JP2003270780A - Photosensitive planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate excellent in sensitivity, printing resistance, stain recovery and dot reproducibility. <P>SOLUTION: In the photosensitive planographic printing plate having a photopolymerizable photosensitive layer comprising an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator and a polymeric binder, two or more sensitizing dyes are comprised in the photopolymerizable photosensitive layer and the relation among the wavelength λ1abs (nm) at which the first sensitizing dye has absorption maximum, the wavelength λ1emi (nm) at which the first sensitizing dye has emission maximum, the wavelength λ2abs (nm) at which the second sensitizing dye has absorption maximum and the maximum wavelength λe (nm) of exposure satisfy the formulae λ1abs-50≤λe≤λ1abs+50 and λ1emi-25≤λ2abs≤λ1emi+25. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate, and more particularly to a photosensitive lithographic printing plate excellent in sensitivity, printing durability, stain recovery and dot reproducibility.

[0002]

2. Description of the Related Art A photosensitive lithographic printing plate (hereinafter also referred to as a lithographic printing plate) in which a photopolymerizable layer and a protective layer are laminated on a support which has been subjected to a hydrophilic surface treatment has been known. Further, particularly in recent years, in order to rapidly obtain a high-resolution lithographic printing plate, and for the purpose of filmlessness, digital exposure is performed based on image information using a laser, and this is developed to produce a lithographic printing plate. The method to do is generalized.

For example, a light source is modulated by an output signal from an electronic plate making system, an image processing system or the like or an image signal transmitted through a communication line or the like, and the photosensitive material is directly scanned and exposed to form a printing plate. The system is known.

The photopolymerizable layer is generally composed of an acrylic monomer, an alkali-soluble resin and a photopolymerizable initiator, and optionally a sensitizing dye for adjusting the wavelength (especially when laser writing). Is known to contain.

As a light source for exposing / making a photopolymerization type lithographic printing plate, an Ar laser (488 nm) or FD-YA is used.
A long wavelength visible light source such as a G laser (532 nm) is used. More recently, for example, InGaN
Of 350 nm to 450 n using a ZnSe-based material
A semiconductor laser that can continuously oscillate in the m range is in a practical stage. Scanning exposure systems that use these short-wave light sources are semiconductor lasers that can be manufactured inexpensively because of their structure.
It has the advantage of being able to build an economical system while having sufficient output. Furthermore, conventional FD-YAG
There is a possibility that a light-sensitive material having a short-wavelength light-sensitive area capable of working under a brighter safe light can be used as compared with a system using an Ar laser.

The most important problem among these is to improve the sensitivity of the light-sensitive material to light rays. It is well known that the photopolymerization initiating system generally has an ability to generate active radicals, whose sensitivity rapidly decreases with respect to light having a wavelength of 450 nm or more. Many proposals have hitherto been made for photopolymerizable photosensitive materials capable of being sensitive to light rays in the visible light region. For example, certain sensitive dyes described in U.S. Pat. No. 2,850,445, complex initiation system of dye and amine (Japanese Patent Publication No. 44-20189), combination system of hexaarylbiimidazole, radical generator and dye. (Japanese Patent Publication Sho 45-3
7377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-
No. 2528, JP-A-54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-8).
No. 4183), a system of substituted triazine and merocyanine dye (JP-A-54-151024), a system of 3-ketocoumarin and an activator (JP-A-52-112681, 58-1).
5503), biimidazole, styrene derivative, thiol system (JP-A-59-140203), organic peroxide and dye system (JP-A-59-140203, 59-140203).
189340), a system of a dye having a rhodanine skeleton and a radical generator (JP-A-2-244050), a system of an aliphatic amino acid salt and a pyromethene borate sensitizing dye (JP-A-200).
0-250206) and the like.

The fact that titanocene is effective as a photopolymerization initiator is disclosed in JP-A Nos. 59-152396 and 61-61.
No. 151197, No. 63-10602, No. 63-4
No. 1484 and JP-A No. 3-12403, and examples of use as a combination system include titanocene and 3-
A system of ketocoumarin dyes (JP-A-63-221110)
No.), a system in which a titanocene and a xanthene dye are combined with an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group (JP-A-4-221958,
JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061, JP-A-6-295061).
328505) and the like.

However, although these prior arts are certainly effective for visible light, they cannot be put to practical use due to problems such as insufficient sensitivity.

Further, in the photopolymerization type lithographic printing plate, usually, after image exposure and, if necessary, heat treatment, washing with water for removing the protective layer, developing treatment for dissolving and removing unexposed portion, washing treatment. Then, a finisher gum treatment for making the non-image area hydrophilic is performed to obtain a lithographic printing plate. At this time,
When the protective layer component is not sufficiently removed from the exposed portion of the photosensitive layer, or when the finisher gum component is firmly formed in the image portion, ink inking is poor at the start of printing and the amount of waste paper increases. In some cases, JP-A-10-3155
Japanese Unexamined Patent Publication No. 98 etc. discloses a technique for controlling the residual solvent amount in the photosensitive layer before applying the protective layer, but these methods have been insufficient.

On the other hand, as a developing solution for a lithographic printing plate, in order to completely remove the photosensitive layer in the non-image area, that is, to perform development, it is usually used as an aqueous alkaline developing solution having a pH of 12.5.
It was generally used in the above. However, in recent years, treatment with an alkaline developer having a lower pH has been desired from the viewpoint of workability, safety, environmental suitability and the like.

Under these circumstances, with respect to the conventional photopolymerization type lithographic printing plate, problems such as an increase in developability and the amount of development sludge become apparent in the development with such an alkaline developing solution having a low pH, and on the other hand, it is low. When it is attempted to enhance the developability of the photosensitive polymer layer by developing with a developing solution having a pH, there is a problem that printing durability and ink receptivity deteriorate.

When producing a photopolymerization type lithographic printing plate, the coating material is generally dissolved or dispersed in an organic solvent,
It is applied by wire bar coating, roll coating, die coating, etc., and dried under predetermined drying conditions to finish as a lithographic printing plate. At that time, the coating solvent used is methyl ethyl ketone, 1-methoxy-2-propanol, cyclopentanone, cyclohexanone, etc. as described in JP-A-8-272085, or JP-A-9-132738. As has been done,
Diethoxymethane, or ethanol, butanol, cyclopentanone described in JP-A-10-315598,
Organic solvents such as acetone are known.

However, when the lithographic printing plate thus produced is subjected to a laser exposure and a developing treatment, the developing solution is not exchanged for a long period of time, and when the running treatment is carried out by replenishing the developing solution appropriately, the developing solution is added to the developing solution. Precipitates (sludge) were generated, often causing spot-like stains on non-printing areas, light stains on non-printing areas, or entanglement of ink in halftone areas during printing, causing printing problems. . Similarly, during long-term running, changes in halftone dots, particularly small dots, changes in halftone dots in shadow portions, and changes in thin line portions were caused, and printed matter of stable quality could not be obtained. This tendency is particularly strong when printing is performed using a printing ink that does not use petroleum-based volatile organic compounds as an environmental measure.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive lithographic printing plate excellent in sensitivity, printing durability, stain recovery and halftone dot reproducibility.

