JP2005099285A - Stacked body of planographic printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stacked body of negative planographic printing original plates corresponding to an IR laser and to provide a stacked body of negative planographic printing original plates in which scratches on the surface of a recording layer can be prevented during carrying, exposure and transfer, or the like. <P>SOLUTION: The stacked body of planographic printing original plates is prepared by alternately stacking planographic printing original plates and slip sheets. The planographic printing original plate has a negative recording layer formed on a supporting body, the recording layer containing: (A) a compound which generates a radical by light or heat; (B) a polymer having phenyl group having a vinyl group substituted in the side chain; (C) a monomer having two or more phenyl groups having a vinyl groups substituted; and (D) an IR absorbent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminate comprising a lithographic printing plate precursor and a slip sheet, and in particular, a so-called infrared laser-compatible lithographic printing plate precursor for direct plate making that can be directly made from a digital signal from a computer or the like, and its negative recording layer It is related with the laminated body which laminates | stacks the slip sheet which contacts and protects.

In recent years, the development of lasers has been remarkable. In particular, solid lasers and semiconductor lasers having a light emitting region from the near infrared region to the infrared region have been increasing in output and size. Therefore, these lasers are very useful as an exposure light source when making a plate directly from digital data such as a computer.
An infrared laser-compatible negative lithographic printing plate precursor using an infrared laser having a light emitting region in the infrared region as described above comprises a photosensitive composition containing an infrared absorber, a radical generator, and a polymerizable compound. When it has a negative recording layer and a radical generated by light or heat is used as an initiator to cause a polymerization reaction to cure the recording layer of the exposed area to form an image area, or when the infrared absorber is a dye A recording system is used in which a radical is generated by electron transfer from a dye that has absorbed infrared rays to initiate a polymerization reaction to cure the recording layer in the exposed area to form an image area.

  JP-A-7-20629 and JP-A-7-271029 disclose photosensitive compositions and lithographic printing plates comprising a combination of a resole resin, a novolak resin, an infrared absorber, and a photoacid generator. JP-A-11-212252 and JP-A-11-231535 disclose lithographic printing plates comprising a combination of a specific polymer, a photoacid generator and a near-infrared sensitizing dye. These disclosed photosensitive compositions and lithographic printing plates have a mechanism of forming a cured portion (image portion) by causing a curing reaction using an acid generated from a photoacid generator as an initiator. Yes.

For a photosensitive composition that forms an image area by a curing reaction using a photopolymerization initiator or a photoacid generator as described above, it is difficult to impart sufficiently high photosensitivity in the near-infrared region. However, the photosensitivity was insufficient for application to scanning exposure using infrared laser light.
In addition, the curing reaction using a photopolymerization initiator or a photoacid generator is often insufficient only by exposure, and it is necessary to heat treatment after exposure or development processing to accelerate and complete the curing reaction. Processing was an important plate making process. However, the heat treatment not only lowers the production efficiency but also includes factors that make the quality unstable. For example, it is difficult to keep the difference in solubility between exposed and unexposed areas constant. If sufficient heating is not performed, the exposed area is dissolved by the developer, or conversely, the heating temperature is too high. However, there is a problem that the unexposed portion is partially insolubilized and development is not sufficiently performed.

  Therefore, for these problems, for example, Patent Document 1 and Patent Document 2 have sufficiently high photosensitivity in the near infrared region, that is, excellent sensitivity, and as a result, heat treatment and an overcoat layer are required. A photosensitive lithographic printing plate material capable of scanning exposure is disclosed. It is disclosed that this lithographic printing plate material prevents a reduction in production efficiency and improves the stability of the plate making process.

On the other hand, in order to store, transport and transport a plurality of lithographic printing plate precursors, the lithographic printing plate precursors are often laminated to form a laminate. However, when the laminate is transported, when the laminate is transported by an autoloader during CTP setter exposure, or when each lithographic printing plate precursor is peeled from the laminate, the surface of one lithographic printing plate precursor (on the recording layer side) Friction between the outermost layer) and the back surface of the lithographic printing plate precursor adjacent to it (back surface of the support) may trigger the surface of the recording layer. As described above, when a scratch is generated in the recording layer, an undesired curing reaction occurs from that portion, and as a result, there is a problem that a stain occurs in a non-image portion. In particular, in the case of a laminate composed of a lithographic printing plate precursor that does not have an overcoat layer that protects the surface of the recording layer, the effect of scratches generated on the surface is very large, and this causes a problem of reducing image quality. It has become.
JP 2001-290271 A JP 2002-278081 A

An object of the present invention is to solve the above problems and achieve the following object.
That is, an object of the present invention is a laminate of a negative lithographic printing plate precursor corresponding to an infrared laser, and capable of preventing scratches on the surface of the recording layer during transportation, exposure transportation, etc. The object is to provide an original laminate.

The above object of the present invention has been achieved by the lithographic printing plate precursor laminate shown below.
The lithographic printing plate precursor laminate of the present invention comprises, on a support, (A) a compound that generates radicals by light or heat, (B) a polymer having a phenyl group substituted with a vinyl group on the side chain, (C) It is formed by alternately laminating a lithographic printing plate precursor provided with a monomer having two or more phenyl groups substituted with vinyl groups, and (D) a negative recording layer containing an infrared absorber, and a slip sheet. The lithographic printing plate precursor laminate is characterized.
In the planographic printing plate precursor laminate of the present invention, the support is preferably an aluminum support, and the thickness of the aluminum support is preferably 0.25 mm to 0.55 mm.

Thus, according to the planographic printing plate precursor laminate of the present invention, when the planographic printing plate precursor having the negative recording layer as described above is laminated, a slip sheet is inserted between them. Therefore, the friction between the outermost surface on the negative recording layer side and the back surface of the other lithographic printing plate precursor that contacts the outermost surface (the opposite side of the recording layer to the support) is reduced, Even if the outermost surface is the recording layer, it is possible to prevent the surface from being scratched. Therefore, the lithographic printing plate precursor constituting such a lithographic printing plate precursor laminate can form a high-quality image free from stains in the non-image area.
In addition, when the support of the lithographic printing plate precursor is an aluminum support, and the thickness of the aluminum support is 0.25 mm to 0.55 mm, the handling property at the time of printing mounted on the plate cylinder is good and no nick is generated. High quality lithographic printing plate precursor can be supplied.

  According to the present invention, a laminate of a negative lithographic printing plate precursor corresponding to an infrared laser, and capable of preventing scratches on the surface of the recording layer during transportation, exposure transportation, etc. The body can be provided.

Hereinafter, the planographic printing plate precursor laminate of the present invention will be described in detail.
The lithographic printing plate precursor laminate of the present invention comprises, on a support, (A) a compound that generates radicals by light or heat, (B) a polymer having a phenyl group substituted with a vinyl group on the side chain, (C) A lithographic printing plate precursor (hereinafter referred to as a specific lithographic printing plate precursor) provided with a monomer having two or more phenyl groups substituted with vinyl groups, and (D) a negative recording layer containing an infrared absorber; It is characterized by being alternately laminated with paper.
Such a planographic printing plate precursor laminate is suitable for storage, storage, transportation and the like because the interleaf has a function of protecting the surface of the negative recording layer.
Here, first, the slip sheet constituting the planographic printing plate precursor laminate will be described.

<Interleaf>
The interleaving paper of the present invention is laminated with a specific lithographic printing plate precursor in order to reduce mechanical impact during storage and unnecessary impact / friction during transportation on the negative recording layer of the specific lithographic printing plate precursor. When it is inserted in between. Therefore, the lithographic printing plate precursor laminate of the present invention has a structure in which specific lithographic printing plate precursors and slip sheets are alternately laminated.

