JP2002122983A - Method for producing planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a planographic printing plate by which plate making conditions for a negative image forming material for an IR laser for direct plate making are adjusted and the quality of the resulting planographic printing plate is kept constant so as to continuously form uniform images. SOLUTION: In the method for producing a planographic printing plate by which a negative original plate of the planographic printing plate with a photosensitive layer containing an IR absorbent, a compound which generates a radical or an acid under heat and a polymerizable compound or a crosslinkable compound on the base is exposed and processed by using an automatic processing machine provided with a developing part, a washing part, a finisher part and planographic printing plate conveying members, planographic printing plate conveying rollers are disposed at the inlet and/or outlet of the washing part of the automatic processing machine in such a way that the rollers come in contact with the photosensitive layer of the planographic printing plate and the rotational speed of the planographic printing plate conveying rollers is different from the planographic printing plate conveying speed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of making a negative type lithographic printing plate for an infrared laser for direct plate making, which can be used as an offset printing master and can make a plate directly from a digital signal of a computer or the like.

[0002]

2. Description of the Related Art In recent years, the development of lasers has been remarkable. In particular, solid-state lasers and semiconductor lasers having a light-emitting region from the near infrared to the infrared have been increasing in output and miniaturization. Therefore, these lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like. The negative type lithographic printing plate material for an infrared laser, which uses an infrared laser having an emission region in the infrared region as an exposure light source, includes an infrared absorber, a compound that generates a radical or an acid by heat, a polymerizable compound, or a cross-linkable compound. A lithographic printing plate material having a photosensitive layer containing a hydrophilic compound.

Usually, such a negative-type image recording material forms an image portion by using an acid generated by heat as an initiator to cause a cross-linking reaction by the acid to cure the recording layer in the exposed portion, Alternatively, a recording method is used in which a polymerization reaction is caused by using a radical generated by heat as an initiator, and a recording layer in an exposed portion is cured to form an image portion. Such a negative type image forming material has low image forming property as compared with a negative type which causes the recording layer to be solubilized by the energy of infrared laser irradiation, and promotes a curing reaction such as cross-linking or polymerization. In general, a heat treatment is performed before the developing step to form an image portion.

However, in such a negative type lithographic printing plate material for infrared laser, the latitude with respect to the activity of the developing solution is narrower than that of the negative type lithographic printing plate material made by UV exposure, so that the activity becomes higher. When the activity is lowered, such as lowering the density of the image area and lowering the printing durability, poor development is easily caused, and there is a problem that deposits of the recording layer having a diameter of about 0.2 to 3.0 mm adhere to the plate. The problem is caused by the following essential difference in the plate making mechanism between the negative type lithographic printing plate material for infrared laser and the negative type lithographic printing plate material made by UV exposure.

[0005] Many of the negative type lithographic printing plate materials to be made by UV exposure contain a diazonium compound and a polymer as a binder as essential components. Image forming properties vary depending on the diazonium compound and binder used,
Generally, since the binder has a large molecular weight and a small copolymerization ratio with a hydrophilic group such as a carboxyl group, the non-image portion (unexposed portion) is easily dissolved in a developing solution to which an organic solvent such as benzyl alcohol is added. Can be removed. On the other hand, UV
Due to the light exposure, the binder and the diazonium compound cause a photoreaction in the exposed area to form a network structure, and therefore, it becomes difficult to dissolve even when a developer containing an organic solvent is used. Therefore, in the negative type lithographic printing plate material made by the UV exposure, since the difference in solubility between the exposed part and the non-exposed part in the developing solution is very large, adhesion of scum due to deterioration in printing durability and poor development is prevented. Does not occur.

On the other hand, in the above-mentioned negative type lithographic printing plate material for infrared laser, at the time of exposure, light is converted into heat energy by an infrared absorber in an exposed portion (non-image portion), and acid or acid is converted by the heat. Although components such as radicals contributing to the curing of the image area are generated, a heat treatment is required to accelerate the reaction, and the image area is cured only after the crosslinking reaction or the polymerization reaction proceeds by heating. In addition, although the image portion and the non-image portion are formed by adjusting the heating temperature, the temperature range of the heat treatment for obtaining a lithographic printing plate at a level which can be actually used is very narrow. Furthermore, the polymerizable compound or the cross-linkable compound used here has an overwhelmingly large number of hydrophilic groups as compared with the binder used for the image forming material for UV exposure, so that even after curing, it can be used in an alkaline developer. Easy to dissolve. For this reason, in the negative type lithographic printing plate material for infrared laser, the difference in solubility between the non-exposed portion and the exposed portion is small. In order to continuously form a stable image using an image forming material having a small latitude with respect to the activity of the developer, it is very difficult to control the process. In particular, since a negative type lithographic printing plate for an infrared laser forms an image by a heat treatment, poor development is likely to occur due to deterioration of a developing solution in a non-image area, and scum of a recording layer easily adheres to the plate.

[0007] The above point does not cause a serious problem because a normal lithographic printing plate using UV exposure has a wide latitude, but a negative photosensitive lithographic printing plate for an infrared laser has a narrow latitude as described above. It easily causes quality problems of the lithographic printing plate, such as adhesion of scum due to poor development due to a decrease in the activity of the developer.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and achieve the following objects. That is, the present invention provides a plate making method for adjusting the plate making conditions of a negative type image forming material for an infrared laser for direct plate making, keeping the quality of a lithographic printing plate constant, and continuously forming a uniform image. The purpose is to provide.

[0009]

As a result of the study, the present inventors have found that by adjusting the conditions of the transport roller disposed in the washing section after development, stable lithographic printing can be obtained. Thus, the present invention has been completed.

That is, the method of making a lithographic printing plate according to claim 1 of the present invention comprises the steps of: providing an infrared absorbing agent, a compound capable of generating radicals or acids by heat, a polymerizable compound or a crosslinkable compound on a support; After exposure of a negative-working lithographic printing plate precursor having a photosensitive layer containing, a lithographic printing plate making method for making a plate using an automatic developing device having a developing unit, a washing unit, a finisher unit, and a lithographic printing plate transport member. A transport roller for the lithographic printing plate is disposed at an inlet and / or an outlet of the washing section of the automatic developing device so as to come into contact with the photosensitive layer of the lithographic printing plate,
It is characterized in that the rotation speed of the transport roller of the lithographic printing plate is different from the transport speed of the lithographic printing plate.

According to a second aspect of the present invention, there is provided a method for making a lithographic printing plate, comprising: on a support, an infrared absorbing agent, a compound generating a radical or an acid by heat, and a polymerizable compound or a crosslinkable compound. A method of making a lithographic printing plate, comprising: exposing a negative-working lithographic printing plate precursor having a photosensitive layer, followed by making a plate using an automatic developing apparatus having a developing unit, a washing unit, a finisher unit, and a lithographic printing plate transport member. An activity evaluation for detecting a decrease in the activity of the developer by observing the occurrence of a residual film of the photosensitive layer in the non-image area of the lithographic printing plate at the exit of the washing section of the automatic developing apparatus and the adhesion of the precipitate. When a decrease in the activity of the developer is detected in the step and the activity evaluation step, the developer is disposed at the inlet and / or outlet of the washing section of the automatic developing device so as to come into contact with the photosensitive layer of the lithographic printing plate. Set the rotation speed of the transport rollers to And having a an adjustment step of controlling to be different from the conveying speed of the printing plate.

In the plate making method of the present invention, since the rotation speed of the conveying roller in the washing section of the automatic developing machine is different from the conveying speed of the lithographic printing plate, the lithographic printing plate is conveyed with the conveying roller in contact with the photosensitive layer side. The stress resulting from the speed difference of the lithographic printing plate is applied to the surface of the photosensitive layer, and the residual film and the scum adhering to the plate surface can be efficiently removed. The rotation speed of the transport roller in the rinsing section may always be adjusted so as to have a certain difference with respect to the transport speed of the lithographic printing plate. Depending on the activity of the developing solution, such as a phenomenon that a residual film of the layer is generated or a residue of the deposited photosensitive layer adheres to the plate surface, the rotation speed of the transport roller of the washing section and the lithographic printing plate are changed. May be adjusted to adjust the difference between the transfer speed and the removal speed of the attached matter and the residual film.

[0013]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows a typical automatic developing apparatus capable of implementing the present invention. The automatic developing device 10
Lithographic printing plate precursor (hereinafter, appropriately referred to as plate material) 12 on which an image is recorded by an infrared laser exposure device (not shown) 12
Is performed.

First, an outline of the automatic developing apparatus will be described. The automatic developing device 10 includes a developing unit 18, a washing unit 24 for washing a developing solution attached to the plate material 12 with water and a washing process, and a finisher for applying a gum solution to the washed plate material 12 to make the plate material desensitized. And a drying unit 16 for drying the printing plate 12. The developing unit 18 includes the developing tank 14 and the washing unit 2.
4 is a washing tank 28, and the finisher 26 is a gum solution tank 3.
0 is provided.