[0015]

The above object of the present invention can be achieved by the following means.

1. On a support having a hydrophilic surface, an addition-polymerizable ethylenic double bond-containing monomer, in a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing a photopolymerization initiator and a polymer binder, The photopolymerizable photosensitive layer contains two or more sensitizing dyes, and the absorption maximum wavelength λ of the first sensitizing dye is λ.
1 abs (nm), maximum emission wavelength λ1 emi (nm)
And the absorption maximum wavelength λ2abs (nm) of the second sensitizing dye
And a relationship with the maximum wavelength λe (nm) of exposure satisfy the following formula:

Λ1abs-50 ≦ λe ≦ λ1abs + 50 λ1emi-25 ≦ λ2abs ≦ λ1emi + 25 1. On a support having a hydrophilic surface, an addition-polymerizable ethylenic double bond-containing monomer, in a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing a photopolymerization initiator and a polymer binder, A photosensitive lithographic printing plate comprising the compound represented by the general formula (1) as the ethylenic double bond-containing monomer.

3. On a support having a hydrophilic surface, an addition-polymerizable ethylenic double bond-containing monomer, in a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing a photopolymerization initiator and a polymer binder, A photosensitive lithographic printing plate comprising the compound represented by the general formula (2) as the ethylenic double bond-containing monomer.

4. 2. The photosensitive lithographic printing plate as described in 1 above, wherein the photopolymerizable photosensitive layer contains the compound represented by the general formula (1).

5. 2. The photosensitive lithographic printing plate as described in 1 above, wherein the photopolymerizable photosensitive layer contains the compound represented by the general formula (2).

The present invention will be described in detail below. As a result of earnest research, the present inventor, as described in claim 1, has two or more kinds of sensitizing dyes contained in the photopolymerizable photosensitive layer, and the absorption maximum wavelength λ1abs (nm) of the first sensitizing dye, emission. Maximum wavelength λ1
and the maximum absorption wavelength λ2 of the second sensitizing dye
It has been found that the effect of the present invention can be obtained by combining sensitizing dyes so that the relationship between abs (nm) and the maximum wavelength of exposure λe (nm) has a specific relationship.

Although the mechanism for these effects has not been fully clarified, the following is considered. The sensitizing dye excited by laser light or the like injects electrons or energy to the photopolymerization initiator (for example, titanocene), but when electron injection or energy transfer to the photopolymerization initiator is not possible, it fluoresces to the ground state. Returns and does not contribute to photopolymerization. At this time, by using two or more kinds of sensitizing dyes and making the second sensitizing dye that absorbs the fluorescence of the first sensitizing dye coexist, the second sensitizing dye becomes an excited state and a photopolymerization initiator. It is possible to increase the probability of electron injection into or energy transfer to.

Further, as described in claims 2 and 3, it was found that the effect of the present invention can be obtained by using an ethylenic double bond-containing monomer having a specific structure.

(Sensitizing Dye) The plurality of sensitizing dyes used in the present invention are the maximum absorption wavelength λ1abs of the first sensitizing dye.
(Nm), the emission maximum wavelength λ1emi (nm), the absorption maximum wavelength λ2abs (nm) of the second sensitizing dye, and the exposure maximum wavelength λe (nm) must satisfy the following formula. .

Λ1abs-50 ≦ λe ≦ λ1abs + 50 λ1emi-25 ≦ λ2abs ≦ λ1emi + 25 It is preferable that the sensitizing dye used in the present invention emits fluorescence due to the above estimation mechanism. It is presumed that the excited state of the fluorescent dye is relatively stable, and electron injection to the photopolymerization initiator or establishment of energy transfer is high.

Any sensitizing dye satisfying the above relationship can be used without particular limitation. As a specific example, EXC
Examples of laser dyes manufactured by ITON are listed in Tables 1 to 3, but not limited thereto.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

In addition to these, Japanese Patent Laid-Open No. 2000-9860
5, ibid 2000-147763, ibid 2000-2066
90, 2000-258910, 2000-309.
724, 2001-42524, 2001-100
412 and the sensitizing dyes described in
Dyes and the like from ar Probes can be used.

The wavelength range of the exposure light source is not limited, and infrared,
It may be visible light or ultraviolet light, but in the case of the combination of the sensitizing dyes of the present invention, especially FD-Y near 532 nm.
The effect is large in exposure to AG laser and violet laser near 400 nm, and is particularly remarkable in violet laser.

The absorption maximum wavelength and the emission maximum wavelength of the sensitizing dye can be measured by a usual measuring method. In the measurement of the present invention, the sensitizing dye is an organic solvent MEK (methyl ethyl ketone).
And dissolved at 25 ° C. The sensitizing dye is weighed in an amount such that the absorbance at the absorption maximum wavelength of the spectrum is 1.5 to 4 and dissolved in MEK. Those having a low solubility in MEK are measured while being kept low, or are dissolved by adding methanol, DMF or the like to MEK. The absorption spectrum is measured by
It measured using Hitachi spectrophotometer U-3300. The fluorescence spectrum was measured using a fluorescence / phosphorescence spectrophotometer LS55 manufactured by Perkin Elmer.

The closer the exposure maximum wavelength λe (nm) and the absorption maximum wavelength of the first sensitizing dye are, the more preferable, and the difference is 50.
When it exceeds nm, the sensitivity and printing durability are significantly deteriorated. Also, the first
It is preferable that the maximum emission wavelength of the sensitizing dye and the maximum absorption wavelength of the second sensitizing dye are close to each other. If the difference exceeds 25 nm, the sensitivity and printing durability are significantly deteriorated.

The type of sensitizing dye to be added may be two or more, and may be three, four or more. For example, when four types of sensitizing dyes 1 to 4 are added, the sensitizing dye 1 has a maximum emission wavelength rather than an emission maximum wavelength of the sensitizing dye 2, the sensitizing dye 3, and the sensitizing dye 4 that are close to each other. The emission maximum wavelength of the sensitizing dye 1 is close to the absorption maximum wavelength of the sensitizing dye 2, the emission maximum wavelength of the sensitizing dye 2 is close to the absorption maximum wavelength of the sensitizing dye 3, and the emission maximum wavelength of the sensitizing dye 3 is close to It is preferable to make the absorption maximum wavelength of the sensitizing dye 4 close.

In the present invention, the amount of the sensitizing dye added is preferably 0.1 to 10% by mass, and more preferably 1 to 6% by mass of the non-volatile components in the photopolymerizable photosensitive layer.

(Ethylene Double Bond-Containing Monomer) Next,
The ethylenic double bond-containing monomer represented by the general formula (1) used in the present invention will be described.