  In order to control material costs, low-cost raw materials are often selected for the slip sheets used in the present invention. For example, paper using 100% wood pulp and synthetic pulp mixed with wood pulp are used. And paper having a low density or high density polyethylene layer on the surface thereof can be used. In particular, a paper that does not use synthetic pulp or a polyethylene layer has a low material cost, so that a slip sheet can be produced at a low cost.

Specifically, bleached kraft pulp is beaten, and a sizing agent is added to a paper stock diluted to a concentration of 4% so that the weight of the base paper is 0.1% and the paper strength agent is 0.2%. Paper made by using a paper stock to which aluminum is added until the pH reaches 5.0, and has a basis weight of 29 to 60 g / m ² , preferably 25 to 50 g / m ² (as defined in JIS P 8124). The thickness is 42 to 80 μm, preferably 45 to 55 μm, more preferably 40 to 50 μm (both are according to the measurement method specified in JIS P 8118). Finely cut into 100 g of pure water, sealed and heated at 110 ° C. for 10 minutes, then detected with the NH ₃ gas detection method of measuring NH ₃ gas with a Kitagawa gas detector tube (for 20 ppm), and 6 ml of distilled water Underwater Put interleaf samples 3 ml, in chloride detecting method of observing the presence or absence of white turbidity of a 1% silver nitrate solution 2 drops dripped chloride therein, slip sheet as no cloudiness is observed are preferred. Further, regarding the mechanical and strength properties, preferable requirements for the slip sheet are shown in Table 1 below together with the above-described filling degree and chemical requirements, but are not limited thereto.

The notes in Table 1 are as follows.
(Note 1) The difference between the maximum value and the minimum value obtained by measuring the thickness at an arbitrary position of one sheet in accordance with JIS P 8118.
(Note 2) When the dimension (A) dried for 1 hour at 110 ° C. and the dimension (B) allowed to stand for 3 hours at 20 ° C. and 65% RH, “stretch degree (rate) = (B · A)” The expansion / contraction rate represented by “/ A × 100”.
(Note 3) The slip sheet is cut into a 150 mm × 150 mm sheet, and this sheet is left at a temperature of 20 ° C. and a humidity of 65% RH for 3 hours or more. The volume resistance value (Rv) is measured by a vibration capacity type universal electrometer (MMAI · 17 and P-601), and the product of the volume resistance value (Rv) and the electrode area (19.62 cm ² ) of the measuring device is combined. By dividing the paper thickness (t), ρv =
19. Volume resistivity (ρv) obtained from the relationship of 19.62 / t × Rv.
(Note 4) The mount is cut into a 150 mm x 150 mm sheet, and this sheet is left at a temperature of 20 ° C and a humidity of 65% RH for 3 hours or more. The surface resistance value was measured by a capacitive universal electrometer (MMAII · 17 and P · 601). The surface resistivity (ρs) obtained by ρs = 18.7 × Rs from the product of this surface resistance (Rs) and the coefficient (18.7) calculated from the electrode area of the measuring instrument.
(Note 5) Static friction coefficient with the image forming surface of a lithographic printing plate.
(Note 6) Value measured with a Kitagawa gas detector tube (for 20 ppm) after cutting 20 g of sample into 100 g of pure water and heating at 110 ° C. for 10 minutes.
(Note 7) Put 3 ml of slip paper sample in 6 ml of distilled water, drop 2 drops of 1% silver nitrate solution into it, and visually check for cloudiness.

Among the specifications of the above-mentioned slip sheets, preferable specifications include a basis weight of 30 to 60 g / m ² , a smoothness of 10 to 100 seconds in a Beck smoothness measuring method defined in JIS P 8119, and a moisture content of JIS. In the moisture content measuring method specified in P8127, the density is 4 to 8% and the density is 0.7 to 0.9 g / cm ³ .

<Dynamic friction coefficient of the outermost surface on the negative recording layer side with respect to the slip sheet>
The lithographic printing plate precursor laminate of the present invention preferably has a dynamic friction coefficient of 0.2 to 0.7 on the outermost surface on the negative recording layer side with respect to the slip sheet from the viewpoint of slipperiness and scratch resistance. It becomes an aspect. A more preferable range of the dynamic friction coefficient is 0.2 to 0.5.
Here, in the present invention, the “outermost surface on the negative recording layer side” means the surface of the negative recording layer when only the negative recording layer is provided on the support. When an arbitrary upper layer is provided on the mold recording layer, the surface of the arbitrary upper layer is indicated.

  The means for controlling the dynamic friction coefficient of the outermost surface on the negative recording layer side with respect to the interleaving paper within the above range is as follows: Can be performed by performing at least one of the above-described lubrication treatment and the adjustment of the composition of the outermost surface layer that forms the outermost surface on the negative recording layer side.

  Specifically, as the dynamic friction coefficient control means, for example, when the negative recording layer forms the outermost surface on the negative recording layer side, the constituent components of the negative recording layer include fluorine-containing compounds and silane compounds, There is a method using a compound that can reduce the surface energy of the recording layer. As described above, examples of the compound used in the method for controlling the dynamic friction coefficient by the component itself of the negative recording layer include the fluorine-based polymer compounds described in Japanese Patent Application No. 2001-28869, and Japanese Patent Application No. 2001- A surface-oriented infrared absorbing alkali-soluble resin or the like described in 193251 is used. In particular, the dynamic friction coefficient can be easily controlled by adjusting the content of these compounds within a range that does not impair the characteristics of the negative recording layer.

  Further, the dynamic friction coefficient may be controlled by adding other components to the negative recording layer. For example, there are methods using a nonionic surfactant and an amphoteric surfactant containing fluorine or silicon atoms, or adding a conventionally known slip agent such as wax. Furthermore, the coefficient of dynamic friction can be controlled by adding a compound having a long-chain alkyl group exhibiting orientation on the surface of the coating liquid for the negative recording layer. Furthermore, the dynamic friction coefficient can also be controlled by adding a compound represented by the general formula (1) described in Japanese Patent Application No. 2001-97299. The dynamic friction coefficient of these additives can be easily controlled by adjusting the selection and content of each type.

Furthermore, since the friction characteristics can be controlled by adjusting the surface roughness of the negative recording layer, it is also effective to adjust various conditions and forming means when forming the negative recording layer and any upper layer. is there.
In addition, the layer that forms the outermost surface on the negative recording layer side, for example, the above-described arbitrary upper layer, the upper layer containing the compound that controls the dynamic friction coefficient, or the surface roughness is adjusted to obtain the dynamic friction coefficient. A separate controlled upper layer may be provided.

  Any known method can be used as a method for measuring the dynamic friction coefficient of the outermost surface on the negative recording layer side with respect to the interleaving paper, but in particular, the method presented in JIS P 8147 is simple and practically sufficient. Can be measured with high accuracy. In the test, measurement is performed on the outermost surface on the negative recording layer side and the surface of the slip sheet that is actually in contact with the outermost surface on the negative recording layer side.

<Specific lithographic printing plate precursor>
The specific lithographic printing plate precursor according to the invention comprises, on a support, (A) a compound that generates radicals by light or heat, (B) a polymer having a phenyl group substituted with a vinyl group on the side chain, and (C) vinyl. A negative recording layer containing a monomer having two or more phenyl groups substituted with a group, and (D) an infrared absorber is provided.
Hereinafter, each element constituting the specific planographic printing plate precursor according to the invention will be described.