The outer panel 20 on the side of the developing section 18 is provided with a slit-shaped insertion opening 22 into which the plate 12 is inserted. A pair of transport rollers 32 is provided inside the insertion port 22, and the plate material 12 inserted from the insertion port 22 is nipped and transported by the transport rollers 32,
The developer is fed toward the developing tank 14 at a predetermined angle with respect to the horizontal direction. The developing tank 14 has a substantially inverted mountain shape having an opening at the top and a bottom center part protruding downward. The developing tank 14 has an upstream side along the transport direction of the printing plate 12. In order, a pair of transport rollers 34,
Brush rollers 36 and 38 and a pair of squeezing rollers 40 are provided. The transport roller 34, the brush rollers 36 and 38, and the squeeze roller 40 are rotated by a drive mechanism (not shown).

Further, backup rollers 44 and 46 are disposed opposite to each other with the brush roller 36 interposed therebetween, and a backup roller 48 is disposed opposite the brush roller 38. These backup rollers 44, 46,
The drive force is not transmitted to 48, and it is rotatable.

In the developing section 18, the developing solution in the developing tank 14 is sucked through a joint pipe 50 provided on the bottom wall, and is discharged through a discharging port (not shown) formed in the side wall. The developer is discharged into the circulator 14 to circulate and agitate the developer.

The washing section 24 on the downstream side of the developing section 18 has a pair of delivery rollers 54 and 56 above the washing tank 28, respectively.
Are arranged. These transport rollers 54 and 56 are
The plate 12 is rotatably supported by the side plate, and the driving force of the driving unit is transmitted to form a transport path for the plate material 12 sent from the developing unit 18.

A spray pipe 58 is arranged between the transport rollers 54 and 56 so that the spray port is directed toward the transport path. Rinsing water pumped up by a pump from a rinsing water tank (not shown) is ejected from the spray pipe 58, and the front and back surfaces of the printing plate 12 are washed with the rinsing water. The washing water after washing flows to the washing tank 28. The transport rollers 32 and 34 mainly have a function of controlling the transport speed of the lithographic printing plate precursor or the lithographic printing plate after development, and determine the transport speed of the lithographic printing plate (original plate). On the other hand, the transport roller 5 provided in the washing section 24
4 and 56 are controlled by a drive mechanism different from the transport rollers 32 and 34 so that they are rotated by a drive mechanism that changes the rotation speed of the transport rollers 32 and 34. The rotation speed of the transport rollers 54 and 56 is
It is preferable that the rotation speed is different from the rotation speed of 2 and 34, that is, the transport speed of the planographic printing plate by 1 to 50%.
It is more preferable that the difference is 10% from the viewpoint of the effect of preventing the deposit from adhering. The rotation speed of the transport rollers 54 and 56 disposed in the washing unit 24 may be controlled with a certain difference compared to the rotation speed of the transport rollers 32 and 34,
Control can also be performed to adjust the difference appropriately according to the activity of the developer. Further, the speed adjustment may be performed only for the transport roller 54 provided at the entrance, only for the transport roller 56 provided at the exit, or both.

A pair of squeezing rollers 60 are provided above the gum solution tank 30 of the finisher unit 26, which is a desensitizing unit downstream of the washing unit 24. Then, the plate material 12 sent out by the transport roller 56 is sent to the squeezing roller 60. On the upstream side of the squeezing roller 60, a spray pipe 62 is vertically opposed to each other, and the ejection port is directed to the transport path. From the spray pipe 62, the gum solution sucked by the pump from the gum solution tank 30 is jetted out and applied to the front and back surfaces of the printing plate 12.

Thereafter, the plate material 12 on which the gum solution is uniformly applied by the squeezing roller 60 is guided to the drying unit 16 through a passage opening 66 opened and closed by a shutter 64. In the drying section 16, the dried plate material 12 conveyed and dried by the guide roller 68 and the pair of skewer rollers 70 and 72 is discharged out of the automatic developing device 10 through the discharge port 74.

As the conveying roller and the squeezing roller, any material can be used as long as it can withstand the processing chemicals. Preferably, silicone rubber, butyl rubber, ethylene / propylene rubber (EPT / EPDM), acrylonitrile / butadiene rubber (NBR), styrene / butadiene rubber (SBR), polybutadiene rubber (B
R), chloropyrene rubber (CR) and the like can be used.

It is preferable to use a roller containing a fungicide or an antibacterial agent for the conveying roller and the squeezing roller. . As the antifungal agent and the antibacterial agent, generally known substances can be used, but preferably, 2- (4-thiazolyl) -benzimidazole (Hokuster HP manufactured by Hokuko Chemical Industry Co., Ltd.) is used.
And thiazoline based on Amorden SK-950 (trade name, manufactured by Daiwa Chemical Co., Ltd.), as well as binazine (Vinyzene, trade name, manufactured by Morton Thiokol, USA). The addition amount of the fungicide and the antibacterial agent is preferably 0.1 to 5% by weight of the rubber roller.

In the developing step, if scum adheres due to a decrease in the activity of the developing solution, it is possible to increase or decrease the rotation speed of the transport rollers 54 and 56 with respect to the transport speed of the planographic printing plate. Means for controlling the transport speed of the lithographic printing plate to sufficiently differ from the transport speed may be taken.
Further, in addition to the adjustment of the rotation speed of the transport roller of the washing section, a general method for improving the activity of the developer as described below can be used in combination. In the case where the developing property is reduced and poor development or adhesion of scum occurs, other measures include the following measures.In the heating step, (1) lower the heating temperature. (2) shorten the heating time. (Increase the transfer speed in the oven) (3) Decrease the amount of hot air (4) Increase the distance between the plate and the heater.

In the development process, (1) add a replenisher (2) increase the dilution ratio of the replenisher (3) increase the replenishment amount setting of the automatic developing machine (4) increase the development temperature (5) develop Prolong the time (reduce the transport speed of the automatic developing machine) (6) Increase the pressure of the developing brush of the automatic developing machine (7) Increase the number of developing brushes of the automatic developing machine (8) Increase the spray discharge amount ( 9) It is possible to take measures such as replacing the developing solution with a new solution.

Hereinafter, a negative type lithographic printing plate precursor to which the plate making method of the present invention can be applied will be described. The method of the present invention may be any negative-working lithographic printing plate precursor that can be written by an infrared laser, that is, a lithographic printing plate precursor having a negative-type photosensitive layer in which an infrared laser-irradiated portion is cured to form an image area. It can be applied to any of them. One of such negative photosensitive layers is a photopolymerizable layer. The photopolymerization layer preferably contains (A) an infrared absorber, (B) a radical generator (radical polymerization initiator), and (C) a radical polymerizable compound which is cured by causing a polymerization reaction by the generated radicals. Contains (D) a binder polymer. The infrared ray absorbed by the infrared absorbent is converted into heat, and the heat generated at this time decomposes a radical polymerization initiator such as an onium salt to generate a radical. The radical polymerizable compound is selected from compounds having at least one ethylenically unsaturated double bond and having at least one, and preferably two or more, terminal ethylenically unsaturated bonds, and is polymerized in a chain by generated radicals. A reaction takes place and hardens.

Another embodiment of the photosensitive layer is an acid cross-linking layer. The acid crosslinked layer includes (E) a compound that generates an acid by light or heat (hereinafter, referred to as an acid generator),
(F) a compound capable of crosslinking by the generated acid (hereinafter, referred to as a crosslinking agent), and further capable of reacting with the crosslinking agent in the presence of an acid for forming a layer containing the compound (G). Contains an alkali-soluble polymer. In the acid cross-linked layer, the acid generated by the decomposition of the acid generator by light irradiation or heating promotes the action of the cross-linking agent, and a strong cross-linking structure between the cross-linking agents or between the cross-linking agent and the binder polymer. Is formed, whereby the alkali solubility decreases and the developer becomes insoluble. At this time, in order to efficiently use the energy of the infrared laser, (A)
An infrared absorber is blended.

Each compound used in the photosensitive layer of the negative type lithographic printing plate precursor is described below. [(A) Infrared Absorber] The photosensitive layer of the lithographic printing plate precursor according to the invention has a structure capable of recording an image with a laser emitting infrared rays. It is preferable to use an infrared absorber for such a photosensitive layer. The infrared absorbent has a function of converting the absorbed infrared light into heat. The heat generated at this time decomposes the radical generator and the acid generator to generate radicals and acids. The infrared absorber used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm.

As the dye, commercially available dyes and known dyes described in literatures such as "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, Japan, 1970) can be used. Specifically, for example, those described in paragraph numbers [0050] to [0051] of JP-A-10-39509 can be exemplified. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes. Further, a cyanine dye is preferable, and a cyanine dye represented by the following general formula (I) is most preferable.

