the photosensitive layer
In addition to the organic undercoat layer as a heat insulating layer, the base and photosensitive layer
Good adhesion, stable over time, during development and printing
Resins with high solvent resistance to solvents used for
Xy resin, polyurethane resin, phenol resin, acrylic
Resin, polyester resin, polyamide resin, urea tree
Those containing fat, casein, gelatin and the like are used. This
These resins are used alone or as a mixture of two or more.
Can be used to cure similar compositions
May be. The coating amount of this heat insulating layer is 0.5 to 50 g / m
^Two Is suitable, and preferably 1 to 10 g / m ^TwoIt is.

Next, image exposure of the prepared lithographic printing plate will be described. This lithographic printing plate has a wavelength of 760 nm to 12
Image exposure is performed using a solid-state laser and a semiconductor laser that emit 00-nm infrared rays. In particular, image exposure is performed with good sensitivity by a semiconductor laser emitting around 830 nm.

Subsequently, the development processing of the above and the examples will be described. First, after performing a heat treatment as needed, it is developed with an alkaline aqueous solution. As the developer and replenisher for the lithographic printing plate material according to the invention, known alkaline aqueous solutions can be used. For example, sodium silicate, potassium silicate, trisodium phosphate,
Potassium phosphate, tribasic ammonium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, borane And inorganic alkali salts such as sodium silicate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine,
Organic alkaline agents such as diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used. Can be These alkaline agents can be used alone or
Used in combination of more than one species.

Among these alkali agents, particularly preferred developers are aqueous solutions of silicates such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and concentration of silicon oxide SiO2 and alkali metal oxide M2 O, which are silicate components. For example, Japanese Patent Application Laid-Open No. 54-62004, 57-74
Alkali metal silicates as described in No. 27 public information are effectively used.

Further, when developing using an automatic developing machine, an aqueous solution having a higher alkali strength than the developing solution (replenisher)
It has been known that a large amount of lithographic printing plate material can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. This replenishment system is also preferably applied in the present invention. Various surfactants and organic solvents can be added to the developing solution and the replenishing solution as required for the purpose of accelerating or suppressing the developing property, dispersing the developing residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, if necessary, the developer and replenisher may be hydroquinone, resorcin, sulfurous acid,
A reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as bisulfite, an organic carboxylic acid, an antifoaming agent, and a water softener can also be added. The printing plate developed using the above developer and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. When the lithographic printing plate material according to the present invention is used as a printing plate material, these processes can be used in various combinations as a post-treatment.

The lithographic printing plate developed as described above can be subjected to a printing step after applying a desensitizing gum as required, but when a lithographic printing plate having a higher printing durability is desired, Is subjected to a burning process. When the lithographic printing plate is subjected to the burning process, the burning process surface is described in JP-B-61-2518, public information, 55-28062.
No., JP-A No. 62-31859, No. 61-15
It is preferable to carry out treatment with a surface-regulating liquid as described in each publication of No. 9655. As the method, a method of applying the printing solution on a lithographic printing plate with a sponge or absorbent cotton impregnated with the surface conditioning solution, or immersing the printing plate in a vat filled with the surface conditioning solution, Application by an automatic coater is applied. Also, after applying, squeegee, or
With a squeegee roller, to make the coating amount uniform,
Gives more favorable results. In general, it is appropriate that the application amount of the surface conditioning liquid is 0.03 to 0.8 g / m ² (dry weight).

The planographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then heated to a high temperature by a burning processor or the like. The heating temperature and time in this case depend on the type of the component forming the image, but may be 180 to 300 ° C.
Is preferably in the range of 1 to 20 minutes. The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming as needed, but a surface conditioning liquid containing a water-soluble polymer compound or the like is used. In this case, a so-called desensitization treatment such as gumming can be omitted.

Next, development of the waterless planographic printing plate described above will be described. Waterless lithographic printing plate, after exposure,
In particular, when an acid precursor is added, heating is performed to promote an insolubilization reaction by an acid generated from the acid precursor. This heating step is preferably performed at a temperature in the range of 80 to 150 ° C. for 5 seconds to 20 minutes.

The lithographic printing plate without water, which has been exposed and optionally subjected to a heating step, is a developer capable of dissolving or swelling a part or all of the photosensitive layer in the image area, or a developer capable of swelling the silicone rubber layer. It is developed or developed by friction treatment in the presence or absence of water, an organic solvent, or a developer. In this case, there are cases where the photosensitive layer in the image area and the silicone rubber layer thereon are removed, and cases where only the silicone rubber layer in the image area is removed, which can be controlled by the strength of the developer. .