[Negative recording layer]
The negative recording layer in the invention contains the essential components (A) to (D) described above and has an image portion forming mechanism as shown below.
That is, (D) infrared rays absorbed by the infrared absorbent are converted into heat, and the generated heat and / or light generates (A) radicals from the compound that generates radicals by light or heat. Then, using the generated radical as an initiator, a polymerization reaction of a monomer having (C) two or more phenyl groups substituted with vinyl groups occurs in a chain and is cured. In the present invention, since (B) a polymer having a phenyl group substituted with a vinyl group in the side chain is used as the binder polymer, a styryl radical is generated by a radical generated from the component (A), and a styryl radical is generated. In order to recombine with each other and effectively crosslink, the formed film has hydrophobic characteristics, and a surface with excellent development resistance can be obtained, so it can form a cured film with excellent characteristics It has a function.

From these facts, the negative recording layer in the present invention containing such components (A) to (D) comprises (A) a compound that generates radicals by light or heat, and (D) an infrared absorber. The combination can achieve high sensitivity, can be cured sufficiently without providing an overcoat layer that prevents the influence of oxygen in the atmosphere, and does not require heat treatment after exposure. Can be mentioned as a feature.
Each component used in the negative recording layer will be described below.

[(A) Compound that generates radicals by light or heat (radical generator)]
As the compound that generates radicals by light or heat used in the present invention (hereinafter, appropriately referred to as a radical generator), any compound that can generate radicals by light or heat can be used. .
Examples of the radical generator include organic boron salts, trihaloalkyl-substituted compounds (for example, trihaloalkyl-substituted nitrogen-containing heterocyclic compounds include s-triazine compounds, oxadiazole derivatives, and trihaloalkylsulfonyl compounds. .), Hexaarylbisimidazole, titanocene compound, ketoxime compound, thio compound, organic peroxide and the like.
In the present invention, among these radical generators, organic boron salts and trihaloalkyl-substituted compounds are particularly preferably used. More preferably, an organic boron salt and a trihaloalkyl-substituted compound are used in combination.

  The organoboron anion constituting the organoboron salt is represented by the following general formula (1).

In the general formula (1), R ¹¹ , R ¹² , R ^13, and R ¹⁴ may be the same or different, and may be an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, or a cycloalkyl group. Represents a heterocyclic group. Of these, it is particularly preferred that one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is an alkyl group and the other substituent is an aryl group.

The above-mentioned organoboron anion is present simultaneously with the cation that forms a salt with the anion. Examples of the cation in this case include alkali metal ions, onium ions, and cationic sensitizing dyes.
Examples of the onium ions include ammonium ions, sulfonium ions, iodonium ions, and phosphonium ions.
When a salt of an organic boron anion and an alkali metal ion or onium ion is used as the organic boron salt, a dye is added by adding a sensitizing dye (in the present invention, (D) refers to an infrared absorber). It imparts photosensitivity in the wavelength range of light to be absorbed. Further, when a salt having an organic boron anion as a counter anion of a cationic sensitizing dye is used as the organic boron salt, photosensitivity is imparted according to the absorption wavelength of the cationic sensitizing dye. However, in the latter case, it is preferable to further contain a salt of an alkali metal ion or onium ion and an organic boron anion.

The organic boron salt used in the present invention is a salt containing an organic boron anion represented by the above general formula (1), and alkali metal ions and onium ions are preferably used as cations forming the salt. Particularly preferred examples are salts of organic boron anions and onium ions, specifically, ammonium salts such as tetraalkylammonium salts, sulfonium salts such as triarylsulfonium salts, and phosphonium salts such as triarylalkylphosphonium salts. Can be mentioned.
Specific examples (BC-1) to (BC-6) of particularly preferred organic boron salts are shown below.

  In the present invention, other preferred radical generators include trihaloalkyl-substituted compounds. Specifically, the trihaloalkyl-substituted compound is a compound having at least one trihaloalkyl group such as a trichloromethyl group or a tribromomethyl group in the molecule. As a preferable example, the trihaloalkyl-substituted compound has a nitrogen-containing complex. Examples of the compound bonded to the ring group include s-triazine derivatives and oxadiazole derivatives, or trihaloalkylsulfonyl compounds in which the trihaloalkyl group is bonded to an aromatic ring or a nitrogen-containing heterocycle via a sulfonyl group. It is done.

  Particularly preferred specific examples (T-1) to (T-15) of compounds in which a trihaloalkyl group is bonded to a nitrogen-containing heterocyclic group, and particularly preferred specific examples (BS-1) to (BS-) of trihaloalkylsulfonyl compounds. 10) is shown below.

  In the present invention, other preferable radical generators include organic peroxides. Examples of the organic peroxide include cumene hydroperoxide, tert-butyl hydroperoxide, dichloroperoxide, di-tert-butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, and compounds having the structure shown below. Is mentioned.

  The content of the radical generator as described above is preferably included in the range of 1 to 100% by mass with respect to the polymer having (B) a vinyl group-substituted phenyl group in the side chain described below, Is preferably contained in the range of 1 to 40% by mass.

[(B) Polymer having phenyl group substituted by vinyl group in side chain (binder polymer)]
In the present invention, a polymer having a phenyl group substituted with a vinyl group in a side chain used as a binder polymer (hereinafter, appropriately referred to as a specific polymer) is a phenyl group substituted with a vinyl group directly or linked. It is bonded to the main chain through a group. The linking group is not particularly limited, and includes an arbitrary group, an atom, or a complex group thereof. In addition to the vinyl group, the phenyl group may be substituted with a substitutable group or atom. Specific examples of the substitutable group or atom include a halogen atom, a carboxy group, and a sulfo group. Group, nitro group, cyano group, amide group, amino group, alkyl group, aryl group, alkoxy group, aryloxy group and the like. Furthermore, the vinyl group may be substituted with a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, an amide group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or the like.
The polymer having a phenyl group substituted with a vinyl group in the side chain is more specifically a polymer having a group represented by the following general formula (2) in the side chain.

In general formula (2), Z ¹ represents a linking group, and R ¹ , R ² , and R ³ each independently represent a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, or an amide group. Represents an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and the like, and these groups are substituted with an alkyl group, an amino group, an aryl group, an alkenyl group, a carboxy group, a sulfo group, a hydroxy group, and the like. It may be. R ⁴ represents a substitutable group or atom. n represents 0 or 1, m ¹ represents an integer of 0 to 4, and k ¹ represents an integer of ¹ to 4.

The group represented by the general formula (2) will be described in more detail. As the linking group represented by Z ¹ , an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, an arylene group, —N (R ⁵ ) —, —C (O) —O—, —C (R ⁶ ) = Examples thereof include N-, -C (O)-, a sulfonyl group, groups shown below, a heterocyclic structure, or a group in which two or more are combined. Here, R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, an aryl group, or the like. Furthermore, the above linking group may further have a substituent such as an alkyl group, an aryl group, or a halogen atom.

The heterocyclic structure constituting the linking group represented by Z ¹ includes pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring , Thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzthiazole ring, benzselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring , Triazine ring, quinoline ring, quinoxaline ring and the like nitrogen-containing heterocycle, furan ring, thiophene ring, etc., and these heterocyclic structures further include alkyl groups, amino groups, aryl groups, alkenyl groups, carboxy groups, sulfo groups. Group, hydroxy It may have a substituent like.

Examples of the substitutable group or atom represented by R ⁴ include a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, an amide group, an amino group, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. Furthermore, these groups or atoms may have a substituent such as an alkyl group, an amino group, an aryl group, an alkenyl group, a carboxy group, a sulfo group, or a hydroxy group.

  Specific examples (K-1) to (K-20) of groups represented by the following general formula (2) are shown below, but are not limited to these specific examples.

Among the groups represented by the general formula (2), those having the following structure are preferable. That is, it is preferable that R ¹ and R ² in the general formula (2) are hydrogen atoms and R ³ is a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (such as a methyl group or an ethyl group). Further, the linking group represented by Z ¹ preferably includes a heterocyclic structure, and k ¹ is preferably 1 or 2.