[0030]

Embedded image

In the general formula (I), X¹Is a halogen atom,
Or X^Two-L¹Is shown. Where X^TwoIs an oxygen atom or
Represents a sulfur atom;¹Is a carbon having 1 to 12 carbon atoms
Shows a hydride group. R¹And R^TwoAre each independently charcoal
It represents a hydrocarbon group having 1 to 12 elementary atoms. Of photosensitive layer coating solution
From storage stability, R¹And R^TwoIs 2 or more carbon atoms
And preferably a hydrocarbon group of¹And R^Two
Is bonded to each other to form a 5- or 6-membered ring
Is particularly preferred. Ar¹, Ar^TwoAre the same for each
May be different, and may have a substituent.
Represents a group hydrocarbon group. Y¹, Y^TwoAre the same but different
And may have 12 or more sulfur atoms or carbon atoms.
The lower dialkylmethylene group is shown. R ^Three, R^FourEach
May be the same or different, and may have a substituent
Shows good hydrocarbon groups having 20 or less carbon atoms. Preferred
Substituents include alkoxy having 12 or less carbon atoms.
Group, carboxyl group and sulfo group. R^Five,
R⁶, R⁷And R⁸Are the same but different
Hydrogen atoms or hydrocarbons having 12 or less carbon atoms
Represents an elementary group. From the availability of raw materials, it is preferably a hydrogen atom
is there. Also, Z^1-Represents a counter anion. Where R¹
~ R⁸Is substituted with a sulfo group,
Z^1-Is not required. Preferred Z^1-Is to store the photosensitive layer coating solution
Halogen ion, perchlorate ion, tetra
Fluoroborate ion, hexafluorophosphate
And sulfonate ions, particularly preferred
Is perchlorate ion, hexafluorophosphate
And arylsulfonate ions.

In the present invention, specific examples of the cyanine dye represented by the general formula (I) which can be suitably used include paragraph [0] of Japanese Patent Application No. 11-310623.
017] to [0019].

The pigment used in the present invention includes:
Commercial Pigment and Color Index (CI) Handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
Can be used.

The types of pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Details of these pigments are described in paragraph [005] of JP-A-10-39509.
2] to [0054], which can be applied to the present invention. Preferred among these pigments is carbon black.

The content of the above dye or pigment in the photosensitive layer is 0.0
It is preferably 1 to 50% by weight, more preferably 0.1 to 10% by weight, and in the case of a dye, 0.5 to 10% by weight.
Is most preferable, and in the case of a pigment, 1.0 to 10% by weight
Is most preferred. If the content is less than 0.01% by weight, the sensitivity may be low. If the content is more than 50% by weight, the non-image area of a lithographic printing plate precursor may be stained.

[(B) Radical-Generating Compound] Examples of the radical-generating compound suitably used in the present invention include onium salts, specifically, iodonium salts, diazonium salts, and sulfonium salts. These onium salts also have a function as an acid generator,
When used in combination with a radical polymerizable compound described later, it functions as an initiator for radical polymerization. Onium salts suitably used in the present invention are represented by the following general formulas (III) to (III).
An onium salt represented by (V).

[0037]

Embedded image

In the formula (III), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms which may have a substituent. When the aryl group has a substituent, preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a 12 or less carbon atom. Aryloxy groups. Z ^11- represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, and is preferably a perchlorate ion or a hexafluorophosphate. And arylsulfonate ions.

In the formula (IV), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and a 12 or less carbon atom. Alkylamino group, dialkylamino group having 12 or less carbon atoms, 1 carbon atom
An arylamino group having 2 or less or a diarylamino group having 12 or less carbon atoms is exemplified. Z ^{21 -} is Z ^11-
Represents a counter ion having the same meaning as

In the formula (V), R ³¹ , R ³² and R ³³ may be the same or different and represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, and an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

In the present invention, specific examples of onium salts that can be suitably used include Japanese Patent Application No. 11-3106.
No. 23, paragraphs [0030] to [0033].

The onium salt used in the present invention is
Preferably, the maximum absorption wavelength is 400 nm or less,
Further, the thickness is preferably 360 nm or less. By setting the absorption wavelength in the ultraviolet region, the lithographic printing plate precursor can be handled under a white light.

These onium salts are used in an amount of 0.1 to 50% by weight, preferably 0.5 to 50% by weight, based on the total solid content of the coating solution for the photosensitive layer.
It can be added to the photosensitive layer coating solution at a ratio of 30% by weight, particularly preferably 1 to 20% by weight. 0.1
If it is less than 50% by weight, the sensitivity will be low, and if it exceeds 50% by weight, the non-image area will be stained during printing. One of these onium salts may be used alone, or two or more thereof may be used in combination. Further, these onium salts may be added to the same layer as other components, or another layer may be provided and added thereto.

[(C) Radical polymerizable compound] The radical polymerizable compound used in the photosensitive layer according to the present invention is a radical polymerizable compound having at least one ethylenically unsaturated double bond, and has a terminal ethylenic compound. It is selected from compounds having at least one, preferably two or more unsaturated bonds. Such compounds are widely known in the industrial field, and they can be used in the invention without any particular limitation. These are, for example, monomers,
It has a chemical form such as a prepolymer, ie, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and their copolymers include unsaturated carboxylic acids (eg, acrylic acid,
Methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids An amide of the compound and an aliphatic polyamine compound is used. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of an amide with a monofunctional or polyfunctional isocyanate, an epoxy, a monofunctional or A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further, halogen A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving group such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds in which the above unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene or the like.

Specific examples of the radically polymerizable compound, which is an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, such as acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester and maleic acid ester For example, Japanese Patent Application No. Hei 11-3
No. 10623, paragraphs [0037] to [004]
2], and these can be applied to the present invention.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240 and JP-A-59-5240. 59-524
1, those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.

Specific examples of the amide monomer of an aliphatic polyamine compound and an unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

Examples of other preferred amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

Further, urethane-based addition-polymerizable compounds produced by an addition reaction between an isocyanate and a hydroxyl group are also suitable.
JP-A-8-41708 discloses a polyisocyanate compound having two or more isocyanate groups in one molecule to which a vinyl monomer having a hydroxyl group represented by the following formula (VI) is added. And vinyl urethane compounds containing at least two polymerizable vinyl groups.

Formula (VI) CH ₂ ＣC (R ⁴¹ ) COOCH ₂ CH (R ⁴² ) OH (where R ⁴¹ and R ⁴² represent H or CH ₃ )

Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, and JP-B-58-167.
No. 49860, No. 56-17654, No. 62
Urethane compounds having an ethylene oxide skeleton described in JP-B-39417 and JP-B-62-39418 are also suitable.

Further, radical polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277563, JP-A-63-260909 and JP-A-1-105238 can be used. good.

Another example is described in JP-A-48-641.
No. 83, JP-B-49-43191, JP-B-52-30
No. 490, polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in each publication. Also,
JP-B-46-43946, JP-B-1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinyl phosphonic acid compounds described in JP-A-2-25493 can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesion Association Journal vol. 20, No. 7, pages 300-308 (198
(4 years) as photocurable monomers and oligomers can also be used.

With respect to these radically polymerizable compounds,
Details of the method of use, such as what kind of structure is used, whether it is used alone or in combination, and how much is added, can be arbitrarily set in accordance with the final performance design of the recording material. For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a large content of unsaturated groups per molecule is preferable, and in many cases, a bifunctional or more functional structure is preferable. In order to increase the strength of the image area, that is, the cured film, a compound having three or more functional groups is preferable, and a compound having a different functional number and a different polymerizable group (for example, an acrylate compound, a methacrylate ester) It is also effective to control both the photosensitivity and the intensity by using a combination of a compound and a styrene compound. Compounds with large molecular weight and compounds with high hydrophobicity are excellent in sensitivity and film strength,
It may not be preferable in terms of development speed and precipitation in a developer. In addition, the selection and use of the radical polymer compound is also an important factor for the compatibility and dispersibility with other components (for example, a binder polymer, an initiator, a colorant, and the like) in the photosensitive layer. Use of low purity compounds, 2
The compatibility may be improved by the combined use of at least one compound. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support, the overcoat layer, and the like. Regarding the compounding ratio of the radical polymerizable compound in the image recording layer (photosensitive layer), the larger the ratio, the more advantageous in sensitivity.
If the amount is too large, undesired phase separation occurs, problems in the manufacturing process due to the stickiness of the image recording layer (for example, transfer of photosensitive layer components, manufacturing defects due to sticking), and precipitation from the developer. Problems may occur. From these viewpoints, a preferable compounding ratio of the radical polymerizable compound is, in many cases, from 5 to 80% by weight, and preferably from 20 to 75% by weight, based on all components of the composition. These may be used alone or in combination of two or more. In addition, the use of radically polymerizable compounds depends on the magnitude of polymerization inhibition for oxygen,
From the viewpoints of resolution, fogging property, change in refractive index, surface tackiness, etc., an appropriate structure, blending and addition amount can be arbitrarily selected, and in some cases, a layer structure and a coating method such as undercoating and overcoating may be performed.