As the developer used for the waterless lithographic printing plate, known ones can be used. For example, aliphatic hydrocarbons (hexane, heptane, gasoline, kerosene, etc.),
Preferred are aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (trichlene, etc.) to which the following polar solvents are added, and polar solvents themselves.・ Alcohols (methanol, ethanol, propanol, benzyl alcohol, ethylene glycol monophenyl ether, 2-methoxyethanol, 2-ethoxyethanol, carbitol monomethyl ether, carbitol monoethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, propylene glycol,
Polypropylene glycol, triethylene glycol,
Tetraethylene glycol), ketones (acetone, methyl ethyl ketone), esters (ethyl acetate, methyl lactate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, carbitol acetate, dimethyl phthalate, diethyl phthalate), others (triethyl phosphate) , Tricresyl phosphate)

Further, water is added to the organic solvent-based developer, or the solvent is solubilized in water with a surfactant, and an alkali agent such as sodium silicate, potassium silicate, sodium hydroxide is further added thereon. , Potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate,
An inorganic alkali agent such as ammonia water or an organic alkali agent such as tetraalkylammonium hydride, monoethanolamine, diethanolamine, triethanolamine and the like can be added.

In some cases, tap water or alkaline water can be used simply as a developer, and a surfactant or an organic solvent as described above can be added as necessary. Further, it is also possible to add a dye such as crystal violet or Astrazone Red to the developing solution and simultaneously perform the dyeing. The development can be performed by a known method, such as rubbing the plate surface with a developing pad containing the above-described developer, or rubbing with a developing brush after pouring the developer onto the plate surface. The developer can be developed at any temperature, but is preferably from 10 to 50 ° C.

In the case of the so-called non-processing type printing plate shown in the example, printing may be carried out by mounting the plate on a printing machine immediately after laser drawing, but it is preferable to perform heat treatment after laser irradiation. The heat treatment is preferably performed at a temperature of 80 to 150 ° C. for 10 seconds to 5 minutes. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

Next, the method of inspecting the lithographic printing plate shown in the following examples will be described. Plate inspection refers to the operation of confirming image formation after laser irradiation and image exposure. The lithographic printing plate that has been subjected to the image exposure and development steps can be detected by dyeing the exposed image portion with a dye solution in order to confirm image forming properties. When the developing solution does not contain a dye for dyeing the exposed image portion, it is dyed with the dyeing solution after development. By impregnating the dyeing solution into a soft pad and rubbing the image area lightly, only the image area is stained, whereby it can be confirmed that the development is sufficiently performed up to the highlight area. As the dyeing solution, one or more selected from water-soluble disperse dyes, acid dyes and basic dyes are dissolved in water, alcohols, ketones, ethers or the like alone or in a mixture of two or more. Alternatively, those dispersed are used. It is also effective to add carboxylic acids, amines, surfactants, dyeing auxiliaries, defoamers and the like in order to improve the dyeability.

The printing plate dyed with the dyeing solution is preferably washed with water and then dried, whereby the stickiness of the printing plate surface can be suppressed and the handling of the printing plate can be improved. When printing plates thus processed are stacked and stored, it is preferable to insert and insert a slip sheet to protect the plate surface.

The above-described development and plate inspection (dyeing), or subsequent washing and drying, are preferably performed by an automatic processor. A preferable example of such an automatic processor is described in JP-A-2-22661.

Next, a method for synthesizing the compound represented by the general formula (1) used in the present invention will be described. According to the method described in Japanese Examined Patent Publication No. 5-37119, this compound can be synthesized into a symmetric compound as shown in Table 1 No. 1 by a synthesis route shown in the following formula (A).

[0061]

Embedded image

In the above synthetic route, RA is the above R1
And R2 and RB represent R3 and R4, and X has the same meaning as described above.

More specifically, in a solvent such as methanol, ethanol, isopropyl alcohol, glycol, dimethylformamide or acetic acid or acetic anhydride, the raw material [], the raw material [] and the raw material [] are charged, and the reaction temperature is 50 ° C. The reaction is carried out at 140 ° C. for 1 hour to 12 hours to obtain the desired compound. In this reaction, a base catalyst such as piperazine, piperidine or sodium acetate may be optionally added as a catalyst.

[0064]

EXAMPLES The method of synthesizing the compounds used in the present invention will be described more specifically with reference to the following synthetic examples, but the synthetic method is not limited to these synthetic examples. In addition, in a synthetic example, a part represents a weight part unless there is particular limitation.