In a preferred embodiment, the specific polymer in the present invention is soluble in an alkaline aqueous solution. Therefore, the specific polymer in the present invention includes a monomer having a phenyl group substituted by a vinyl group (more specifically, a group represented by the above general formula (2)), and a carboxyl group-containing monomer as a copolymerization component. It is particularly preferable that it is a copolymer.
In this case, the proportion of the monomer having a phenyl group substituted with a vinyl group in the copolymer composition (group represented by the general formula (2)) is 1% by mass or more and 95% by mass with respect to 100% by mass of the total composition. The mass is preferably 10% by mass or less, more preferably 10% by mass or more and 80% by mass or less, and further preferably 20% by mass or more and 70% by mass or less. If the ratio is less than this, the introduction effect may not be recognized. Moreover, when 95 mass% or more is contained, a copolymer may not melt | dissolve in alkaline aqueous solution.
Furthermore, the ratio of the carboxyl group-containing monomer in the copolymer is preferably 5% by mass or more and 99% by mass or less, and the copolymer may not be dissolved in the alkaline aqueous solution at a ratio below this.

Examples of the carboxyl group-containing monomer used as a copolymerization component include acrylic acid, methacrylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, crotonic acid, maleic acid, fumaric acid, monoalkyl maleate Examples include esters, monoalkyl esters of fumaric acid, 4-carboxystyrene and the like.
Further, the specific polymer in the present invention contains a carboxyl group by using polyacetal containing benzoic acid in the side chain, carboxybenzaldehyde-modified polyvinyl alcohol, or the like as a copolymer component constituting the specific copolymer. Also good.

The polymer having a phenyl group substituted with a vinyl group in the side chain in the present invention may be a multi-component copolymer by introducing other monomer components into the copolymer in addition to the monomer having a carboxyl group. In such a case, examples of the monomer that can be incorporated into the copolymer include:
Styrene derivatives such as styrene, 4-methylstyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-carboxystyrene, 4-aminostyrene, chloromethylstyrene, 4-methoxystyrene;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate;
Methacrylic acid aryl esters or alkyl methacrylate aryl esters such as phenyl methacrylate and benzyl methacrylate;
Methacrylic acid esters having an alkyleneoxy group such as methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, methacrylic acid methoxydiethylene glycol monoester, methacrylic acid methoxypolyethylene glycol monoester, methacrylic acid polypropylene glycol monoester;
Methacrylic acid esters containing amino groups such as 2-dimethylaminoethyl methacrylate and 2-diethylaminoethyl methacrylate;
Acrylic esters corresponding to these methacrylic esters;

Monomers having a phosphate group such as vinylphosphonic acid;
Monomers having an amino group such as allylamine and diallylamine;
Monomers having a sulfonic acid group such as vinyl sulfonic acid and its salt, allyl sulfonic acid and its salt, methallyl sulfonic acid and its salt, styrene sulfonic acid and its salt, 2-acrylamido-2-methylpropane sulfonic acid and its salt Kind;
Monomers having a nitrogen-containing heterocycle such as 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, N-vinylcarbazole;
4-vinylbenzyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, quaternized product of dimethylaminopropylacrylamide with methyl chloride, quaternized product of N-vinylimidazole with methyl chloride, 4-vinylbenzyl Monomers having a quaternary ammonium base such as pyridinium chloride;
Acrylamide or methacrylamide derivatives such as acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, N-methylolacrylamide, N-methoxyethylacrylamide, 4-hydroxyphenylacrylamide;
Vinyl esters such as acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate,
Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;
In addition, various monomers such as phenylmaleimide, hydroxyphenylmaleimide, N-vinylpyrrolidone, acryloylmorpholine, tetrahydrofurfuryl methacrylate, vinyl chloride, vinylidene chloride, allyl alcohol, vinyltrimethoxysilane, glycidyl methacrylate can be used as appropriate. it can.

  As a ratio of these monomers in the copolymer, a preferable ratio of the monomer having the group represented by the general formula (2) and the carboxyl group-containing monomer in the copolymer composition described above is maintained. As long as it can be introduced at any ratio.

  There is a preferred range for the molecular weight of the polymer as described above, and the weight average molecular weight is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 10,000 to 300,000.

  Examples (P-1) to (P-13) of polymers having a group represented by the general formula (2) according to the present invention in the side chain are shown below. In the structural formula, the number represents the mass% of each repeating unit in 100% by mass of the total composition of the copolymer.

The (B) specific polymer as the binder polymer used in the present invention may be used alone or in combination of two or more.
These binder polymers are 10 to 90% by mass, preferably 20 to 80% by mass, based on the total solid content of the negative recording layer, from the viewpoint of image portion strength (film properties, film strength) and image formability. Added in proportions.
Moreover, the (B) specific polymer in this invention can also be mixed and used for the conventionally well-known other binder polymer in the range which does not impair an effect.

[(C) Monomer having two or more phenyl groups substituted with vinyl groups (polymerizable compound)]
In the present invention, a monomer having two or more phenyl groups substituted with vinyl groups (hereinafter referred to as a specific monomer) used as a polymerizable compound is generated by radicals generated from the aforementioned (A) radical generator. Since crosslinking is effectively performed by recombination of styryl radicals, a negative recording layer that is highly sensitive and does not require heat treatment can be produced.
The specific monomer in the present invention is typically a compound represented by the following general formula (3).

In the general formula (3), Z ² represents a linking group, and R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, an amide group, An amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and the like, and these groups are further substituted with an alkyl group, an amino group, an aryl group, an alkenyl group, a carboxy group, a sulfo group, a hydroxy group, and the like. May be. R ²⁴ represents a substitutable group or atom. m ² represents an integer of 0 to 4, and k ² represents an integer of 2 or more.

The compound represented by the general formula (3) will be described in more detail. As the linking group for Z ² , an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, an arylene group, —N (R ⁵ ) —, —C (O) —O—, —C (R ⁶ ) ═N—, Examples include —C (O) —, a sulfonyl group, a heterocyclic structure, a benzene ring structure, or a group in which two or more are combined. Here, R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, an aryl group, or the like. Furthermore, the above-described linking group may have a substituent such as an alkyl group, an aryl group, or a halogen atom.

The heterocyclic structure constituting the linking group represented by Z ² includes pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring , Thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzthiazole ring, benzselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring , Triazine ring, quinoline ring, quinoxaline ring-containing nitrogen-containing heterocycle, furan ring, thiophene ring, etc., and these heterocyclic structures are further alkyl groups, amino groups, aryl groups, alkenyl groups, carboxy groups, sulfo groups. Group, hydroxy It may have a substituent like.

Examples of the substitutable group or atom represented by R ²⁴ include a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, an amide group, an amino group, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. Furthermore, these groups or atoms may have a substituent such as an alkyl group, an amino group, an aryl group, an alkenyl group, a carboxy group, a sulfo group, or a hydroxy group.

Among the compounds represented by the general formula (3), those having the structure shown below are preferable. That is, R ²¹ and R ²² in the general formula (3) are hydrogen atoms, R ²³ is a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (methyl group, ethyl group, etc.), and k ² is an integer of 2-10. Is preferred.
Specific examples (C-1) to (C-11) of the compound represented by the general formula (3) are shown below, but are not limited to these specific examples.

The (C) specific monomer as a polymerizable compound used in the present invention may be used alone or in combination of two or more.
The amount of the specific monomer added is in the range of 0.01 to 10 parts by mass with respect to 1 part by mass of the polymer (binder polymer) having the phenyl group substituted with the vinyl group (B) described above in the side chain. It is preferable that it is contained in the range of 0.05 to 1 part by mass.
Moreover, the (C) specific monomer in this invention can also be used by mixing with other conventionally well-known polymerizable compounds in the range which does not impair an effect.