[(D) Binder polymer] In the present invention, a binder polymer is further used. It is preferable to use a linear organic polymer as the binder. Any of such “linear organic polymers” may be used. Preferably, a linear organic polymer which is soluble or swellable in water or weakly alkaline water is selected to enable development with water or weakly alkaline water. The linear organic polymer is selected and used not only as a film forming agent for forming a photosensitive layer but also as a developer for water, weakly alkaline water or an organic solvent.
For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in a side chain, for example,
Nos. 9-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048. Those described, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is useful.

Among these, a (meth) acrylic resin having a benzyl group or an allyl group and a carboxyl group in the side chain is preferable because of excellent balance of film strength, sensitivity and developability.

In addition, Japanese Patent Publication No. 7-12004,
JP-A-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271174,
The urethane-based binder polymer containing an acid group described in Japanese Patent Application No. 10-116232 is very excellent in strength and is advantageous in terms of printing durability and low exposure suitability.

Further, as the water-soluble linear organic polymer, polyvinyl pyrrolidone, polyethylene oxide and the like are useful. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, more preferably Is in the range of 2000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably in the range of 1.1 to 10.

These polymers are random polymers,
Any of a block polymer and a graft polymer may be used, but a random polymer is preferable.

The polymer used in the present invention can be synthesized by a conventionally known method. As a solvent used in the synthesis, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy -2-propanol, 1-methoxy-2-propyl acetate, N, N-
Dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate,
Dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.

As the radical polymerization initiator used when synthesizing the polymer used in the present invention, known compounds such as an azo initiator and a peroxide initiator can be used.

The binder polymer used in the present invention may be used alone or as a mixture. These polymers are 20 to 95% by weight based on the total solid content of the photosensitive layer coating solution,
Preferably, it is added to the photosensitive layer at a ratio of 30 to 90% by weight. When the addition amount is less than 20% by weight, the strength of the image portion is insufficient when an image is formed. 95% by weight
If the number exceeds, no image is formed. The weight ratio of the radical polymerizable compound having an ethylenically unsaturated double bond and the linear organic polymer is preferably in the range of 1/9 to 7/3.

Next, the components of the acid crosslinked layer will be described. As the infrared absorber used here, the same one as the infrared absorber (A) described in the photopolymerization layer can be used. The preferred content is preferably 0.01 to 50% by weight, and more preferably 0.1 to 50% by weight based on the total solid weight of the photosensitive layer.
-10% by weight is more preferable, and in the case of a dye,
0.5 to 10% by weight is most preferable, and in the case of a pigment,
1.0 to 10% by weight is most preferred. The content is
If the amount is less than 0.01% by weight, the sensitivity may be low. If the amount is more than 50% by weight, stains may occur on a non-image portion of a lithographic printing plate precursor.

[(E) Acid Generator] In the present embodiment, the acid generator which is decomposed by heat to generate an acid is 200
A compound that generates an acid when irradiated with light in the wavelength region of ５００500 nm or heated to 100 ° C. or higher.
Examples of the acid generator include a photo-initiator for photo-cationic polymerization, a photo-initiator for photo-radical polymerization, a photo-decolorizing agent for dyes, a photo-discoloring agent, or a known acid generator used in micro resists and the like. And known compounds capable of generating an acid upon thermal decomposition, and mixtures thereof. For example,
I. Schlesinger, Photogr. Sc
i. Eng. , 18, 387 (1974); S. B
al et al, Polymer, 21, 423 (1
980), U.S. Pat.
Ammonium salts described in US Pat. No. 9,055, JP-A-4-365049, and the like, US Pat. No. 4,069,055.
Nos. 4,069,056, EP 104,143 and U.S. Pat.
39,049 and 410,201, iodonium salts described in JP-A-2-150848 and JP-A-2-296514, European Patent 370,693,
390,214, 233,567, 297,
Nos. 443 and 297,442; U.S. Pat.
No. 3,377, No. 161, 811, No. 410, 201
Nos. 339,049, 4,760,013, 4,734,444, 2,833,827, German Patent Nos. 2,904,626, 3,604,580
No. 3,604,581, the sulfonium salt described in each specification,

J. V. Crivello et al,
Macromolecules, 10 (6), 1307
(1977); V. Crivello et a
1, J .; Polymer Sci. , Polymer
Chem. Ed. , 17, 1047 (1979); S. Wen et al, Te
h, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), US Pat.
05,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, and JP-A-61-169835.
JP-A-61-169837, JP-A-62-582
No. 41, JP-A-62-212401, JP-A-63-7
No. 0243, organic halogen compounds described in JP-A-63-298339, organic metal / organic halides described in JP-A-2-161445, European Patent No. 0290,
No. 750, No. 046,083, No. 156,535,
Nos. 271,851, 0,388,343, U.S. Pat. Nos. 3,901,710 and 4,181,531, JP-A-60-198538 and JP-A-53-5331.
No. 133022, a photoacid generator having an o-nitrobenzyl-type protecting group, EP 0199,672, 84515, 199,672, 044,115.
No. 0101,122, U.S. Pat. No. 4,618,5.
No. 64, No. 4,371,605, No. 4,431,77
4, JP-A-64-18143, JP-A-Hei 2-18
Compounds which generate sulfonic acid upon photolysis, such as iminosulfonates described in JP-A-245756 and Japanese Patent Application No. 3-140109, and disulfone compounds described in JP-A-61-166544. Can be.

Also preferred are compounds in which these acid-generating groups or compounds are introduced into the main chain or side chain of the polymer. For example, US Pat.
9,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164.
No. 824, JP-A-62-269263, JP-A-63-1
No. 46037, JP-A-63-163452, JP-A-6-163452
Compounds described in JP-A-2-153853 and JP-A-63-146029 can be mentioned. Further, V.I. N. R. Pil
lai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedr
on Lett. , (47) 4555 (1971),
D. H. R. Barton et al, J. M .; Che
m, Soc,. (B), 329 (1970), U.S. Pat. No. 3,779,778, and European Patent 126,712, etc., which can generate an acid by light can also be used. Among the above-mentioned acid generators, compounds represented by the following general formulas (I) to (V) are preferable.

[0068]

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In the general formulas (I) to (V), R ¹ , R ² ,
R ⁴ and R ⁵ may be the same or different and represent an optionally substituted hydrocarbon group having 20 or less carbon atoms.
R ³ represents a halogen atom, an optionally substituted hydrocarbon group having 10 or less carbon atoms or an alkoxy group having 10 or less carbon atoms. Ar ¹ and Ar ² may be the same or different and each represents an optionally substituted aryl group having 20 or less carbon atoms. R ⁶ represents a divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent. n represents the integer of 0-4. In the above formula, R ¹ , R ² , R ⁴ and R ⁵ are preferably a hydrocarbon group having 1 to 14 carbon atoms.

Preferred embodiments of the acid generators represented by formulas (I) to (V) are described in Japanese Patent Application No. 11-320997, paragraph No. [0197] to Japanese Patent Application No. 11-320997, proposed by the present inventors.
[0222]. These compounds are described, for example, in JP-A Nos. 2-100054 and 2-1.
It can be synthesized by the method described in No. 00005.

As the acid generator (E), an onium salt having a counter ion of a halide, sulfonic acid or the like can also be mentioned. Among them, the following general formulas (VI) to (VIII)
Preferred are those having any of the structural formulas of iodonium salt, sulfonium salt and diazonium salt represented by

[0072]

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In the above general formulas (VI) to (VIII), X
^- is a halide _{^{ion, ClO 4 -, PF 6 -}} , SbF 6
^— , BF ₄ ^— or R ⁷ SO ₃ ^— , wherein R ⁷ represents an optionally substituted hydrocarbon group having 20 or less carbon atoms. Ar ³ and Ar ⁴ each independently represent an optionally substituted aryl group having 20 or less carbon atoms. R ⁸ ,
R ⁹ and R ¹⁰ represent a hydrocarbon group having 18 or less carbon atoms which may have a substituent. Such onium salts are described in paragraphs [0010] to [00] of JP-A-10-39509.
35] as compounds of the general formulas (I) to (III).

The amount of the acid generator added is preferably 0.01 to 50% by weight based on the total solid weight of the photosensitive layer.
The content is more preferably 1 to 25% by weight, most preferably 0.5 to 20% by weight. If the amount is less than 0.01% by weight, an image may not be obtained. If the amount is more than 50% by weight, stains may occur on a non-image portion during printing when used as a lithographic printing original plate. Sometimes. The above-mentioned acid generators may be used alone or in combination of two or more.