Synthesis Example 1 2 parts of 5-methoxy-1,3,3-trimethyl-2-methyleneindoline, 1 part of 2-chloro-1-formyl-3-hydroxymethylenecyclohexene, 1 part of paratoluenesulfonic acid and 0 part of sodium acetate anhydride After boiling 0.5 parts in 10 parts of acetic anhydride under reflux cooling for 1 hour and then cooling to room temperature, the reaction solution is subjected to suction filtration to remove insoluble impurities. Then, the reaction solution is poured into 30 parts of ice water, and the precipitated crystals are filtered by suction, washed with 20 parts of methanol, and dried to obtain 2 parts of a compound shown in Table 1 No. 1.

Synthesis Example 2 The same operation as in Synthesis Example 1 was carried out except that 1-methoxyethyl-
When 2 parts of 5-methoxy-3,3-dimethyl-2-methyleneindoline are used, 2 parts of the compound shown in Table 1 No. 6 are obtained.

Synthesis Examples 3 to 28 Nos. 2 to 5 and Nos. 7 to 50 according to Synthesis Examples 1 and 2
Is obtained.

[0068]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 "Preparation of negative type lithographic printing plate" 0.30 mm
The aluminum plate was washed with trichlorethylene and degreased, and then a nylon brush and 400 mesh pamistone-
The surface was grained with a water suspension and washed well with water. This plate is immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds, etched, washed with water, and further washed with 2% H 2.
It was immersed in NO3 for 20 seconds and washed with water. Current density 15
After providing a direct current anodic oxide film of 3 g / m ² at A / dm ² , the film was washed with water and dried. An undercoat liquid having the following composition was applied on the aluminum plate subjected to the degreasing treatment,
° C., and dried for 3 minutes, provided with a layer of 0.02 g / m ^2.

<Undercoat layer> (a) 1 part of β-alanine (b) 0.5 part of phenylsulfonic acid (c) 500 parts of a solvent (methanol: pure water = 2: 3) 500 parts Then, on this layer, The photosensitive layer composition was applied and dried at 80 ° C. for 1 minute to provide a heat-sensitive layer having a coating weight of 3 g / m ² . A negative photosensitive lithographic printing plate having a heat-sensitive light having a dry film thickness of 2 g / m ² was obtained by applying and drying a photosensitive layer composition having the following composition. <Photosensitive layer composition> (a) Table 1 1 part 2 parts (b) 4- (pN, N-bis (ethoxycarbonylmethyl) aminophenyl) -2,6-bis (trichloromethyl) -s-triazine 2 parts (c) Consisting of cresol and formaldehyde Novolak resin (meta: para ratio = 8: 2, average molecular weight 6000) 25 parts (d) Resol resin obtained from bisphenol A and formaldehyde 20 parts (e) Victoria pure blue BOH 1 part (f) Fluorosurfactant 1 2 parts (g) 55 parts of a solvent (methyl ethyl ketone: methanol = 8: 3)

Then, the obtained printing plate precursor was placed on a semiconductor laser (830 nm, beam diameter 20 μm, output 0.50
W) was used for scanning exposure at a linear velocity of 8 m / s. After exposure,
After heat treatment at 110 ° C. for 30 seconds with a panel heater, development was performed using an alkaline developer. Printing was performed using the lithographic printing plate precursor obtained at this time. As a result, 60,000 good printed matters having no stain on the non-image area were obtained.

[0071]

Example 2 In Example 1, Table 1 was used as an infrared absorbent.
No. Except for using the compound of Example 6, the same operation as in Example 1 was carried out to obtain a negative type lithographic printing plate material. The obtained printing plate precursor was placed in a semiconductor laser (830 nm, beam diameter 20 μm).
(m, output 0.10 W) at a linear velocity of 8 m / s. After the exposure, heat treatment was performed at 110 ° C. for 30 seconds with a panel heater, and then development was performed using an alkaline developer. Printing was performed using the lithographic printing plate precursor obtained at this time. As a result, 70,000 good printed matters having no stain on the non-image area were obtained.

[0072]

Comparative Example 1 In Example 1, a dispersion of carbon black was used as an infrared absorbent. The coating solution was uniform immediately after mixing, but agglomeration occurred over 3 days, and a uniform coating could not be obtained.