[(D) Infrared absorber]
The infrared absorbent used in the present invention has a function of converting absorbed infrared light into heat and a function of generating excited electrons. When the infrared absorber absorbs light, the radical generator (A) described above is decomposed to generate radicals.
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 documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.

  Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

  Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Moreover, as another example preferable as a dye, the near-infrared absorptive dye described as the formula (I) and (II) in US Patent 4,756,993 can be mentioned.

  Specific examples (S-1) to (S-14) of dyes as infrared absorbers preferably used are shown below, but are not limited thereto.

In addition, as described above, an infrared absorber in which the counter anion of the infrared absorber (cationic sensitizing dye) exemplified here is substituted with an organic boron anion can also be used.
These dyes may be used alone or in combination of two or more.
The content of the dye as the infrared absorber is suitably about 3 to 300 mg per 1 m ^{2 of the} negative recording layer. Preferably it is 10-200 mg / m < ² >.

  Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. Within this preferred particle size range, excellent dispersion stability of the pigment in the negative recording layer coating solution can be obtained, and a uniform negative recording layer can be obtained.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

  From the viewpoint of uniformity in the negative recording layer and durability of the negative recording layer, the pigment as these infrared absorbers is 0.01 to 50% by mass with respect to the total solid content constituting the negative recording layer, Preferably it is 0.1-10 mass%, Most preferably, it can add in the ratio of 0.1-10 mass%.

  In addition to the above essential components (A) to (D), the negative recording layer of the lithographic printing plate precursor according to the invention may further contain other components suitable for its use and production method. . Hereinafter, it illustrates about a preferable other component.

(Polymerization inhibitor)
In the negative recording layer of the present invention, a compound having a polymerizable ethylenically unsaturated double bond, that is, (C) a specific monomer (polymerizable compound) is unnecessary during the production or storage of the negative recording layer. In order to prevent thermal polymerization, it is desirable to add a small amount of 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-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the nonvolatile components in the entire composition.
In addition, if necessary, a higher fatty acid derivative such as behenic acid or behenamide is added to prevent polymerization inhibition by oxygen, and it is unevenly distributed on the surface of the negative recording layer during the drying process after coating. Also good. The addition amount of the higher fatty acid derivative is preferably about 0.5% by mass to about 10% by mass with respect to the nonvolatile components in the entire composition.

[Colorant]
Further, a dye or pigment may be added to the negative recording layer in the present invention for the purpose of coloring. Thereby, so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a printing plate can be improved. As the colorant, it is preferable to use a dye or a pigment. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment as the colorant is preferably about 0.5% by mass to about 5% by mass with respect to the non-volatile components in the entire composition. In the case of dyes, those containing no halogen ions as counter anions are preferred.

[Other additives]
In the negative recording layer of the lithographic printing plate precursor according to the invention, depending on the purpose, oxygen removing agent and reducing agent such as phosphine, phosphonate, phosphite, fading inhibitor, surfactant, plasticizer, antioxidant, Ultraviolet absorbers, fungicides, antistatic agents, and other additives that impart various characteristics may be mixed with a diluting solvent or the like.

Moreover, you may add well-known additives, such as an inorganic filler for improving the physical property of a cured film, other plasticizers, and a fat-sensitizing agent which can improve the ink inking property of the negative type recording layer surface.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like (B) specific polymer It can generally add in the range of 10 mass% or less with respect to the total mass of (binder polymer) and (C) specific monomer.
Further, in order to enhance the effect of heating / exposure after development for the purpose of improving the film strength (printing durability) described later, a UV initiator, a thermal crosslinking agent, or the like can also be added.

  Furthermore, for the purpose of accelerating the polymerization, a polymerization accelerator represented by amine, thiol, disulfide and the like, a chain transfer agent and the like can be added. Specific examples thereof include N-phenylglycine, triethanolamine, N, N-diethylaniline and the like.

In the present invention, when a negative recording layer is applied, the negative recording layer components are dissolved in various organic solvents and applied onto a support or intermediate layer (undercoat layer) described later.
Solvents used here include dioxane, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl. Ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, Examples include ethyl lactate. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount (thickness) of the negative recording layer mainly affects the sensitivity, developability, exposure film strength and printing durability of the negative recording layer, and can be appropriately selected according to the application. desirable.
The lithographic printing plate precursor for scanning exposure, which is the main object of the present invention, has a coating amount in the range of about 0.1 to about 10 g / m ² in terms of mass after drying from the viewpoint of printing durability, sensitivity, and the like. Is appropriate. More preferably from 0.5 to 5 g / m ^2.

(Physical properties of negative recording layer)
The physical properties of the negative recording layer in the present invention are as follows: the developing speed of the unexposed area with respect to an alkaline developer having a pH of 10 to 13.5 is 80 nm / sec or more, and the penetration speed of the alkaline developer in the exposed area is 100 nF. / Sec or less is preferable.
Here, the development speed with an alkaline developer having a pH of 10 to 13.5 is a value obtained by dividing the film thickness (m) of the negative recording layer by the time (sec) required for development, and the penetration of the alkaline developer. The speed is a value indicating the change speed of the capacitance (F) when the negative recording layer is formed on a conductive support and immersed in a developer.
Hereinafter, a method for measuring “development speed with respect to an alkali developer” and “penetration speed of an alkali developer” in the present invention will be described in detail.

[Measurement of development speed for alkaline developer]
Here, the developing speed of the negative recording layer with respect to the alkaline developer is a value obtained by dividing the film thickness (m) of the negative recording layer by the time required for development (sec).
As a method for measuring the developing speed in the present invention, as shown in FIG. 1, a sample having an unexposed negative recording layer (indicated as a photosensitive layer in FIG. 1) on an aluminum support has a pH of 10 to 13.5. The film was immersed in a certain alkaline developer (30 ° C.) in the range of 1 to 3, and the dissolution behavior of the negative recording layer was examined with a DRM interference wave measuring apparatus. FIG. 1 shows a schematic diagram of a DRM interference wave measuring apparatus for measuring the dissolution behavior of a negative recording layer. In the present invention, a change in film thickness was detected by interference using light of 640 nm. When the development behavior is non-swelling development from the surface of the negative recording layer, the film thickness gradually decreases with respect to the development time, and an interference wave corresponding to the thickness is obtained. Further, in the case of swelling dissolution (film removal dissolution), the film thickness changes due to the penetration of the developer, so that a clean interference wave cannot be obtained.

Measurement is continued under these conditions, and the development speed is calculated from the time (s) until the film thickness reaches zero (development completion time) (s) and the film thickness (μm) of the negative recording layer. Can be obtained by the following equation. It is determined that the higher the development speed, the easier the film is removed by the developer and the better the developability.
Development speed (in unexposed area) = [negative recording layer thickness (μm) / recording completion time (sec)]

[Measurement of penetration rate of alkaline developer]
The permeation rate of the alkaline developer is a value indicating the change rate of the capacitance (F) when the negative recording layer is formed on a conductive support and immersed in the developer.
As shown in FIG. 2, a method for measuring the capacitance, which is a measure of permeability in the present invention, is a predetermined method on an aluminum support in a constant alkaline developer (28 ° C.) in the range of pH 10 to 13.5. Is exposed to an exposure amount of 1, and a hardened negative recording layer (indicated as a recording layer in FIG. 2) is immersed as one electrode, a lead wire is connected to an aluminum support, and the other is a normal electrode The method of applying a voltage using is mentioned. After the voltage is applied, the developer permeates the interface between the support and the negative recording layer as the immersion time elapses, and the capacitance changes.