In the general formula (1), R ⁴ is (m-
When n) is 2 or more, they may be different from each other. m and n
Compounds having the same value of are preferred. R ⁴ is an alkyl group,
In the case of a hydroxyalkyl group, the carbon number is preferably 2-8, more preferably 2-4. When R ⁴ is an aryl group, it is preferably monocyclic or bicyclic, more preferably monocyclic,
And may be substituted with an alkyl group having up to 5 carbon atoms, an alkoxyalkyl group, or a halogen atom.

When R ¹ and R ² are an alkyl group or an alkoxyalkyl group, it preferably has 1 to 5 carbon atoms.

R ³ is preferably a methyl group. X ¹ is 4 to 10
Aliphatic or cycloaliphatic radicals having 4 carbon atoms are preferred.

X ² has 2 to 15 carbon atoms, of which up to 5 methylene groups may be replaced by oxygen atoms.

D ¹ and D ² may be the same or different,
And a 6-membered saturated heterocycle containing 2 nitrogen atoms is preferred.

When E is a saturated hydrocarbon group, it preferably has 2 to 6 carbon atoms, when E is an arylene group, a phenylene group is preferred, and when it is a cycloaliphatic group, a cyclohexylene group is preferred, In the case of a heterocyclic aromatic group, a 5- or 6-membered ring containing a nitrogen atom or a sulfur atom is preferable.

C is preferably 1. In order to obtain the compound represented by the general formula (1), when Q ¹ is N, n and m are the same value, and b is 1, an acrylate or alkyl acrylate having a hydroxyl group is prepared by a known method. Is reacted with the same mole of diisocyanate to react excess isocyanate groups with hydroxyalkylamine. When n is 3 and b is 0, it can be obtained by reacting a hydroxyalkylamine with an acrylate or alkyl acrylate having an isocyanate group.

In these reactions, it is preferable to use, for example, toluene, pyridine or methyl ethyl ketone as an inert solvent, and to add a quinone, particularly benzoquinone, in order to thermally stabilize the product.

Next, the ethylenic double bond-containing monomer represented by the general formula (2) used in the present invention will be described.

In the general formula (2), R ⁸ is (g-
When f) is 2 or more, they may be different from each other. g and f
Compounds having the same value of are preferred. R ⁸ is an alkyl group,
In the case of a hydroxyalkyl group, the carbon number is preferably 2-8, more preferably 2-4. When R ⁸ is an aryl group, it is preferably monocyclic or bicyclic, more preferably monocyclic,
And may be substituted with an alkyl group having up to 5 carbon atoms, an alkoxyalkyl group, or a halogen atom.

When R ⁵ and R ⁶ are an alkyl group or an alkoxyalkyl group, it preferably has 1 to 5 carbon atoms.

R ⁷ is preferably a methyl group. D ³ and D ⁴ may be the same or different and are preferably 6-membered saturated heterocycles containing 2 nitrogen atoms.

When F is a saturated hydrocarbon group, it preferably has 2 to 6 carbon atoms, when F is an arylene group, it is preferably a phenylene group, and when it is a cycloaliphatic group, it is preferably a cyclohexylene group, In the case of a heterocyclic aromatic group, a 5- or 6-membered ring containing a nitrogen atom or a sulfur atom is preferable.

To obtain the compound represented by the general formula (2), when Q ² is N and n and m are the same value, glycidyl acrylate or alkyl acrylate is reacted with a hydroxyalkylamine. Other compounds can be similarly obtained.

The addition amount of the compounds represented by the general formulas (1) and (2) is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass of the nonvolatile components of the photopolymerizable photosensitive layer.

(Support) The support relating to the lithographic printing plate of the present invention includes, for example, a metal plate made of aluminum, stainless steel, chromium, nickel or the like, or a plastic film such as a polyester film, a polyethylene film or a polypropylene film and the above-mentioned metal. A thin film laminated or vapor-deposited, or a polyester film, a vinyl chloride film, a nylon film or the like having a surface subjected to a hydrophilic treatment can be used, but an aluminum plate is preferably used, and in this case, a pure aluminum plate and It may be an aluminum alloy plate or the like.

As the aluminum alloy for the support, various ones can be used. For example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium and iron. Is used.

The support according to the present invention is preferably subjected to a degreasing treatment in order to remove rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as trichlene and thinner, an emulsion degreasing treatment using an emulsion such as kesilon, triethanol and the like are used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment.
When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is possible to remove stains and oxide films which cannot be removed only by the above degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is formed on the surface of the support. In this case, dip it in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof to desmut it. It is preferable to apply a treatment.

Examples of the roughening method include a mechanical method and an electrolytic etching method.

The mechanical surface roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is performed by, for example, rotating a rotating brush using brush bristles having a diameter of 0.2 to 0.8 mm, and, for example, a particle diameter of 10 to 100 μm on the support surface.
It can be carried out by pressing a brush while supplying a slurry in which the particles of the volcanic ash are uniformly dispersed in water. Roughening by honing polishing is performed, for example, with a particle size of 10 to 100.
Particles of μm volcanic ash can be evenly dispersed in water, pressure is applied from a nozzle to eject, and the surface of the support can be obliquely collided for roughening. Further, for example, 100 to 2 abrasive particles having a particle diameter of 10 to 100 μm are provided on the surface of the support.
2.5 × 10 ³ to 10 × 10 ³ pieces / c at intervals of 00 μm
It is also possible to carry out roughening by laminating sheets coated so as to exist at a density of m ² and applying pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the above-mentioned mechanical surface roughening method, it is preferable to immerse it in an aqueous solution of acid or alkali in order to remove the abrasive, the aluminum scraps and the like that have invaded the surface of the support. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, and examples of the base include sodium hydroxide, potassium hydroxide and the like. Among these, it is preferable to use an alkaline aqueous solution such as sodium hydroxide. The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . It is preferable to carry out the neutralization treatment by immersing in an alkaline aqueous solution and then immersing it in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

The electrochemical surface-roughening method is not particularly limited, but the method of electrochemically surface-roughening in an acidic electrolytic solution is preferable. As the acidic electrolytic solution, an acidic electrolytic solution which is usually used in an electrochemical roughening method can be used,
It is preferable to use a hydrochloric acid-based or nitric acid-based electrolyte. For the electrochemical roughening method, for example, Japanese Patent Publication No. 48-2
The methods described in Japanese Patent No. 8123, British Patent No. 896,563, and Japanese Patent Laid-Open No. 53-67507 can be used. This roughening method is generally 1-5.
It can be carried out by applying a voltage in the range of 0 V, but it is preferable to select it in the range of 10 to 30 V. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. Electricity is 100-5000c /
A range of dm ² can be used, but from 100 to 200
It is preferable to select from the range of 0 c / dm ² . The temperature for carrying out this surface roughening method may be in the range of 10 to 50 ° C, but is preferably selected in the range of 15 to 45 ° C.