[(F) Crosslinking Agent] Next, the crosslinking agent will be described. The following are mentioned as a crosslinking agent. (I) Aromatic compound substituted with hydroxymethyl group or alkoxymethyl group (ii) Compound having N-hydroxymethyl group, N-alkoxymethyl group or N-acyloxymethyl group (iii) Epoxy compound

Hereinafter, the compounds (i) to (iii) will be described in detail. Examples of the (i) aromatic compound substituted with a hydroxymethyl group or an alkoxymethyl group include an aromatic compound or a heterocyclic compound poly-substituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. . However, resinous compounds obtained by condensation polymerization of phenols and aldehydes known as resol resins under basic conditions are also included. Among aromatic compounds or heterocyclic compounds poly-substituted with a hydroxymethyl group or an alkoxymethyl group, a compound having a hydroxymethyl group or an alkoxymethyl group at a position adjacent to the hydroxy group is preferable. Further, among aromatic compounds or heterocyclic compounds poly-substituted with an alkoxymethyl group, a compound having an alkoxymethyl group of 18 or less carbon atoms is preferable, and the following general formula (1)
Compounds represented by (4) to (4) are more preferred.

[0077]

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[0078]

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In the general formulas (1) to (4), L _{1 to} L
Each ₈ independently represents a hydroxymethyl group or an alkoxymethyl group substituted with an alkoxy group having 18 or less carbon atoms, such as methoxymethyl and ethoxymethyl. These crosslinking agents are preferred in that they have high crosslinking efficiency and can improve printing durability.

(Ii) As the compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group, European Patent Publication (hereinafter referred to as “EP-
A ". No. 0,133,216, German Patent Nos. 3,634,671 and 3,711,264, monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate, EP
-A No. 0,212,482 and the like. Among them, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups or N-acyloxymethyl groups are preferred, and N-alkoxymethyl derivatives are most preferred.

(Iii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds having one or more epoxy groups.
Reaction products of bisphenol A with epichlorohydrin, reaction products of low molecular weight phenol-formaldehyde resin with epichlorohydrin, and the like can be mentioned. In addition, U.S. Pat. No. 4,026,705, British Patent No. 1,
No. 5,39,192, and the epoxy resins described and used.

When the compounds (i) to (iii) are used as a crosslinking agent, the amount added is preferably from 5 to 80% by weight, more preferably from 10 to 75% by weight, based on the total solid weight of the photosensitive layer. Preferably, 20 to 70% by weight is most preferable.
If the addition amount is less than 5% by weight, the durability of the photosensitive layer of the obtained image recording material may decrease, and if it exceeds 80% by weight, the storage stability may decrease.

In the present invention, (iv)
A phenol derivative represented by the following general formula (5) can also be suitably used.

[0084]

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In the general formula (5), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. From the viewpoint of availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. The substituent is preferably a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, or the like.

Among the above, in that high sensitivity can be achieved,
Ar ¹ represents an unsubstituted benzene ring or naphthalene ring, or a halogen atom, a hydrocarbon group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, an alkylthio group having 6 or less carbon atoms, or a nitro group. And a benzene ring or a naphthalene ring having such substituents.

[(G) Alkaline Water-Soluble Polymer Compound] Examples of the alkali water-soluble polymer compound that can be used in the crosslinked layer according to the present invention include a novolak resin and a polymer having a hydroxyaryl group in a side chain. Examples of the novolak resin include resins obtained by condensing phenols and aldehydes under acidic conditions.

Among them, for example, novolak resins obtained from phenol and formaldehyde, novolak resins obtained from m-cresol and formaldehyde, novolak resins obtained from p-cresol and formaldehyde, novolak resins obtained from o-cresol and formaldehyde, octylphenol Novolak resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol (m-, p-, o- or m- / p)
-, M- / o-, o- / p-) and a novolak resin obtained from formaldehyde or phenol and paraformaldehyde as raw materials.
A high molecular weight novolak resin having a high ortho-bonding ratio obtained by reacting under high pressure in a closed state without using a catalyst is preferred. The novolak resin has a weight average molecular weight of 800 to
300,000 and number average molecular weight of 400-60,00
A suitable one may be selected from zero and used according to the purpose.

Further, a polymer having a hydroxyaryl group in the side chain is also preferable, and examples of the hydroxyaryl group in the polymer include an aryl group having one or more OH groups bonded thereto. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group and the like. Among them, a phenyl group or a naphthyl group is preferable from the viewpoint of availability and physical properties. Examples of the polymer having a hydroxyaryl group in the side chain that can be used in the present embodiment include, for example, the following general formula (I)
Any one of the structural units represented by X) to (XII)
Mention may be made of polymers containing species. However, the present invention is not limited to these.

[0090]

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In the general formulas (IX) to (XII), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, or an aryloxy group having 10 or less carbon atoms. Also,
R ¹² and R ¹³ may combine and condense to form a benzene ring or a cyclohexane ring. R ¹⁴ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁵ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁶ is
It represents a single bond or a divalent hydrocarbon group having 10 or less carbon atoms.
X ¹ represents a single bond, an ether bond, a thioether bond, an ester bond or an amide bond. p represents an integer of 1 to 4. q and r each independently represent an integer of 0 to 3.

These alkali-soluble polymers include:
Details are described in Japanese Patent Application No. 11-320997, paragraphs [0130] to [0163], proposed by the present inventors. The alkali water-soluble polymer compound that can be used in the present embodiment may be used alone or in combination of two or more.

The amount of the alkali water-soluble polymer compound to be added is preferably from 5 to 95% by weight, more preferably from 10 to 95% by weight, most preferably from 20 to 90% by weight, based on the total solid content of the photosensitive layer. If the amount of the alkali water-soluble resin is less than 5% by weight, the durability of the photosensitive layer may be deteriorated. If the amount exceeds 95% by weight, an image may not be formed.

Examples of known recording materials to which the method of the present invention can be applied include negative-type image recording materials containing a phenol derivative described in JP-A-8-276558 and JP-A-7-306528. Negative recording material containing diazonium compound, Japanese Patent Application Laid-Open No. 10-20303
Patent Document 7 discloses a negative-type image-forming material utilizing a polymer having a heterocyclic group having an unsaturated bond in a ring and utilizing an acid-catalyzed crosslinking reaction. Can be applied to the acid crosslinked layer as the negative photosensitive layer according to the invention.

[Other Components] In the present invention, various compounds other than these may be further added, if necessary.
For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide can be suitably used. These colorants are preferably added because the image area and the non-image area can be easily distinguished after image formation. The amount of addition is 0.01 to 10% by weight based on the total solid content of the photosensitive layer coating solution.

In the present invention, when the photosensitive layer is a photopolymerizable layer, unnecessary thermal polymerization of a compound having a radically polymerizable ethylenically unsaturated double bond can be prevented during preparation or storage of a coating solution. For this purpose, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-
t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3
-Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% by weight based on the weight of the whole composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The added amount of the higher fatty acid derivative is preferably from about 0.1% to about 10% by weight of the whole composition.

The photosensitive layer coating solution of the present invention may contain a nonionic solvent such as that described in JP-A-62-251740 and JP-A-3-208514 in order to widen the stability of processing under development conditions. Surfactant, JP-A-59
An amphoteric surfactant as described in JP-A-121044 and JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene nonyl phenyl ether and the like.

Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N , N-betaine type (for example,
(Trade name: Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.).

The proportion of the above nonionic surfactant and amphoteric surfactant in the coating solution for the photosensitive layer is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer is added to the coating solution for the photosensitive layer according to the present invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and the like are used.

Image forming materials applicable to the method of the present invention,
That is, in order to produce a lithographic printing plate precursor, usually, each of the above-mentioned components required for a photosensitive layer coating solution is dissolved in a solvent and then applied onto a suitable support. As the solvent used here,
Ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-
2-propanol, 2-methoxyethyl acetate, 1
-Methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, Examples include toluene and water, but are not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight.

The coating amount (solid content) of the photosensitive layer on the support obtained after coating and drying varies depending on the application, but is generally 0.5 to 5.0 g / lithographic printing plate precursor.
m ² is preferred. As a method of applying, various methods can be used. For example, bar coater application, spin coating, spray application, curtain application, dip application,
Examples include air knife application, blade application, roll application, and the like. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive layer that performs the function of image recording deteriorate.

[Support] In the lithographic printing plate precursor to which the method of the present invention can be applied, the support to which the photosensitive layer can be applied is a dimensionally stable plate-like material such as paper, plastic ( Paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, butyric acid acetate) laminated with polyethylene, polypropylene, polystyrene, etc. Cellulose, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited. Preferred supports include a polyester film or an aluminum plate.

As the support used in the lithographic printing plate precursor according to the present invention, it is preferable to use an aluminum plate which is lightweight and has excellent surface treatment properties, workability and corrosion resistance. Aluminum materials used for this purpose include JIS 1050
Material, JIS 1100 material, JIS 1070 material, Al-
Mg-based alloy, Al-Mn-based alloy, Al-Mn-Mg-based alloy, Al-Zr-based alloy. Al-Mg-Si alloys and the like can be mentioned.

Suitable aluminum plates are a pure aluminum plate and the above-mentioned alloy plate containing aluminum as a main component and 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,
There are iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of the foreign element in the alloy is 10% by weight or less. As the aluminum plate, pure aluminum is preferable. However, since pure aluminum is difficult to produce due to refining technology, it may contain a slightly different element. As described above, the composition of the aluminum plate is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate is preferably about 0.1 to 0.6 mm, and 0.15 to 0.4 mm.
mm is more preferable, and 0.2 to 0.3 mm is particularly preferable.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. 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.