From the time (s) required until the capacitance changes and the film thickness (μm) of the negative recording layer, it can be obtained by the following equation. It is determined that the smaller the permeation rate, the lower the permeability of the developer.
Developer penetration rate (of exposed area) =
[Negative recording layer thickness (μm) / Time required for capacitance change to be constant (s)]

  As a preferable physical property of the negative recording layer in the present invention, the development rate of an unexposed portion with an alkaline developer having a pH of 10 to 13.5 according to the above measurement is preferably 80 to 400 nm / sec. The penetration rate with respect to the negative recording layer is preferably 90 nF / sec or less. Further, the development rate of the unexposed area with an alkaline developer having a pH of 10 to 13.5 as measured above is more preferably 90 to 200 nm / sec, and the penetration rate of the similar alkaline developer into the negative recording layer is 80 nF / It is preferable that it is sec or less. The upper limit of the development speed or the lower limit of the permeation speed is not particularly limited, but considering the balance between the two, the development speed of the unexposed area is more preferably in the range of 90 to 200 nm / sec. The permeation rate of the alkali developer into the negative recording layer is preferably 80 nF / sec or less.

Control of the development speed of the unexposed portion of the negative recording layer and the penetration speed of the alkaline developer into the negative recording layer after curing can be performed by a conventional method. Addition of a hydrophilic compound is useful for improving the developing speed, and means for adding a hydrophobic compound is useful for suppressing the penetration of the developer into the exposed area.
In the present invention, by adjusting the content of each component constituting the negative recording layer according to the present invention described above, the development speed of the negative recording layer and the penetration speed of the developer can be easily within the above preferred ranges. Can be controlled. The negative recording layer in the present invention is preferably in the range of the physical property values.

[Support]
As the support for the lithographic printing plate precursor in the invention, a conventionally known hydrophilic support for use in the lithographic printing plate precursor can be used without limitation.
The support used is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc). , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), Paper or plastic film, etc. on which such metals are laminated or vapor-deposited are included. Appropriately known physical and chemical treatments are applied to these surfaces for the purpose of imparting hydrophilicity and improving strength as necessary. You may give it.

  In particular, preferred supports include paper, polyester film or aluminum plate, among which dimensional stability is good, relatively inexpensive, and a surface with excellent hydrophilicity and strength is provided by surface treatment as required. An aluminum plate that can be formed is more preferable. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.

  An aluminum plate is a metal plate mainly composed of dimensionally stable aluminum. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or aluminum (alloy) is laminated. Or it is chosen from the vapor-deposited plastic film or paper. In the following description, the above-mentioned support made of aluminum or an aluminum alloy is generically used as an aluminum support. Examples of the foreign element contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of the foreign element in the alloy is 10% by mass or less. In the present invention, a pure aluminum plate is suitable, but since completely pure aluminum is difficult to manufacture in the refining technique, it may contain a slightly different element. Thus, the composition of the aluminum plate applied to the present invention is not specified, and it is a conventionally known material such as JIS A 1050, JIS A 1100, JIS A 3103, JIS A 3005, etc. Can be used as appropriate.

Further, the thickness of the aluminum support used in the present invention can be appropriately changed depending on the size of the printing press, the size of the printing plate, and the user's request. However, handling properties, occurrence of jamming in the CTP exposure apparatus, etc. In view of the above, 0.25 mm to 0.55 mm is preferable, and 0.3 to 0.50 mm is more preferable.
Furthermore, the aluminum support suitable for the present invention preferably has a surface shape as shown below.

<Surface shape of aluminum support>
The aluminum support in the present invention preferably has Ra, ΔS, and a45, which are surface shape factors, satisfy the following conditions (i) to (iii), respectively.
(I) Ra: 0.2-0.40 μm
(Ii) ΔS: 35 to 85%
(Iii) a45: 25-55%
Here, Ra represents the surface roughness.
ΔS is obtained by the following equation from the actual area S _x obtained by the approximate three-point method and the geometric measurement area S ₀ .
ΔS (%) = (S _x −S ₀ ) / S ₀ × 100
a45 represents an area ratio of a portion having an inclination of 45 ° or more obtained by extracting a component having a wavelength of 0.2 μm or more and 2 μm or less.
Hereinafter, these surface shapes will be described in detail.

  (I) Ra represents the surface roughness. Here, the surface roughness (Ra) of the aluminum support means the centerline average roughness (arithmetic average roughness) in the direction perpendicular to the aluminum rolling direction. From the roughness curve measured with a stylus meter, When the portion of the measurement length L is extracted in the direction of the center line, the center line of the extracted portion is the X axis, and the axis perpendicular to the X axis is the Y axis, the roughness curve is expressed by Y = f (X). The value given by is expressed in μm. (The determination of L and the measurement of average roughness are in accordance with JIS B 0601.)

In general, it is effective to increase the surface roughness in order to improve the water retention. However, if the surface roughness is increased, deep recesses are likely to occur locally. Since a film tends to be formed, Ra needs to be in the range shown below.
That is, in the present invention, Ra is preferably in the range of 0.20 to 0.40 μm, more preferably in the range of 0.20 to 0.35 μm, and still more preferably in the range of 0.25 to 0.35 μm. It is a range.

As will be described in detail later, ΔS is an actual area S _x obtained by an approximate three-point method from three-dimensional data obtained by measuring 512 × 512 points of 50 × 50 μm of the support surface using an atomic force microscope. And the geometric measurement area (apparent area) S ₀ is obtained by the following equation.
ΔS (%) = (S _x −S ₀ ) / S ₀ × 100
The surface area ratio ΔS is a factor indicating the degree of increase in the actual area S _x by the roughening process with respect to the geometric measurement area S ₀ .

When ΔS increases, the contact area with the negative recording layer increases, and as a result, the printing durability can be improved. Therefore, ΔS is preferably in the range shown below.
That is, in the present invention, ΔS is preferably in the range of 35 to 85%, more preferably in the range of 40 to 85%, and still more preferably in the range of 40 to 80%.

As described in detail later, a45 extracts components having a wavelength of 0.2 μm or more and 2 μm or less from three-dimensional data obtained by measuring 512 × 512 points of 50 × 50 μm of the support surface using an atomic force microscope. Represents the area ratio of the portion having the inclination of 45 ° or more.
The steepness is a factor representing the sharpness of the fine shape of the support surface. Specifically, it represents the ratio of the area having an inclination of a certain angle or more to the actual area in the unevenness of the support surface.

The area ratio (steepness) a45 of the slope having an inclination of 45 ° or more is preferably increased in order to improve the adhesion between the negative recording layer and the support and to improve the printing durability. . On the other hand, in order to suppress ink catching in the non-image area and improve stain resistance, it is preferable to make it smaller. For these reasons, a45 is preferably in the following range.
That is, in this invention, it is preferable that a45 is 25 to 55% of range, More preferably, it is 30 to 55% of range, More preferably, it is 30 to 50% of range.

  In the aluminum support in the present invention, ΔS and a45 are determined as follows.

(1) Measurement of surface shape by atomic force microscope In the present invention, in order to obtain ΔS and a45, first, the surface shape is measured by an atomic force microscope (AFM) to obtain three-dimensional data. .
The measurement can be performed, for example, under the following conditions. That is, the aluminum support is cut to a size of 1 cm square, set on a horizontal sample stage on a piezo scanner, the cantilever is approached to the sample surface, and when it reaches the region where the atomic force works, it scans in the XY direction. At that time, the unevenness of the sample is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan 150 μm in the XY direction and 10 μm in the Z direction is used. A cantilever having a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m (SI-DF20, manufactured by NANOPROBE) is used for measurement in a DFM mode (Dynamic Force Mode). Further, the reference plane is obtained by correcting the slight inclination of the sample by approximating the obtained three-dimensional data by least squares.
At the time of measurement, the surface of 50 × 50 μm is measured at 512 × 512 points. The resolution in the XY direction is 1.9 μm, the resolution in the Z direction is 1 nm, and the scan speed is 60 μm / sec.