Electrification using nitric acid-based electrolyte as electrolyte
When performing a surface roughening, a range of 1 to 50 volts is generally used.
Can be done by applying a voltage of
It is preferable to select from the range of 10 to 30 volts. Current density
10 to 200 A / dm ²The range of
Can, but 20-100A / dm²It is preferable to choose from the range
Good Electricity is 100-5000c / dm²Range of
Can be used, but 100 to 2000 c / dm²
It is preferable to select from the range. Performs an electrochemical roughening method
The heating temperature may be in the range of 10 to 50 ° C.
Is preferably selected from the range of 15 to 45 ° C. Electrolyte
The nitric acid concentration in is preferably 0.1 to 5 mass%. electrolytic
The solution should contain nitrates, chlorides, amines, and
Luthedes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid
Etc. can be added.

When a hydrochloric acid-based electrolyte is used as the electrolyte,
Generally, it can be performed by applying a voltage in the range of 1 to 50 V, but it is preferable to select from the range of 2 to 30 V. Current density is 10 to 200 A / d
A range of m ² can be used, but 50 to 150 A /
It is preferable to select from the range of dm ² . The amount of electricity is 100
A range of up to 5000 c / dm ² can be used,
100 to 2000 c / dm ² , further 200 to 1000
It is preferable to select from the range of c / dm ² . The temperature for carrying out the electrochemical graining method may be in the range of 10 to 50 ° C, but is preferably selected in the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like can be added to the electrolytic solution.

After the surface is roughened by the above-mentioned electrochemical surface roughening method, it is preferable to immerse it in an aqueous solution of acid or alkali in order to remove aluminum dust and the like on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, and examples of the base include sodium hydroxide, potassium hydroxide and the like. Among these, it is preferable to use an aqueous solution of alkali. The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . Further, it is preferable that after the dipping treatment is carried out with an alkaline aqueous solution, the dipping treatment is carried out by dipping in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

The mechanical surface-roughening treatment method and the electrochemical surface-roughening method may be used alone for surface-roughening, or the mechanical surface-roughening method may be followed by the electrochemical surface-roughening method. You may carry out and roughen.

After the surface-roughening treatment, anodizing treatment can be performed. The method of anodizing treatment that can be used in the present invention is not particularly limited, and a known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. The anodizing treatment includes
A method in which an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% is used as an electrolytic solution and electrolysis is performed at a current density of 1 to 10 A / dm ² is preferably used. In addition, US Pat. No. 1,412,768 is used. The method of electrolyzing in sulfuric acid at a high current density described in Japanese Patent No. 3,511,661, the method of electrolysis using phosphoric acid described in Japanese Patent No. 3,511,661, chromic acid, oxalic acid, malonic acid, etc. Examples thereof include a method using a solution containing one kind or two or more kinds. The formed anodic oxide coating amount is appropriately 1 to 50 mg / dm ² , and preferably 10 to 40 mg / dm ² . The amount of anodized coating is
For example, an aluminum plate is treated with a chromic acid phosphoric acid solution (phosphoric acid 85%
Liquid: 35 ml, chromium oxide (IV): 20 g is dissolved in 1 L of water) to dissolve the oxide film, and the mass change of the plate before and after dissolution is measured.

The anodized support may be subjected to a pore-sealing treatment if necessary. These sealing treatments can be performed by using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment and ammonium acetate treatment.

Further, after these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (eg boric acid). Zinc) or yellow dye,
An undercoat of an amine salt or the like is also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently bonded as disclosed in JP-A-5-304358 is also suitably used.

As the support, various materials can be used as described above, and, for example, a polyester film, a vinyl chloride film, a nylon film or the like whose surface has been hydrophilized can also be used. As a hydrophilic treatment method for the film, sulfuric acid treatment, oxygen plasma etching treatment, corona discharge treatment, provision of a water-soluble resin layer coating layer and the like are preferably used. In the practice of the present invention, the surface is roughened, anodized, sealed,
And an aluminum plate subjected to undercoating treatment is particularly preferable.

(Polymer Binder) The photopolymerizable photosensitive layer according to the present invention contains a polymer binder. The polymer binder preferably contains a vinyl-based copolymer composed of at least one of the monomers (monomers) described in (1) to (17) below.

(1) A monomer having an aromatic hydroxyl group, for example, o- (or p-, m-) hydroxystyrene, o
-(Or p-, m-) hydroxyphenyl acrylate and the like.

(2) Monomers having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5 -Hydroxypentyl methacrylate, 6-
Hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

(3) A monomer having an aminosulfonyl group, for example, m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like.

(4) Monomers having a sulfonamide group such as N- (p-toluenesulfonyl) acrylamide and N- (p-toluenesulfonyl) methacrylamide.

(5) α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride.

(6) Substituted or unsubstituted alkyl acrylate, such as methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, acrylic acid 2-chloroethyl, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.

(7) Substituted or unsubstituted alkyl methacrylate, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.

(8) Acrylamide or methacrylamide, such as acrylamide, methacrylamide, N
-Ethyl acrylamide, N-hexyl acrylamide, N-cyclohexyl acrylamide, N-phenyl acrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N-phenyl acrylamide, N
-(4-hydroxyphenyl) acrylamide, N-
(4-hydroxyphenyl) methacrylamide and the like.

(9) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl Methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

(10) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether,
Propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc.

(11) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(12) Styrenes such as styrene, methylstyrene, chloromethylstyrene and the like.

(13) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(14) Olefins such as ethylene,
Propylene, i-butylene, butadiene, isoprene and the like.

(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

(16) Monomers having a cyano group, for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene. etc.

(17) A monomer having an amino group, for example, N, N-diethylaminoethyl methacrylate, N,
N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethyl acrylamide, acryloyl morpholine, N-i-propyl acrylamide, N, N- Diethyl acrylamide etc.

If desired, the above-mentioned polymer binder may be any other polymer binder such as polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, novolac resin, natural resin and the like. You may use together with the vinyl-type copolymer which concerns on this invention.

The content of the above-mentioned polymer binder in the photopolymerizable photosensitive layer is preferably 10 to 90% by mass of the photopolymerizable photosensitive layer, more preferably 15 to 70% by mass, and 20 to 50% by mass.
From the viewpoint of sensitivity, it is particularly preferable to use the compound in mass. Furthermore, the vinyl copolymer preferably accounts for 50 to 100% by mass in the polymer binder,
More preferably, it is mass%.

The acid value of the polymer contained in the polymer binder according to the present invention is preferably 10 to 150, more preferably 30 to 150.
120 is more preferable, and 50 to 90 is particularly preferable from the viewpoint of balancing the polarities of the entire photosensitive layer, which can prevent aggregation of the pigment in the photosensitive layer coating liquid.

(Photopolymerization Initiator) As the photopolymerization initiator according to the present invention, those which can be preferably used are described, for example, in J. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar.
Azo compounds, diazo compounds, halogen compounds, photoreducible dyes and the like can be mentioned, and the compounds disclosed in British Patent 1,459,563 are also preferable.