The aluminum plate thus roughened is
Alkaline etching treatment and neutralization treatment as necessary
After removal, if necessary, the water retention and abrasion resistance of the surface can be increased.
Anodizing treatment is performed for the purpose. Anodizing, by anodizing
1.0 g / m ^TwoThe above is preferred. Anodic acid
1.0 g / m^TwoIf less than, press life
Is insufficient or used as a lithographic printing plate
Indicates that the non-image area is easily scratched and
So-called "scratch stain" that ink adheres to the surface
Sometimes. After being subjected to the anodizing treatment,
The surface of the minium is subjected to a hydrophilic treatment if necessary.
You.

Further, such an aluminum support is treated with an organic acid or a salt thereof after anodizing treatment, or
An undercoat layer applied to a photosensitive layer can be applied for use.

An intermediate layer for improving the adhesion between the support and the photosensitive layer may be provided. To improve adhesion,
Generally, the intermediate layer is made of a diazo resin or a phosphoric acid compound adsorbed on aluminum, for example. The thickness of the intermediate layer is arbitrary, and must be a thickness capable of performing a uniform bond-forming reaction with the upper photosensitive layer upon exposure. Normal,
The dry solid has a good coating ratio of about 1 to 100 mg / m ² ,
5-40 mg / m ² are particularly good. The usage ratio of the diazo resin in the intermediate layer is 30 to 100%, preferably 60 to 100%.

After the above-mentioned treatment or undercoating is applied to the surface of the support, a back coat is provided on the back surface of the support, if necessary. As such a back coat, a coating layer comprising a metal oxide obtained by hydrolysis and polycondensation of an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174 is used. It is preferably used.

The preferred characteristics of the lithographic printing plate support are center line average roughness of 0.10 to 1.2 μm. If it is less than 0.10 μm, the adhesion to the photosensitive layer is reduced,
Significant reduction in printing durability occurs. If it is larger than 1.2 μm, the stain on printing will be deteriorated. Further, the color density of the support is 0.15 to 0.5 as a reflection density value.
65, and when it is whiter than 0.15, the halation at the time of image exposure is too strong and hinders image formation.
When it is darker than 0.65, the image is difficult to see in the plate inspection work after development, and the plate inspection property is extremely poor.

As described above, a negative type lithographic printing plate precursor to which the method of the present invention can be applied can be prepared.
This lithographic printing plate precursor can be recorded with an infrared laser. Also, thermal recording with an ultraviolet lamp or a thermal head is possible. In the present invention, a wavelength of 760 nm to 1
It is preferable that the image is exposed by a solid-state laser and a semiconductor laser that emit infrared light of 200 nm. The output of the laser is preferably 100 mW or more, and in order to shorten the exposure time, it is preferable to use a multi-beam laser device. Further, the exposure time per pixel is preferably within 20 μsec. The energy applied to the recording material is preferably from 10 to 300 mJ / cm ² .

After exposure with an infrared laser, the lithographic printing plate precursor is preferably developed with water or an aqueous alkaline solution. Here, when applying the plate making method of the present invention,
It controls the rotation speed of the transport roller of the washing section as described above.

When an alkaline aqueous solution is used as the developer, the developer and the replenisher according to the method of the present invention include:
A conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium,
Same ammonium, sodium hydroxide, same ammonium,
And inorganic alkali salts such as the same potassium and the same lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used. These alkali agents are used alone or in combination of two or more.

Further, when developing using an automatic developing machine, the same solution as the developing solution or an aqueous solution (replenishing solution) having a higher alkali strength than the developing solution is added to the developing solution so that the developing solution can be kept in the developing tank for a long time. It is known that a large amount of a lithographic printing plate precursor can be processed without replacing the developer. This replenishment method is also preferably applied in the present invention. Even when this replenishment is performed, the control according to the plate making method can be applied as needed.

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 increasing the ink affinity of the printing plate image area. . Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred organic solvents include benzyl alcohol and the like. It is also preferable to add polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof. Further, non-reducing sugars such as arabit, sorbit, and mannitol can also be added.

Further, the developing solution and the replenisher may contain, if necessary, an inorganic salt-based reducing agent such as hydroquinone, resorcin, sodium or potassium sulfite or bisulfite, an organic carboxylic acid, an antifoaming agent, a hard water Softeners can also be added.

The printing plate developed using the above-described developing solution 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. Later, it is used for printing.

In recent years, in the plate making and printing industries, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally includes a developing section,
It consists of a post-processing section including a washing section and a finisher section,
It is equipped with a device for transporting printing plate material, each processing solution tank and a spray device, and develops processing by spraying each processing solution pumped up by a pump from a spray nozzle while transporting the exposed printing plate horizontally. is there. The plate making method of the present invention can be suitably applied to such an automatic developing machine. Recently, a method is also known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like. In addition, the electric conductivity can be detected by a sensor and replenished automatically. Even in such an automatic developing machine, a lithographic printing plate having more stable quality can be obtained by applying the plate making method of the present invention for controlling the rotation speed of the transport roller in the washing section. In addition, the plate making method of the present invention can be applied to a developing device of a so-called disposable processing method in which processing is performed with a substantially unused processing solution.

The planographic printing plate obtained as described above is
After applying the desensitized gum if desired, it can be subjected to a printing process. The lithographic printing plate on which an image is formed through a predetermined process by applying the method of the present invention can be maintained in a uniform quality, and thus is applied to an offset printing machine or the like, and is suitably used for printing a large number of sheets. .

[0122]

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) <Synthesis of crosslinking agent [KZ-9]> 1- [α-methyl-α-
(4-hydroxyphenyl) ethyl] -4- [α, α-
Bis (4-hydroxyphenyl) ethyl] benzene
It was reacted with formalin in aqueous potassium hydroxide solution.
The reaction solution was acidified with sulfuric acid, crystallized, and further recrystallized from methanol to give a crosslinking agent [KZ-
9]. The purity was measured by reverse phase HPLC to be 92%.

[0123]

Embedded image

<Acquisition of Binder Polymer [BP-1]> Poly (p-hydroxystyrene) and Marca Linker MS-4P (trade name) manufactured by Maruzen Petrochemical Co., Ltd. were obtained, and [BP-1] and did.

<Preparation of Support> Al 0.30 mm thick
Trichlorethylene cleaning of minium plate (material 1050)
And degrease, then use a nylon brush and 400 mesh
Use a miston-water suspension and grain the surface,
It was washed with water. This plate is heated at 45 ° C in 25% sodium hydroxide
Immersed in aqueous solution for 9 seconds, etched and washed with water,
2% HNO _ThreeFor 20 seconds and washed with water. At this time
The amount of etching of the grained surface is about 3g / m^TwoSo
Was. Next, the plate was set to 7% H_TwoSO_FourCurrent density as electrolyte
Degree 15A / dm^Two3g / m^TwoDC anodized film
After drying, it was washed with water and dried. Next, place this aluminum plate
The undercoat solution was applied and dried at 80 ° C. for 30 seconds. Dry
Later coverage is 10 mg / m^TwoMet.

<Undercoat liquid>-β-alanine ... 0.1 g-Phenylphosphonic acid-0.05 g-Methanol-40 g-Pure water-60 g

Next, the following solution [P-1] was prepared, and this solution was applied to the above-mentioned primed aluminum plate.
After drying at 100 ° C for 1 minute, the negative type lithographic printing plate precursor [P-
1] was obtained. The coating amount after drying was 1.5 g / m ² .

<Solution [P-1]> Nonylphenol (mixture of isomers, manufactured by Aldrich) 0.05 g Acid generator SH-1 0.3 g Crosslinker KZ-9 ··· 0.5 g · Binder polymer [BP-1] ··· 1.5 g · Infrared absorber [IK-1] ··· 0.07 g · AIZEN SPILON BLUE C-RH ··· 0.035 g (Manufactured by Hodogaya Chemical Co., Ltd.)-Fluorosurfactant-0.01 g (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.)-Methyl ethyl ketone-12 g-Methyl alcohol- 10 g 1-methoxy-2-propanol 8 g

The acid generator [SH-
1] and the structure of the infrared absorbent [IK-1] are shown below.

[0130]

Embedded image

Next, 20 parts of an alkaline developing solution A (pH about 13) having the following composition was placed in a developing tank of a commercially available automatic developing machine LP-900H (manufactured by Fuji Photo Film Co., Ltd.) having an immersion developing tank. One liter was charged and kept at 30 ° C. LP
In the second bath of -900H, 8 liters of tap water and in the third bath, FP-2W (manufactured by Fuji Photo Film Co., Ltd.):
8 liters of a finishing gum solution diluted with water = 1: 1 was charged.