"Preparation of positive type lithographic printing plate"

Example 3 The following heat-sensitive layer composition was applied to the surface-treated aluminum plate used in Example 1 to prepare a positive type lithographic printing plate. <Photosensitive layer composition> (a) Table 1 1 part 2 parts (b) Esterified product of naphthoquinone-1,2-diazide-sulfonyl chloride and pyrogallol-acetone resin 18 parts (c) Novolak resin composed of cresol and formaldehyde (meta: para ratio = 6: 4, weight (Average molecular weight 1800) 40 parts (d) p-octylphenol-formaldehyde novolak 1 part (e) naphthoquinone-1,2-diazide-4-sulfonyl chloride 0.2 part (f) 4- (p-N, N-bis ( (Ethoxycarbonylmethyl) aminophenyl) -2,6-bis (trichloromethyl) -s-triazine 0.4 part (g) Victoria Pure Blue 0.6 part (h) Fluorosurfactant 1 part (g) Solvent ( Methyl ethyl ketone: methanol = 8: 3) 100 parts

The obtained positive type planographic printing plate was placed in a semiconductor laser (830 nm, beam diameter 20 μm, output 0.3
0W) at a linear velocity of 8 m / s. After the exposure, heat treatment was performed at 110 ° C. for 30 seconds with a panel heater, and then development was performed using an alkaline developer. Printing was performed using the lithographic printing plate precursor obtained at this time. As a result, 60,000 good printed matters having no stain on the non-image area were obtained.

[0075]

Example 4 In Example 3, Table 1 was used as an infrared absorbent.
No. Except for using the compound of Example 6, the same operation as in Example 3 was performed to obtain a negative type lithographic printing plate material. The obtained printing plate precursor was placed in a semiconductor laser (830 nm, beam diameter 20 μm).
(m, output 0.10 W) at a linear velocity of 8 m / s. After the exposure, heat treatment was performed at 110 ° C. for 30 seconds with a panel heater, and then development was performed using an alkaline developer. Printing was performed using the lithographic printing plate precursor obtained at this time. As a result, 70,000 good printed matters having no stain on the non-image area were obtained.

[0076]

Comparative Example 2 A positive lithographic printing plate was prepared in the same manner as in Example 3 except that the following compound (B) was used as an infrared absorbing agent. I could not get a printing plate. Therefore, when plate making was performed with the laser output set to 0.60 W, printing was performed using the lithographic printing plate precursor obtained at this time. As a result, 60,000 sheets of good printed matter having no stain on the non-image area were obtained. .

[0077]

Embedded image

"Preparation of negative type waterless lithographic printing plate"

Example 5 The following heat-insulating layer was applied to the surface-treated aluminum plate used in Example 1, dried at 200 ° C. for 2 minutes, and dried.
g / m ² of heat insulating layer was provided. <Heat insulation layer> (a) 15 parts of epoxy / phenol resin (b) 0.1 part of crystal violet (c) 85 parts of solvent (dimethylformamide)

Next, a photosensitive layer composition having the following composition was applied on this layer and dried at 80 ° C. for 1 minute to provide a photosensitive layer having a coating weight of 3 g / m ² . <Photosensitive layer composition> (a) Table 1 Compound (1) 5 parts (b) Iron (III) acetylacetonate 15 parts (c) Phenol novolak resin 5 parts (d) Polyurethane resin 25 parts (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyl trimethoxy Silane = 1/3/1 mol ratio Addition product 5 parts (f) Solvent: 650 parts tetrahydrofuran

Next, the following silicone rubber layer was applied at a dry film thickness of 0.2 μm under dry conditions of 120 ° C. for 1 minute. <Silicone Rubber Layer> (a) 100 parts of α-ω divinyl polydimethylsiloxane (polymerization degree: 770) (b) Methylhydrodienesiloxane / dimethylsiloxane copolymer: number of SiH groups / molecular weight = 0.69 mol / g 4 parts (c ) Olefin coordinated platinum 0.02 parts (d) Reaction inhibitor (CH （C-Si (CH3) 2OSi (CH3) 3) 3 parts (e) Isoparaffinic hydrocarbon 1000 parts Laminate obtained as described above An 8 μm thick polypropylene film was laminated on the plate to obtain a waterless negative type lithographic printing plate.

Thereafter, the obtained negative type waterless lithographic printing plate was placed on a semiconductor laser (830 nm, beam diameter 20 μm,
Scanning exposure was performed at a linear velocity of 8 m / s using an output of 0.10 W). Subsequently, when the plate exposed with water was developed, a negative type lithographic printing plate was obtained in which a portion of the silicone rubber layer irradiated with the laser beam was selectively removed. Printing was performed using the lithographic printing plate precursor obtained at this time. As a result, 60,000 good printed matters having no stain on the non-image area were obtained.