Specifically, the following examples can be given, but the invention is not limited thereto. That is, benzoin methyl ether, benzoin-i-propyl ether, α, α
Benzoin derivatives such as -dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-
Benzophenone derivatives such as bis (dimethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butyl Acridone derivatives such as acridone; α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, as well as JP-B-59-1281, JP-A-61-9621 and JP-A-60-60.
The triazine derivative described in JP-A-104-104; JP-A-59-
1504 and 61-243807; organic peroxides; JP-B-43-23684 and 44;
No. 6413, No. 44-6413, No. 47-
1604 and U.S. Pat. No. 3,567,453.
Diazonium compounds described in U.S. Pat.
No. 8,328, No. 2,852,379 and No. 2,
Organic azide compounds described in 940,853; Japanese Patent Publication Sho 3
6-22062, 37-13109, 38-18015 and 45-9610, o-quinone diazides; JP-B-55-391.
62, JP-A-59-14023, and "Macromolecules".
s) ”, various onium compounds described in Vol. 10, p. 1307 (1977); azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patents 109, 851 and 126. , 712 and "Journal of Imaging Science (J.Imag.Sci.)", Vol. 30, p. 174 (19).
1986). Metal allene complexes described in JP-A-5-21386.
No. 1 and No. 5-255347 (oxo) sulfonium organic boron complex; titanocenes described in JP-A-59-152396 and JP-A-61-151197; "Coordination Chemistry Review (Coordination Chemistry Review). R
84), pages 85-277 (1988).
And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701;
2,4,5-Triarylimidazole dimers described in JP-A-209477; carbon tetrabromide, JP-A-59-107.
Organic halogen compounds described in Japanese Patent No. 344, etc.

Among them, titanocenes are preferable. Specific examples of titanocenes include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4. , 5,6-Pentafluorophen-1-yl, di-cyclopentadienyl-Ti
-Bis-2,3,5,6-tetrafluorophenyl-1-
Il, di-cyclopentadienyl-Ti-bis-2,
4,6-Trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-
2,4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-
Pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2, 4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrid-1-yl) phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals) and the like can be mentioned. However, the present invention is not limited to this.

When laser light is used as the light source, it is preferable to add a sensitizing dye to the photosensitive layer.

Examples of the compound for wavelength sensitization from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, flugide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane. , Triphenylmethane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyrromethene compounds,
Examples thereof include pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, and thiobarbituric acid derivatives, and further, European Patent 568,993, US Patents 4,508,811, 5,227,227, and Japanese Unexamined Patent Publication No. 2001-125255, JP-A-11-271
The compounds described in Japanese Patent No. 969 etc. are also used.

In the present invention, a preferable specific example of the combination of the photopolymerization initiator and the sensitizing dye is described in JP-A-200
The combination described in JP-A No. 1-125255 and JP-A No. 11-271969 can be mentioned.

The blending amount of these polymerization initiators is not particularly limited, but preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the addition-polymerizable ethylenically unsaturated double bond-containing monomer according to the present invention. It is a department. The molar ratio of the photopolymerization initiator to the sensitizing dye is preferably 1: 100 to 100: 1.

(Various Additives) The coating composition for the photopolymerizable photosensitive layer according to the present invention contains, in addition to the above-mentioned components, an ethylenically unsaturated double bond capable of being polymerized during the production or storage of the planographic printing plate. To prevent unwanted polymerization of bound monomers,
It is desirable to add a polymerization inhibitor. Suitable 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-nitrosophenylhydroxylamine primary cerium salt, 2-t-butyl-6- (3-t-butyl-2)
-Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and the like.

The addition amount of the polymerization inhibitor is preferably about 0.01% to about 5% with respect to the total solid content of the above composition. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, or may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

A colorant can also be used, and as the colorant, conventionally known ones including commercially available ones can be preferably used. For example, those described in the revised new edition "Pigment Handbook", edited by Japan Pigment Technology Association (Seibundo Shinkosha), Color Index Handbook, etc. may be mentioned.

Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, metal powder pigment and the like. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium and calcium, etc.) and organic pigments (azo, thioindigo) Pigments, anthraquinone pigments, anthanthrone pigments, triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and their derivatives, quinacridone pigments, etc.).

Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength range of the spectral sensitizing dye corresponding to the exposure laser used, and in this case, the pigment at the laser wavelength used is selected. The reflection absorption of the pigment using the integrating sphere is preferably 0.05 or less. The amount of the pigment added is 0.1 with respect to the solid content of the composition.
-10 mass% is preferred, and more preferably 0.2-5 mass%.

As an exposure light source, an argon laser (48
8nm) or SHG-YAG laser (532nm)
In the case of using a violet pigment, a violet pigment or a blue pigment is preferably used from the viewpoint of the absorption of the pigment in the above-mentioned photosensitive wavelength region and the visibility of the image after development. Examples of such materials include cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue farst sky blue, indanthrene blue,
Indico, dioxane violet, isoviolanthrone violet, indanthrone blue, indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferable.

Further, the above composition may contain a surfactant as a coatability improving agent within a range not impairing the performance of the present invention. Among them, the fluorine-based surfactant is preferable.

In order to improve the physical properties of the cured film,
Additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added. The addition amount of these is preferably 10% or less of the total solid content.

(Coating) Examples of the solvent used in preparing the photosensitive composition for the photopolymerizable photosensitive layer according to the present invention include alcohol: polyhydric alcohol derivatives, and
c-butanol, isobutanol, n-hexanol,
Benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-
Pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, and esters: ethyl lactate, butyl lactate, Preferable examples include diethyl oxalate and methyl benzoate.

Prepared Photosensitive Composition (Photosensitive Layer Coating Solution)
Can be coated on a support by a conventionally known method and dried to prepare a lithographic printing plate. As a coating method of the coating liquid, for example, an air doctor coater method, a blade coater method,
The wire bar method, the knife coater method, the dip coater method, the reverse roll coater method, the gravure coater method, the cast coating method, the curtain coater method and the extrusion coater method can be mentioned.

When the drying temperature of the photosensitive layer is low, sufficient printing durability cannot be obtained, and when it is too high, not only Marangoni occurs but also fog in non-image area occurs. As a preferable drying temperature range, a range of 60 to 160 ° C is preferable, a range of 80 to 140 ° C is more preferable, and a range of 90 to 120 ° C is particularly preferable.

(Protective Layer) A protective layer is preferably provided on the upper side of the photopolymerizable photosensitive layer according to the present invention. The protective layer (oxygen barrier layer) preferably has high solubility in a developer (generally an alkaline aqueous solution) described later.

Preferred examples of the material forming the protective layer include polyvinyl alcohol, polysaccharides, polyvinylpyrrolidone, polyethylene glycol, gelatin,
Glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate,
Examples thereof include polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, water-soluble polyamide and the like. These compounds can be used alone or in combination of two or more to form a coating composition. A particularly preferable compound is polyvinyl alcohol.