[Composition of Alkaline Developing Solution A] 4.0% by weight of SiO ₂ · K ₂ O (K ₂ O / SiO ₂ = 1.1 (molar ratio)) 0.5% by weight of citric acid Polyethylene Glycol (weight average molecular weight = 1000) 0.5% by weight ・ Water 95.0% by weight

The exposed lithographic printing plate [P-1] (650 m
mx 550mm x 0.24mm thickness) LP-900H
Each time one plate development processing was performed, processing was performed while replenishing 35 cc of a development replenisher B having the following composition.

[Composition of Development Replenisher B] SiO ₂ · K ₂ O 5.0% by weight (K ₂ O / SiO ₂ = 1.1 (molar ratio)) Citric acid 0.6% by weight Polyethylene glycol (Weight average molecular weight = 1000) 0.6% by weight ・ water 93.8% by weight

The planographic printing plate [P-1] (650 mm × 55)
0mm x 0.3mm thickness) Plate setter Luxce
1 Using a Platesetter 9000 CTP (manufactured by Fuji Photo Film Co., Ltd.) (output: 270 mW, rotation speed: 1000 rpm, resolution: 2438 dpi),
Subsequently, the transfer oven SPC Mini EV34
(Trade name: manufactured by Wisconsin), the plate was heated at a plate surface temperature of 146 ° C. (295 ° F.) for 75 seconds, and then subjected to 100 plate developments per day by the automatic developing machine shown in FIG. Developed for 3 months.

In the first embodiment, the rotation speed of the transport roller, which is provided at the entrance and the exit of the rinsing section and comes into contact with the surface of the photosensitive layer of the lithographic printing plate, is set to 105% with the transport speed of the lithographic printing plate being 100%. A continuous plate-making process was performed under the control described below. In the continuous processing, the non-image area of the photosensitive layer of the lithographic printing plate was observed near the exit of the washing section, and the occurrence of residual film and the presence or absence of deposits were evaluated. No deposit of the photosensitive layer was observed on the non-image area of the lithographic printing plate obtained by the plate making method of the present invention, and the lithographic printing plate could be stably processed for 90 days. According to the plate making method of the present invention, plate making could be stably performed for 90 days. As will be apparent from Example 2 described below, when the processing was performed with the transport speed equal to the transport speed of the washing section roller, the deposit adhered to the non-image area on the 20th day. Without using, the automatic developing machine could operate only for 20 days under the condition that a lithographic printing plate in a favorable state could be obtained. This indicates that the plate making method of the present invention is effective.

(Example 2) A lithographic printing plate precursor similar to that of the above-mentioned Example 1 was used under exposure under the same conditions. In the present Example 2, the lithographic printing plate precursor initially provided at the entrance and exit of the washing section was used. The rotational speed of the transport roller contacting the photosensitive layer surface of the printing plate and the transport speed of the lithographic printing plate are matched (that is, the transport speed of the lithographic printing plate is 100%, and the rotational speed of the transport roller is also 100%). A continuous plate making process is performed, and when the deposit of the photosensitive layer adheres to the non-image area of the obtained lithographic printing plate, it comes into contact with the surface of the photosensitive layer of the lithographic printing plate provided at the entrance and the exit of the washing section. Plate making was performed by changing the rotation speed of the conveying rollers to be 102% to 107% with the conveying speed of the planographic printing plate being 100%. According to the plate making method of the present invention, 9
The plate making process of the lithographic printing plate was stably performed for 0 days. 20
On the day, three deposits having a diameter of about 0.5 to 2 mm were confirmed to have adhered to the non-image area, and the rotation speed of the transport roller disposed at the entrance of the washing section was adjusted to the level of the lithographic printing plate. When the transfer speed was 2% faster (102%) than the transfer speed, no deposits were found on the non-image areas. On the 28th day, it was confirmed that two precipitates having a diameter of about 0.5 to 2 mm had adhered to the non-image area. Therefore, the rotation speed of the transport roller provided at the outlet of the rinsing unit was adjusted to the rotation speed of the lithographic printing plate. When the transfer speed was 3% faster than the transfer speed, the adhesion of the precipitate in the non-image area was not observed. On the 40th day, it was confirmed that five precipitates having a diameter of about 0.5 to 2 mm had adhered to the non-image area. Therefore, the rotation speed of the transport roller provided at the entrance of the rinsing unit was adjusted to the rotation speed of the lithographic printing plate. When the transfer speed was increased by 5% from the transfer speed, no deposits were found on the non-image areas. Further, on the 58th day, three deposits having a diameter of about 0.5 to 2 mm were confirmed to have adhered to the non-image area, and the rotation speed of the transport roller provided at the outlet of the washing section was reduced by lithographic printing. When the transfer speed was 6% faster than the plate conveying speed, the adhesion of the deposit in the non-image area was not observed. On the 75th day, it was confirmed that three precipitates having a diameter of about 0.5 to 2 mm adhered to the non-image area. Therefore, the rotation speed of the transport roller provided at the outlet of the washing section was adjusted to the rotation speed of the lithographic printing plate. When the transfer speed was 7% faster than the transfer speed, the adhesion of the precipitate in the non-image area was not observed. Thereafter, until the 90th day, a stable development state was obtained.

According to the plate making method of the present invention, plate making could be performed stably for 90 days. In addition, since the deposit adhered to the non-image area on the 20th day, unless the plate making method of the present invention was used, the automatic developing machine could operate only for 20 days under the condition that a lithographic printing plate in a preferable state could be obtained. Will be. This indicates that the plate making method of the present invention is effective.
It was also found that effective control can be performed by adjusting the rotation speed of either the transport roll at the entrance of the washing section or the transport roll at the exit as a countermeasure against the remaining film of the photosensitive layer or the adhesion of the deposit.

(Example 3) [Formation of support] 99.5% or more of aluminum and F
e 0.30%, Si 0.10%, Ti 0.02%, C
u A molten metal of JIS A1050 alloy containing 0.013% was subjected to a cleaning treatment and cast. In the cleaning treatment, a degassing treatment was performed to remove unnecessary gases such as hydrogen in the molten metal, and a ceramic tube filter treatment was performed. The casting was performed by DC casting. The solidified 500 mm thick ingot was shaved by 10 mm from the surface, and homogenized at 550 ° C. for 10 hours to prevent the intermetallic compound from becoming coarse. Next, after hot rolling at 400 ° C. and intermediate annealing in a continuous annealing furnace at 500 ° C. for 60 seconds, cold rolling was performed to obtain a rolled aluminum sheet having a sheet pressure of 0.30 mm. The center line average surface roughness Ra after cold rolling was controlled to 0.2 μm by controlling the roughness of the rolling roll. Then, it was subjected to a tension leveler to improve the flatness.

Next, a surface treatment for preparing a lithographic printing plate support was performed. First, in order to remove the rolling oil on the surface of the aluminum plate, a degreasing treatment was performed with a 10% aqueous sodium aluminate solution at 50 ° C. for 30 seconds, and a 30% sulfuric acid aqueous solution was neutralized at 50 ° C. for 30 seconds, and a smut removal treatment was performed.

Next, in order to improve the adhesiveness between the support and the photosensitive layer and to impart water retention to the non-image area, a so-called graining treatment for roughening the surface of the support was performed. 1%
Aqueous solution containing 0.5% nitric acid and 0.5% aluminum nitrate
° C while flowing an aluminum web in an aqueous solution, the anode-side electricity quantity 240 C / dm ² with an alternating waveform having a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect feeding cell.
Electrolytic graining was performed by giving ² . Then 10%
Perform an etching treatment with a sodium aluminate aqueous solution at 50 ° C for 30 seconds, and neutralize with a 30 %% sulfuric acid aqueous solution at 50 ° C for 30 seconds.
Smut removal processing was performed.

In order to further improve abrasion resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. An anodic oxide film of 2.5 g / m ^{2 is} obtained by performing an electrolytic treatment with a direct current of 14 A / dm ² by an indirect power supply cell while carrying an aluminum web through the electrolyte using a 20% aqueous solution of sulfuric acid at 35 ° C. as an electrolyte. It was created.

Thereafter, a silicate treatment was performed to ensure hydrophilicity as a non-image portion of the printing plate. The treatment was carried out by maintaining a 1.5% aqueous solution of sodium silicate No. 3 at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and further washing with water. S
The attached amount of i was 10 mg / m ² . Ra (center line surface roughness) of the support thus prepared was 0.25 μm.

[Undercoating] Next, the following undercoating solution was applied to this aluminum support with a wire bar, and dried at 90 ° C. for 30 seconds using a hot-air drying apparatus. The coating amount after drying was 10 mg / m ² .

<Undercoat liquid> 0.1 g of a copolymer of ethyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt in a molar ratio of 75:15 0.1 g 2-aminoethylphosphonic acid 0.1 g 50 g of methanol 50 g of ion exchange water

[Photosensitive layer] Next, the following solution [P-2] was prepared.
To the primed aluminum plate
And then apply 45 ° C at 115 ° C with a hot air drier.
After drying for 2 seconds, a negative type lithographic printing plate precursor [P-2] was obtained.
The coating amount after drying is 1.2 to 1.3 g / m ^TwoWithin the range
Was.