[0082]

Example 6 In Example 5, Table 1 was used as an infrared absorbent.
No. Except that the compound of No. 6 was used, the same operation as in Example 5 was carried out to obtain the obtained waterless negative type lithographic printing plate with a semiconductor laser (830 nm, beam diameter 20 μm, output 0.10).
W) was used for scanning exposure at a linear velocity of 8 m / s. continue,
When the plate exposed with water was developed, a negative type lithographic printing plate was obtained in which the silicone rubber layer in the portion irradiated with the laser beam was selectively removed. Printing was performed using the lithographic printing plate precursor obtained at this time. As a result, 70,000 good printed matters having no stain on the non-image area were obtained.

[0083]

Comparative Example 3 A negative waterless lithographic printing plate was prepared in the same manner as in Example 5 except that the above compound (C) was used as an infrared absorber, and evaluated in the same manner. And a printing plate could not be obtained. When plate making was performed with the laser output set to 0.60 W, a negative type lithographic printing plate was obtained in which the silicone rubber layer was selectively removed from the portion irradiated with the laser beam. Printing was performed using the lithographic printing plate precursor obtained at this time. As a result, 60,000 good printed matters having no stain on the non-image area were obtained.

[0084]

Embedded image

[0085]

According to the present invention, by using a specific infrared absorber, a laser emitting at around 830 nm can be used as a recording light source to directly make a plate from digital data of a computer or the like, exhibit high sensitivity, and improve printability. An excellent laser direct-writing type printing plate can be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03F 7/004 501 G03F 7/004 501 // C07D 209/14 C07D 209/14 F term (reference) 2H025 AA01 AB03 AB04 AC08 AD03 BE00 BH01 CB42 CC13 CC17 CC20 FA10 2H096 AA06 AA13 BA01 BA09 EA04 EA23 2H114 AA04 AA22 AA23 AA24 BA01 DA04 DA25 DA26 DA35 DA49 DA73 DA78 EA01 EA02 EA04 FA16 GA03 GA05 GA06 GA09 GA34 GA03 4CB204 CB03 BB03 CB04

Claims (7)

[Claims] 1. An infrared absorbing agent for a laser direct drawing type lithographic printing plate represented by the following general formula (1). Embedded image (In Formula (1), R1 and R2 each independently represent a substituted or unsubstituted hydrocarbon group. R3 and R4 each independently represent an unsubstituted alkyl group having up to 12 carbon atoms. The anion present correspondingly is shown.) 2. The direct drawing laser plate according to claim 1, wherein in formula (1), R1 and R2 are each independently a substituted or unsubstituted alkyl group, aryl group or alkenyl group having up to 12 carbon atoms. Infrared absorber for printing plates. 3. In the formula (1), R1 and R2 each independently represent an alkyl group having up to 12 carbon atoms, a cycloalkyl group,
An alkoxy-substituted alkyl group, an alkoxyalkoxy-substituted alkyl group, a sulfonyl-substituted alkyl group, a cyano-substituted alkyl group, an aryl-substituted alkyl group, an acyl-substituted alkyl group, an alkenyloxy-substituted alkyl group or an alkenyl group, and R3 and R4 are each independently methyl The infrared absorbent for a laser direct-drawing lithographic printing plate according to claim 2, which is an ethyl group or an ethyl group. 4. A negative laser comprising a support having thereon a photosensitive layer containing the compound according to any one of the following (a), (b) and (c) and any one of claims 1 to 3. Direct drawing type lithographic printing plate. (A) an alkali-soluble binder (b) a compound that generates an acid by heat (c) a compound that polymerizes or cross-links (a) with an acid to make it insoluble in an aqueous alkali solution (hereinafter referred to as an acid-crosslinkable compound) 5. The following (a) and (d) and claims 1 to 3
A positive laser direct-drawing lithographic printing plate having a photosensitive layer containing the compound according to any one of the above on a support. (A) an alkali-soluble binder (d) in a state where it is thermally decomposable and does not decompose (a)
Compounds that reduce the solubility of 6. A laser direct drawing type lithographic printing plate having a photosensitive layer containing the compound according to claim 1 on a support, wherein a hydrophilic layer such as a silicone rubber layer is exposed to light. Laser direct drawing type lithographic printing plate characterized by having on a layer. 7. A laser direct-drawing lithographic printing plate having a photosensitive layer containing the compound according to claim 1 on a support, wherein no development processing is required. Laser direct drawing type lithographic printing plate characterized by being a mold.