To prepare the protective layer coating composition, the above materials can be dissolved in a suitable solvent to prepare a coating solution.
This coating solution is coated on the photopolymerizable photosensitive layer according to the present invention,
The protective layer can be formed by drying. The thickness of the protective layer is preferably 0.1 to 5.0 μm, particularly preferably 0.
It is 5 to 3.0 μm. The protective layer may further contain a surfactant, a matting agent, etc., if necessary.

As the coating method of the protective layer, the known methods mentioned in the above examples can be preferably used. The drying temperature of the protective layer is more preferably lower than the drying temperature of the photosensitive layer. The difference from the drying temperature of the photosensitive layer is preferably 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit in that case is preferably about 50 ° C. at most.

The drying temperature of the protective layer is preferably lower than the glass transition temperature (Tg) of the binder contained in the photosensitive layer. The difference between the drying temperature of the protective layer and the glass transition temperature (Tg) of the binder contained in the photosensitive layer is preferably 20 ° C. or more, more preferably 40 ° C. or more, and the upper limit of the difference is at most about 60 ° C. Is preferred.

(Image forming method) As a light source for imagewise exposing the planographic printing plate material of the present invention, for example, laser, light emitting diode, xenon lamp, xenon flash lamp, halogen lamp, carbon arc lamp, metal halide lamp, tungsten lamp, high pressure. Examples thereof include a mercury lamp and an electrodeless light source.

In the case of collective exposure, a mask material having a negative pattern of a desired exposure image formed of a light-shielding material may be superposed on the photopolymerizable photosensitive layer and exposed.

When an array type light source such as a light emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp or a tungsten lamp is exposed and controlled by an optical shutter material such as liquid crystal or PLZT, an image signal is used. It is possible and preferable to perform appropriate digital exposure. In this case, direct writing can be performed without using a mask material.

The laser exposure is suitable for direct writing without using a mask material, because light can be focused into a beam and scanning exposure can be performed according to image data. Further, when a laser is used as a light source, it is easy to reduce the exposure area to a minute size, and high-resolution image formation becomes possible.

As the laser light source, any of an argon laser, a He-Ne gas laser, a YAG laser, a semiconductor laser and the like can be preferably used. Laser scanning methods include cylinder outer surface scanning, cylinder inner surface scanning, and plane scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum having a recording material wound on the outer surface, and rotation of the drum is main scanning and movement of laser light is sub scanning. In the cylindrical inner surface scanning, the recording material is fixed to the inner surface of the drum, the laser beam is irradiated from the inner side, and the main scanning is performed in the circumferential direction by rotating a part or the whole of the optical system, and a part of the optical system or Sub-scanning is performed in the axial direction by linearly moving the whole body in parallel with the axis of the drum. In plane scanning, a polygon mirror or a galvanometer mirror and an fθ lens are combined to perform main scanning of laser light, and sub-scanning is performed by moving a recording medium. The scanning of the outer surface of the cylinder and the scanning of the inner surface of the cylinder make it easier to increase the accuracy of the optical system and are suitable for high-density recording.

(Developer) The exposed portion of the photopolymerizable photosensitive layer which is imagewise exposed is cured. By developing this with an alkaline developing solution, the unexposed portion is removed and image formation becomes possible. As such a developing solution, a conventionally known alkaline aqueous solution can be used. For example sodium silicate,
Same potassium, same ammonium; dibasic sodium phosphate, same potassium, same ammonium; sodium bicarbonate, same potassium, same ammonium; sodium carbonate, same potassium,
Examples thereof include alkaline developers using inorganic alkali agents such as ammonium ammonium; sodium hydrogen carbonate, potassium hydrogen, ammonium hydroxide; sodium borate, potassium potassium, ammonium hydrogenate; sodium hydroxide, potassium potassium, ammonium hydrogen and lithium.

Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine,
Di-i-propylamine, tri-i-propylamine,
Organic alkali agents such as butylamine, monoethanolamine, diethanolamine, triethanolamine, mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine and pyridine can also be used.

These alkaline agents may be used alone or in combination of two or more. If necessary, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer.

In the development according to the present invention, it is preferable to develop with a developer containing an alkali silicate and having a pH of less than 12.5, more preferably in the range of 10.5 to 12.4. The effect of the present invention is specifically exhibited by such development. That is, not only can the developability and sensitivity that were conventionally insufficient be brought out as sufficient performance, but also the performance such as improvement of development sludge performance and improvement of printing durability can be improved at the same time.

[0120]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 (Production of Ethylenic Double Bond-Containing Monomer) Tris-3-
Oxypropylamine 100 g, 3 times mole of isocyanoethyl methacrylate, dibutyltin dilaurate 0.0
1 g and 0.01 g of benzoquinone in 4 kg of methyl ethyl ketone in the isocyanate region (2275-225).
Until the IR spectrum at 0 cm ^-1 ) is no longer detected
Reflux for hours. Then, the solvent was distilled off under reduced pressure to obtain a viscous compound 1-1. The yield was quantitative.

Similarly, the compounds 1-2, 1-3, 1-
5 to 1-11 were obtained. Hydroxyethyl methacrylate 100 g, equimolar 2,2,4-trimethylhexamethylene diisocyanate and benzoquinone 0.01 g
Reflux in 8 kg of methyl ethyl ketone for 8 hours, add 1/3 mol tris-3-oxypropylamine of hydroxyethylmethacrylate and add isocyanate region (22
The mixture was refluxed for 8 hours until no IR spectrum at 75-2250 cm ^-1 ) was detected. Then the solvent was distilled off under reduced pressure,
A viscous compound 1-4 was obtained.

The obtained compound is shown below.

[0124]

[Chemical 5]

(Synthesis of Polymer Binder 1) In a three-necked flask under a nitrogen stream, 12 kg of methacrylic acid, 70 kg of methyl methacrylate, 8 kg of acrylonitrile, 10 kg of ethyl methacrylate, 500 kg of ethanol and α, α '.
-Azobisisobutyronitrile (3 kg) was added, and the mixture was reacted in a nitrogen stream in an oil bath at 80 ° C for 6 hours. Then, 3 kg of triethylammonium chloride and 2 kg of glycidyl methacrylate were added and reacted for 3 hours to obtain a polymer binder 1. Mass measured using GPC is about 5
The glass transition temperature (Tg) measured by DSC (differential thermal analysis) was about 85 ° C.

(Production of Support) An aluminum plate (material 1050, temper H16) having a thickness of 0.24 mm was immersed in a 5% by mass aqueous sodium hydroxide solution kept at 65 ° C., and 1
After degreasing treatment for 1 minute, it was washed with water. This degreased aluminum plate was immersed in a 10 mass% hydrochloric acid aqueous solution kept at 25 ° C. for 1 minute for neutralization, and then washed with water. Then, this aluminum plate was placed in a 0.3% by mass aqueous nitric acid solution to
After electrolytic surface roughening was performed for 60 seconds with an alternating current under the conditions of 5 ° C. and a current density of 100 A / dm ² , desmut treatment was performed for 10 seconds in a 5 mass% sodium hydroxide aqueous solution kept at 60 ° C. It was The desmutted roughened aluminum plate was anodized in a 15% by mass sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute.