(2) Correction of three-dimensional data For the calculation of ΔS, the three-dimensional data obtained in the above (1) is used as it is, but for the calculation of a45, the wavelength 0 is calculated from the three-dimensional data obtained in the above (1). Use a correction that removes components of 2 μm to 2 μm. With this correction, when a surface having deep irregularities, such as a support used in a lithographic printing plate precursor, is scanned with an AFM probe, the probe bounces against the edge of the convex portion, or the probe touches the wall surface of the deep concave portion. It is possible to remove noise that occurs when a part other than the tip of the contacted part.
The correction is performed by performing a fast Fourier transform on the three-dimensional data obtained in (1) above to obtain a frequency distribution, removing components having wavelengths of 0.2 μm or more and 2 μm or less, and then performing an inverse Fourier transform. .

(3) Calculation of each factor and calculation of ΔS Using the three-dimensional data (f (x, y)) obtained in (1) above, three adjacent points are extracted, and a micro triangle formed by the three points Is obtained as a real area S _x . The surface area ratio ΔS is obtained from the obtained actual area S _x and the geometric measurement area S _{0 according} to the following formula. S ₀ is a geometric measurement area, which is determined by S ₀ = L _x × L _y , and in the present invention, L _x = L _y = 50 μm.
ΔS (%) = (S _x −S ₀ ) / S ₀ × 100

Calculation of a45 Using the three-dimensional data (f (x, y)) obtained by correcting in (2) above, three adjacent points are extracted, and a micro triangle formed by the three points and a reference plane Are calculated for all data to obtain a gradient distribution curve, and on the other hand, the sum of the areas of the small triangles is obtained as the actual area. From the gradient distribution curve, the area ratio a45 of the portion having a gradient of 45 degrees or more with respect to the actual area is calculated.

In this invention, the aluminum support body which has the surface shape mentioned above can be produced by performing the surface treatment mentioned later.
Hereinafter, the surface treatment applied to the aluminum support will be described.

(Roughening treatment)
Examples of the roughening treatment method include mechanical roughening, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. Furthermore, an electrochemical surface roughening method in which the surface is electrochemically roughened in a hydrochloric acid or nitric acid electrolyte solution, a wire brush grain method in which the aluminum surface is scratched with a metal wire, and the aluminum surface is ground with a polishing ball and an abrasive. A mechanical surface roughening method such as a pole grain method, a brush grain method in which the surface is roughened with a nylon brush and an abrasive, can be used, and the above surface roughening methods can be used alone or in combination. it can.
Among them, a method usefully used for roughening is an electrochemical method in which roughening is chemically carried out in hydrochloric acid or nitric acid electrolyte, and a suitable amount of electricity during anode is 50 C / dm ^{2 to} 400 C / dm ^2. Range. More specifically, in an electrolytic solution containing 0.1 to 50% hydrochloric acid or nitric acid, the temperature is 20 to 80 ° C., the time is 1 second to 30 minutes, and the current density is 10 A / dm ^{2 to} 50 A / dm ^2. It is preferable to perform direct current electrolysis.

The roughened aluminum support may be chemically etched with acid or alkali. Etching agents suitably used are caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide, and the like. Preferred ranges of concentration and temperature are 1 to 50% and 20%, respectively. ~ 100 ° C. Pickling is performed to remove dirt (smut) remaining on the surface after etching. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borohydrofluoric acid and the like are used.
In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65 mass% sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And the alkali etching method described in Japanese Patent Publication No. 48-28123.
After the treatment as described above, if Ra, ΔS, and a45, which are factors of the surface shape of the treated surface, satisfy the above conditions (i) to (iii), the method conditions are particularly limited to these. Not.

(Anodizing treatment)
The aluminum support that has been treated as described above to form an oxide layer is then anodized.
In the anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, or an aqueous solution of boric acid / sodium borate is used as a main component of the electrolytic bath singly or in combination. Under the present circumstances, the component normally contained in at least Al alloy plate, an electrode, tap water, groundwater, etc. may of course be contained in electrolyte solution. Further, the second and third components may be added. Here, the second and third components are, for example, metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, and ammonium ions. Examples include cations, nitrate ions, carbonate ions, chloride ions, phosphate ions, fluorine ions, sulfite ions, titanate ions, silicate ions, borate ions and the like, and the concentration is 0 to 10,000 ppm. May be included. The conditions of the anodizing treatment are such that the amount of the anodized film produced by the treatment is 0.5 to 10.0 g / m ² , more preferably 1.0 to 5.0 g / m ² . The concentration of the acid as the main component is preferably 30 to 500 g / liter, the treatment liquid temperature is 10 to 70 ° C., and the treatment is performed by direct current or alternating current electrolysis in the range of a current density of 1 to 40 A / m ² .

(Hydrophilic treatment)
A widely known method can be applied as the hydrophilic treatment on the surface of the support. As a particularly preferable treatment, a hydrophilic treatment with silicate or polyvinylphosphonic acid is performed. A film | membrane is formed by 2-40 mg / m < ² > as Si or P element amount, More preferably, it is 4-30 mg / m < ² >. The coating amount can be measured by fluorescent X-ray analysis.

  The hydrophilization treatment is carried out by applying an anodized film to an aqueous solution containing 1 to 30% by mass, preferably 2 to 15% by mass of alkali metal silicate or polyvinylphosphonic acid, and having a pH of 10 to 13 at 25 ° C. This is carried out by immersing the aluminum support on which is formed, for example, at 15 to 80 ° C. for 0.5 to 120 seconds.

  As the alkali metal silicate used for the hydrophilization treatment, sodium silicate, potassium silicate, lithium silicate, or the like is used. Examples of the hydroxide used for increasing the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide. In addition, you may mix | blend alkaline-earth metal salt or Group IVB metal salt with said process liquid. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble substances such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. Salt. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium fluoride titanium, potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, etc. Can be mentioned.

Alkaline earth metal salts or Group IVB metal salts may be used alone or in combination of two or more. A preferable range of these metal salts is 0.01 to 10% by mass, and a more preferable range is 0.05 to 5.0% by mass. Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.
Furthermore, a combination of a support with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, and JP-A-52-30503 is combined with the above anodizing treatment and hydrophilization treatment. Surface treatment is also useful.

[Intermediate layer (undercoat layer)]
In the lithographic printing plate precursor according to the invention, an intermediate layer (undercoat layer) may be provided for the purpose of improving adhesion between the negative recording layer and the support and soiling. Specific examples of such an intermediate layer include JP-B-50-7481, JP-A-54-72104, JP-A-59-101651, JP-A-60-149491, JP-A-60-232998, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, JP-A-7-314937, JP-A-8-202025, Special Kaihei 8-320551, JP 9-34104, JP 9-236911, JP 9-269593, JP 10-69092, JP 10-115931, JP 10-161317, JP 10-260536, JP-A-10-282682, JP-A-11-84684, Japanese Patent Application No. 8-225335, Japanese Patent Application No. 8-270098, Japanese Patent Application No. 9-195863, Japanese Patent Application No. 9-195864, Japanese Patent Application No. 9-89646, Japanese Patent Application No. 9-106068, Japanese Patent Application No. 9-183834, Japanese Patent Application No. 9-264411, Japanese Patent Application No. 9 -127232, Japanese Patent Application No. 9-245419, Japanese Patent Application No. 10-127602, Japanese Patent Application No. 10-170202, Japanese Patent Application No. 11-36377, Japanese Patent Application No. 11-165661, Japanese Patent Application No. 11-284091 No., Japanese Patent Application No. 2000-14697, and the like.