<Solution [P-2]> • Infrared absorber [IR-6] 0.08 g • Onium salt [OI-6] 0.30 g • Dipentaerythritol hexaacrylate 1.00 g • Allyl methacrylate and methacrylic acid 80:20 molar ratio copolymer (weight average molecular weight 120,000) 1.00 g ・ Naphthalene sulfonate of Victoria Pure Blue 0.04 g ・ Fluorosurfactant 0.01 g (MegaFac F-176, Dainippon Ink) (Manufactured by Chemical Industry Co., Ltd.)-Methyl ethyl ketone 9.0 g-Methanol 10.0 g-1-methoxy-2-propanol 8.0 g

The infrared absorbent [I] used in the solution [P-2]
The structures of R-6] and the onium salt [OI-6] are shown below.

[0149]

Embedded image

After the exposure, development processing was continuously performed using an automatic developing machine Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As a developing solution, a 1: 1 aqueous dilution of DN-3C manufactured by Fuji Photo Film Co., Ltd. was used for both the charging solution and the replenishing solution. The temperature of the developing bath was 30 ° C. The development time was 20 seconds.
In addition, the finisher was manufactured by Fuji Photo Film Co., Ltd.
A 1: 1 dilution of N-6 in water was used.

The lithographic printing plate [P-2] (650 mm × 55)
0 mm x 0.3 mm thick) Trendsetter 3 made by Creo equipped with a water-cooled 40 W infrared semiconductor laser
At 244 VFS, output 9 W, external drum rotation speed 210
rpm, plate energy 100 mJ / cm ² , resolution 2
Exposure was performed under the conditions of 400 dpi, and subsequently, a transfer oven SPC Mini EV34 (trade name: Wiscons)
The plate surface temperature is 146 ° C.
And then heat-treated for 75 seconds, developed 100 plates per day, and developed for 3 months.

In the third embodiment, the rotation speed of the transport roller, which is provided at the entrance and the exit of the rinsing section and comes into contact with the surface of the photosensitive layer of the lithographic printing plate, is 105%, with the transport speed of the lithographic printing plate being 100%. A continuous plate-making process was performed under the control described below. In the continuous processing, the non-image area of the photosensitive layer of the lithographic printing plate was observed near the exit of the washing section, and the occurrence of residual film and the presence or absence of deposits were evaluated. No deposit of the photosensitive layer was observed on the non-image area of the lithographic printing plate obtained by the plate making method of the present invention, and the lithographic printing plate could be stably processed for 90 days. According to the plate making method of the present invention, plate making could be stably performed for 90 days. As will be apparent from Example 4 described later, when the processing was performed with the transport speed equal to the transport speed of the rinsing section roller, the deposit adhered to the non-image area on the 25th day. If no lithographic printing plate was used, the automatic developing machine could only be operated for 25 days under the condition that a lithographic printing plate in a favorable state could be obtained. This shows that the plate making method of the present invention is also effective for a negative type lithographic printing plate having a photopolymerizable photosensitive layer.

(Example 4) A lithographic printing plate precursor similar to that of the above-mentioned Example 3 was used under exposure under the same conditions. In Example 4, a lithographic printing plate precursor initially provided at the entrance and exit of the washing section was used. The rotational speed of the transport roller contacting the photosensitive layer surface of the printing plate and the transport speed of the lithographic printing plate are matched (that is, the transport speed of the lithographic printing plate is 100%, and the rotational speed of the transport roller is also 100%). A continuous plate making process is performed, and when the deposit of the photosensitive layer adheres to the non-image area of the obtained lithographic printing plate, it comes into contact with the surface of the photosensitive layer of the lithographic printing plate provided at the entrance and the exit of the washing section. Plate making was performed by changing the rotation speed of the conveying roller to 95% to 107% with the conveying speed of the lithographic printing plate as 100%. According to the plate making method of the present invention, 90
The plate making process of the lithographic printing plate was able to be performed stably for a day.

In the continuous processing, the non-image area of the photosensitive layer of the lithographic printing plate was observed near the exit of the washing section, and the occurrence of residual film and the presence or absence of deposits were evaluated. On the 25th day, it was confirmed that three precipitates having a diameter of about 0.5 to 2 mm had adhered to the non-image area, and the rotation speed of the transport roller disposed at the entrance of the washing section was changed to the lithographic printing plate. When the transfer speed was 2% faster than the transfer speed (102%), no deposits were found on the non-image areas. On day 32, the non-image area has a diameter of 0.5 to
Since it was confirmed that two precipitates of about 2 mm were adhered, the rotation speed of the transport roller disposed at the outlet of the washing section was increased by 3% from the transport speed of the lithographic printing plate. No deposits were observed. On the 42nd day, it was confirmed that three precipitates having a diameter of about 0.5 to 2 mm had adhered to the non-image area. Therefore, the rotation speed of the transport roller provided at the outlet of the washing section was adjusted to the rotation speed of the lithographic printing plate. 5% from transport speed
As a result, the deposition of the precipitate in the non-image area was no longer observed. Further, on the 55th day, the non-image portion has a diameter of 0.5 to 2 mm.
Since it was confirmed that three precipitates of about mm were attached, the rotation speed of the conveying roller provided at the entrance of the washing section was increased by 7% from the conveying speed of the lithographic printing plate. No deposits were observed. On the 70th day, it was confirmed that two precipitates having a diameter of about 0.5 to 2 mm had adhered to the non-image area. Therefore, the rotation speed of the transport roller provided at the entrance of the rinsing unit was adjusted to the lithographic printing plate. When the transfer speed was 5% slower than the transfer speed (95%), the adhesion of the deposit in the non-image area was not observed. Thereafter, until the 90th day, a stable development state was obtained.

According to the plate making method of the present invention, development processing could be performed stably for 90 days. In addition, since the deposit adhered to the non-image area on the 25th day, unless the plate making method of the present invention was used, the automatic developing machine could operate only for 25 days under the condition that a lithographic printing plate in a preferable state could be obtained. Will be. This shows that the plate making method of the present invention is also effective for a negative type lithographic printing plate having a photopolymerizable photosensitive layer.

[0156]

According to the method of making a lithographic printing plate according to the present invention, the lithographic printing plate is applied to a negative type image forming material for infrared laser for direct plate making to maintain the quality of the lithographic printing plate constant and to obtain a uniform and excellent image. Can be manufactured continuously.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing a typical automatic developing apparatus applicable to the plate making method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Automatic developing apparatus 12 Lithographic printing plate precursor (plate material) 16 Drying part 18 Developing part 24 Rinsing part 26 Finisher part 32 Conveying roller of lithographic printing plate precursor 54 Conveying roller provided at the inlet of the rinsing part 56 Disposed at the outlet of the rinsing part Transport rollers installed

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) G03F 7/038 601 G03F 7/038 601 7/26 501 7/26 501 7/30 501 7/30 501F Terms (reference) 2H025 AA00 AB03 AC08 AD01 BC31 BC51 BE00 CA43 CB13 CB14 CB43 CC20 FA03 FA14 FA17 2H084 AA14 AA40 AE07 AE08 BB02 BB13 CC05 2H096 AA00 AA07 AA08 BA05 BA06 BA20 EA04 GA22 GA24

Claims (2)

[Claims] A negative lithographic printing plate precursor having a photosensitive layer containing an infrared absorbing agent, a compound capable of generating a radical or an acid by heat, and a polymerizable compound or a crosslinkable compound on a support, A method for making a lithographic printing plate using an automatic developing device having a developing unit, a washing unit, a finisher unit, and a lithographic printing plate conveying member, wherein the plate is provided at an inlet and / or an outlet of a washing unit of the automatic developing device. A lithographic printing plate, wherein a transport roller of the lithographic printing plate is disposed so as to contact the photosensitive layer of the lithographic printing plate, and a rotation speed of the transport roller of the lithographic printing plate is different from a transport speed of the lithographic printing plate. Plate making method. 2. After exposing a negative type lithographic printing plate precursor having a photosensitive layer containing an infrared absorber, a compound generating a radical or an acid by heat, and a polymerizable compound or a crosslinkable compound on a support, A method of making a lithographic printing plate using an automatic developing device including a developing unit, a washing unit, a finisher unit, and a lithographic printing plate conveying member, wherein the lithographic printing plate is provided at an outlet of a washing unit of the automatic developing device. An activity evaluation step of detecting a decrease in the activity of the developer by observing the generation of a residual film of the photosensitive layer in the non-image area and the adhesion of a precipitate; and the activity of the developer in the activity evaluation step. When the decrease of the lithographic printing plate is detected, the rotation speed of the conveying roller disposed at the entrance and / or the exit of the washing section of the automatic developing device so as to come into contact with the photosensitive layer of the lithographic printing plate is set to the conveying speed of the lithographic printing plate. Adjustment to control differently Process for making a lithographic printing plate characterized by having a degree, the.