At this time, the center line average roughness (Ra) of the surface was 0.65 μm. Next, as a pretreatment of the support,
The anodized aluminum plate was passed through a solution of 1.5% by mass of polyvinylphosphonic acid and 0.2% by mass of vinylphosphonic acid at 80 ° C. for 30 seconds and dried.

(Installation of Undercoat Layer on Support) On the support, a coating solution for the undercoat layer having the following composition was dried at 0.1 g / m ²
Was applied with a wire bar so as to obtain the above composition, dried at 90 ° C. for 1 minute, and further heat-treated at 110 ° C. for 3 minutes to prepare an undercoated support.

[0129]   <Undercoat layer coating liquid>   γ-methacryloxypropyltrimethoxysilane 1 part   Methyl ethyl ketone 80 parts   Cyclohexanone 19 parts (Preparation of planographic printing plate)
1.4 g / m when the photopolymerizable photosensitive layer coating liquid of the composition is dried²To
Apply with a wire bar and dry at 95 ° C for 1.5 minutes.
Dried After that, over the photosensitive layer,
Coating layer coating liquid is 2.0g / m when dried ²To become
Apply with a pre-curer and dry at 75 ° C for 1.5 minutes,
Producing a lithographic printing plate with an overcoat layer on the photosensitive layer
did.

[0130]   <Photopolymerizable photosensitive layer coating liquid>   Polymer binder 1 35.0 parts   Sensitizing dye (see Table 4) 4.0 parts                                         2 parts are added for each 2 parts   IRGACURE 784 (manufactured by Ciba Specialty Chemicals)                                                               4.0 copies   EO modified tris (acryloxyethyl) isocyanuric acid (Aronix M-31 5: Toagosei Co., Ltd.) 35.0 parts   Polytetramethylene glycol diacrylate (PTMGA-250: Mutual prosperity) Made by Gakusha) 10.0 copies   Polyfunctional urethane acrylate (U-15HA: Shin-Nakamura Chemical Co., Ltd.)                                                               5.0 copies   Phthalocyanine pigment (MHI454: manufactured by Mikuni dye company) 4.5 parts   2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl ) -4-Methylphenyl acrylate (Sumilyser GS: Sumitomo 3M)                                                               0.5 copy   Sanol LS-770 (manufactured by Sankyosha) 0.5 parts   Fluorine-based surfactant (MegaFac F-178K: Sumitomo 3M)                                                               0.5 copy   Triazine compound 1.0 part   Methyl ethyl ketone (boiling point = 79.6 ° C.) 80 parts   Cyclopentanone (boiling point = 129 ° C.) 820 parts

[0131]

[Table 4]

<Overcoat layer coating liquid> Polyvinyl alcohol (GL-03: manufactured by Nippon Synthetic Chemical Industry) 89 parts Water-soluble polyamide (P-70: manufactured by Toray Industries) 10 parts Surfactant (Surfynol 465: Nissin) Chemical Industry Co., Ltd.) 1.0 part Water 900 parts (image formation) For the prepared photopolymerization type lithographic printing plate, F
CT equipped with a D-YAG laser light source (532 nm)
COBALT-8 (Escher-Grad Tech) equipped with a P exposure device (Tigercat: manufactured by ECRM) or a violet laser light source (408 nm).
Nologies Inc. ) Using 2540 dpi
Image exposure was performed at a resolution of (dpi is the number of dots per 2.54 cm). Then, a pre-washing part for removing the overcoat layer before development, a developing part filled with a developer having the following composition, a washing part for removing the developer adhering to the plate surface, and a gum solution (GW-3 for protecting the image area) : CTP automatic developing machine (PHW32-) equipped with Mitsubishi Chemical's 2-fold dilution)
V: manufactured by Technigraph) was preheated / developed to obtain a lithographic printing plate.

<Developer composition> A Potassium silicate 8.0% by mass Perex NBL (manufactured by Kao Corporation) 2.0% by mass Newcol B13 (manufactured by Nippon Emulsifier Co., Ltd.) 1.0% by mass Caustic potassium pH = 12.3 Amount of water to be 100% by mass in total (evaluation) The lithographic printing plate obtained as described above was evaluated as follows. The results are shown in Table 5.

<Sensitivity> No film loss in the image area was observed, and the halftone dot exposure area of 175 lines and 50% was the exposure amount on the plate surface which could be reproduced 50% on the prepared lithographic printing plate surface. .

<Printing durability> An image of 175 lines was recorded with an appropriate exposure amount (a film loss in the image area was not observed, and 175 lines / 50).
% Of the halftone dot exposure area is twice the amount of light that can be reproduced on the prepared lithographic printing plate surface to 50%), and the developed lithographic printing plate is printed with a printing machine (DAIY manufactured by Mitsubishi Heavy Industries, Ltd.).
A1F-1), using coated paper, printing ink (Toyo Ink Co., Ltd. Toyo King High Echo M Beni) and fountain solution (Tokyo Ink Co., Ltd. H liquid SG-51, concentration 1.5% by mass). After continuous printing of 1000 sheets, the plate surface was wiped with a cleaner, and the number of printed sheets in which the highlight portion was thinned and the shadow portion was entangled was used as an index of printing durability. Printing durability 1 time is 1
This refers to the work of wiping with a cleaner after continuous printing of 000 sheets. The larger the number, the better.

<Stain recovery> After continuous printing of 1000 sheets, wipe with a cleaner and restart printing after 15 minutes, and set the number of sheets to remove the background stain of the non-image area. The less the better.

<Dot Reproducibility> Halftone dots are drawn with the above laser drawing power without linearity correction, and a halftone dot area that is supposed to be reproduced to 90% is photographed with a 500 × optical microscope.
The dot percentage of the image area in the range of 2 mm × 2 mm was calculated and used as the index of dot reproducibility.

[0138]

[Table 5]

Example 2 (Production of Ethylenic Double Bond-Containing Monomer) A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 191 g of tripropanolamine and 500 g of methyl ethyl ketone.
Is added and dissolved, and 6 g of sodium is added with stirring to dissolve. 322 g of glycidyl methacrylate dissolved in 400 g of methyl ethyl ketone is added dropwise at 60 ° C. for 2 hours. After further heating at 60 ° C. for 2 hours and cooling to room temperature, 2,6-di-t-butyl-4-methylphenol 2
Add g. Hydrochloric acid in an equimolar amount to sodium was added, and the mixture was shaken for washing, washed twice with water, dried over sodium sulfate, and dried at 50 ° C to obtain compound 2-1. In the same manner, compounds 2-2 to 2-12 were obtained.

The obtained compound is shown below.

[0141]

[Chemical 6]

A lithographic printing plate was prepared in the same manner as in Example 1 except that the composition of the photopolymerizable photosensitive layer coating solution was changed to the following contents.

<Photopolymerizable Photosensitive Layer Coating Liquid> Polymer binder 1 X part Spectral sensitizing dye 1 4.0 parts IRGACURE 784 (manufactured by Ciba Specialty Chemicals) 4.0 parts Ethylenic double bond-containing unit amount Body (see Table 6) Y part Phthalocyanine pigment (MHI454: manufactured by Mikuni dye company) 4.5 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methyl Phenyl acrylate (Sumilizer GS: Sumitomo 3M) 0.5 part Sanol LS-770 (manufactured by Sankyo) 0.5 part Fluorine-based surfactant (MegaFac F-178K: Sumitomo 3M) 0.5 part Triazine Compound 1.0 part Methyl ethyl ketone (boiling point = 79.6 ° C.) 80 parts Cyclopentanone (boiling point = 129 ° C.) 820 parts X + Y = 85 parts Parts by weight of the ethylenic double bond-containing monomer from 5 parts to the amount obtained by subtracting the.

[0144]

[Chemical 7]

The lithographic printing plate obtained as described above was evaluated in the same manner as in Example 1. The results are shown in Table 6
Shown in.

[0146]

[Table 6]

Example 3 A lithographic printing plate was prepared in the same manner as in Example 1 except that the composition of the photopolymerizable photosensitive layer coating liquid was changed to the following contents.

[0148]   <Photopolymerizable photosensitive layer coating liquid>   Polymer binder 1 35.0 parts   Sensitizing dye (see Table 7) 4.0 parts                                         2 parts are added for each 2 parts   IRGACURE 784 (manufactured by Ciba Specialty Chemicals)                                                               4.0 copies   Ethylenic double bond-containing monomer (see Table 7) 50.0 parts   Phthalocyanine pigment (MHI454: manufactured by Mikuni dye company) 4.5 parts   2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl ) -4-Methylphenyl acrylate (Sumilyser GS: Sumitomo 3M)                                                               0.5 copy   Sanol LS-770 (manufactured by Sankyosha) 0.5 parts   Fluorine-based surfactant (MegaFac F-178K; manufactured by Sumitomo 3M Limited)                                                               0.5 copy   Triazine compound 1.0 part   Methyl ethyl ketone (boiling point = 79.6 ° C.) 80 parts   Cyclopentanone (boiling point = 129 ° C.) 820 parts

[0149]

[Table 7]

[0150]

[Chemical 8]

The lithographic printing plate thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 8
Shown in.

[0152]

[Table 8]

[0153]

According to the present invention, it is possible to provide a photosensitive lithographic printing plate excellent in sensitivity, printing durability, stain recovery and dot reproducibility.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/027 502 G03F 7/027 502 F term (reference) 2H025 AA01 AA04 AA12 AB03 AC01 AC08 AD01 BC14 BC83 CA00 CA41 FA17 2H096 AA06 BA05 CA03 EA04 EA23 GA08 4J011 PA22 PA64 PA67 PA68 PA69 PA70 PC02 QA13 QA18 QA38 SA06 SA22 SA27 SA34 SA62 SA63 SA83 TA03 VA01 WA05 4J026 AA12 AA13 AA14 AA16 AA17 AA31 AA33 AA37 AA38 AA45 AA47 AA49 AA50 AA53 AA60 AA68 AA69 BA29 BA30 BA36 DB36 FA04 FA05 GA08

Claims (5)

[Claims] 1. A photosensitive material having a photopolymerizable photosensitive layer containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator and a polymer binder on a support having a hydrophilic surface. In the lithographic printing plate, the photopolymerizable photosensitive layer contains two or more sensitizing dyes, and the absorption maximum wavelength λ1 of the first sensitizing dye is λ1.
abs (nm), maximum emission wavelength λ1emi (nm),
A photosensitive lithographic printing plate characterized in that the relationship between the absorption maximum wavelength λ2abs (nm) of the second sensitizing dye and the exposure maximum wavelength λe (nm) satisfies the following formula. λ1abs-50 ≦ λe ≦ λ1abs + 50 λ1emi-25 ≦ λ2abs ≦ λ1emi + 25 2. A photosensitive having a photopolymerizable photosensitive layer containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator and a polymer binder on a support having a hydrophilic surface. A lithographic printing plate comprising a compound represented by the following general formula (1) as the ethylenic double bond-containing monomer. [Chemical 1] In the formula, Q ¹ is Or —S—, R ⁴ represents an alkyl group, a hydroxyalkyl group or an aryl group, R ¹ and R ² each represent a hydrogen atom, an alkyl group or an alkoxyalkyl group, and R ³ represents a hydrogen atom, a methyl group or Represents an ethyl group, X ¹ represents a saturated hydrocarbon group having 2 to 12 carbon atoms, and X ² represents a (c + 1) -valent group in which up to 5 methylene groups may be replaced by oxygen atoms. Represents a saturated hydrocarbon group, D ¹ and D ² each represent a saturated hydrocarbon group having 1 to 5 carbon atoms, E represents a saturated hydrocarbon group having 2 to 12 carbon atoms, 5 to 7 A cyclic aliphatic group having up to 2 N, O or S atoms as ring members, an arylene group having 6 to 12 carbon atoms, or having 5 or 6 ring members Represents a heterocyclic aromatic group, where a is 0 or Or represents an integer of 1 to 4, and b is 0
Or 1 represents, c represents an integer of 1 to 3, m represents an integer of 2 to 4 depending on the valence of Q ¹ , n represents an integer of ^{1 to} m, and all groups having the same definition are mutually defined. It can be the same or different. 3. A photosensitive material having a photopolymerizable photosensitive layer containing an addition-polymerizable ethylenic double bond-containing monomer, a photopolymerization initiator and a polymer binder on a support having a hydrophilic surface. A lithographic printing plate comprising a compound represented by the following general formula (2) as the ethylenic double bond-containing monomer. [Chemical 3] In the formula, Q ² is R ⁸ represents an alkyl group, a hydroxyalkyl group or an aryl group, R ⁵ and R ⁶ represent a hydrogen atom,
R ⁷ represents an alkyl group or an alkoxyalkyl group, R ⁷ represents a hydrogen atom, a methyl group or an ethyl group, and D ³ and D ⁴
Each represents a saturated hydrocarbon group having 1 to 5 carbon atoms, F is a saturated hydrocarbon group having 2 to 12 carbon atoms, 5 to 7 ring members and up to 2 N , Cycloaliphatic groups containing O or S atoms as ring members, 6-12
Represents an arylene group having 6 carbon atoms or a heterocyclic aromatic group having 5 to 6 ring members, and d and e are 1 to 4
, G represents an integer of 2 to 4 depending on the valence of Q ² , f represents an integer of 1 to g, and all groups having the same definition can be the same or different from each other. 4. The photosensitive lithographic printing plate according to claim 1, wherein the photopolymerizable photosensitive layer contains the compound represented by the general formula (1). 5. The photosensitive lithographic printing plate according to claim 1, wherein the photopolymerizable photosensitive layer contains the compound represented by the general formula (2).