[Back coat layer]
In the lithographic printing plate precursor according to the invention, a backcoat layer may be provided on the back surface of the support, if necessary. Such a back coat layer comprises 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. A coating layer is preferably used.
Among these coating layers, silicon alkoxy compounds such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , and Si (OC ₄ H ₉ ) ₄ are available at a low price. The coating layer of the metal oxide provided therefrom is particularly preferred because of its excellent development resistance.

<Plate making>
In order to make the lithographic printing plate precursor according to the invention, at least an exposure and development process is performed.
As a light source for exposing the lithographic printing plate precursor according to the invention, an infrared laser is preferable, and thermal recording with an ultraviolet lamp or a thermal head is also possible.
In particular, in the present invention, image exposure is preferably performed with a solid-state laser and a semiconductor laser that emit infrared rays having a wavelength of 750 nm to 1400 nm. The laser output is preferably 100 mW or more, and a multi-beam laser device is preferably used to shorten the exposure time. The exposure time per pixel is preferably within 20 μsec. The energy applied to the planographic printing plate precursor is preferably 10 to 300 mJ / cm ² . If the exposure energy is too low, the curing of the negative recording layer does not proceed sufficiently. If the exposure energy is too high, the negative recording layer may be laser ablated and the image may be damaged.

  The exposure in the present invention can be performed by overlapping the light beams of the light sources. Overlap means that the sub-scanning pitch width is smaller than the beam diameter. The overlap can be expressed quantitatively by FWHM / sub-scanning pitch width (overlap coefficient), for example, when the beam diameter is expressed by the half width (FWHM) of the beam intensity. In the present invention, the overlap coefficient is preferably 0.1 or more.

  The scanning method of the light source of the exposure apparatus used in the present invention is not particularly limited, and a cylindrical outer surface scanning method, a cylindrical inner surface scanning method, a planar scanning method, or the like can be used. The channel of the light source may be a single channel or a multi-channel, but in the case of a cylindrical outer surface system, a multi-channel is preferably used.

  The lithographic printing plate precursor according to the invention is developed after being exposed. As the developer used in such development processing, an alkaline aqueous solution having a pH of 14 or less is particularly preferred, and an alkaline aqueous solution having a pH of 8 to 12 containing an anionic surfactant is more preferably used. For example, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, Examples include inorganic alkaline agents such as potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Moreover, 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.

In the development processing of the lithographic printing plate precursor according to the invention, 1 to 20% by mass of an anionic surfactant is added to the developer, and more preferably 3 to 10% by mass. If the amount is too small, the developability deteriorates. If the amount is too large, the strength such as the abrasion resistance of the image deteriorates. Anionic surfactants include, for example, sodium salt of lauryl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, such as sodium salt of isopropyl naphthalene sulfonic acid, sodium salt of isobutyl naphthalene sulfonic acid, polyoxy Higher carbon number such as sodium salt of ethylene glycol mononaphthyl ether sulfate ester, sodium salt of dodecylbenzene sulfonic acid, alkylaryl sulfonate such as sodium salt of metanitrobenzene sulfonic acid, secondary sodium alkyl sulfate, etc. Aliphatic alcohol phosphates such as alcohol sulfates, sodium salts of cetyl alcohol phosphates, eg C _{17 H 33 CON (CH 3)} CH 2 CH 2 SO 3 sulfonates of alkylamides such as Na, for example, sodium sulfosuccinate dioctyl ester, sulfonate of dibasic aliphatic esters such as sodium sulfosuccinate dihexyl ester Salts are included.

  Moreover, you may add the organic solvent which mixes with water, such as benzyl alcohol, to a developing solution as needed. As the organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol, 1,4-phenylbutanol, 2,2-phenylbutanol, 1,2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m -Methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, 3-methylcyclohexanol and the like can be mentioned. The content of the organic solvent is preferably 1 to 5% by mass with respect to the total mass of the developer at the time of use. The amount used is closely related to the amount of surfactant used, and it is preferable to increase the amount of anionic surfactant as the amount of organic solvent increases. This is because when the amount of the organic solvent is large and the amount of the anionic surfactant is small, the organic solvent is not dissolved, so that it is impossible to expect good developability.

Furthermore, additives such as an antifoaming agent and a hard water softening agent can be further contained as necessary. Examples of the hard water softener include Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , Calgon (sodium polymetaphosphate) Such as polyphosphates, aminopolycarboxylic acids (eg, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt Hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2 -Propanol tetraacetic acid, its potassium salt, Sodium salt), other polycarboxylic acids (for example, 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salt thereof, sodium salt thereof; 2 monophosphonobutanone tricarboxylic acid-2,3,4, Potassium salt, sodium salt thereof, etc., organic phosphonic acids (eg, 1-phosphonoethanetricarboxylic acid-1,2,2, potassium salt, sodium salt thereof; 1-hydroxyethane-1,1-diphosphonic acid, Potassium salt, sodium salt thereof; aminotrimethylenephosphonic acid, potassium salt thereof, sodium salt thereof and the like. The optimum amount of such a hard water softener varies depending on the hardness of the hard water used and the amount used, but is generally 0.01 to 5% by weight, more preferably in the developer at the time of use. It is made to contain in 0.01-0.5 mass%.

  Furthermore, when developing a lithographic printing plate precursor using an automatic processor, the developer becomes fatigued according to the amount of processing, so that the processing capacity can be restored using a replenisher or fresh developer. Also good. In this case, it is preferable to replenish by the method described in US Pat. No. 4,882,246. Developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, 56-42860, and 57-7427 are also preferable.

  The lithographic printing plate precursor thus developed is subjected to washing water, surface activity as described in JP-A Nos. 54-8002, 55-11545, 59-58431, and the like. It may be post-treated with a rinsing liquid containing an agent, a desensitizing liquid containing gum arabic, starch derivatives, and the like. In the post-treatment of the lithographic printing plate precursor according to the invention, these treatments can be used in various combinations.

In the plate making of the lithographic printing plate precursor according to the present invention, it is effective to subject the image after development to full post-heating or full exposure for the purpose of improving image strength and printing durability.
Although extremely strong conditions can be used for heating after development, the heating temperature is usually set from the viewpoint of obtaining a sufficient image strengthening action and suppressing damage to the support and the image area due to heat. It implements in the range of 200-500 degreeC.

The planographic printing plate obtained by the above processing is loaded on an offset printing machine and used for printing a large number of sheets.
In addition, the stain | pollution | contamination of the lithographic printing plate used for printing can be removed with a plate cleaner. As plate cleaners used for removing stains on the plate during printing, conventionally known plate cleaners for PS plates are used. For example, CL-1, CL-2, CP, CN-4, CN, CG-1, PC-1, SR, IC (made by Fuji Photo Film Co., Ltd.), etc. are mentioned.

EXAMPLES Hereinafter, although this invention is demonstrated according to the following examples, the scope of the present invention is not limited to these examples.
First, synthesis examples of (B) a polymer having a phenyl group substituted with a vinyl group in the side chain and (C) a monomer having two or more phenyl groups substituted with a vinyl group are shown below. .

[Synthesis Example 1: (B) Synthesis Example of Specific Polymer (P-1)]
150 g of bismuthiol (2,5-dimercapto-1,3-4-thiadiazole) was suspended in 600 ml of methanol, and 101 g of triethylamine was gradually added while cooling to obtain a uniform solution. While maintaining at room temperature, p-chloromethylstyrene (manufactured by Seimi Chemical Co., CMS-14) was added dropwise over 10 minutes, and stirring was further continued for 3 hours. The reaction product gradually precipitated. After stirring, the reaction product was transferred to an ice bath, the internal temperature was cooled to 10 ° C., and the product was separated by suction filtration. The compound (monomer) shown below was obtained with a yield of 75% by washing with methanol and drying for one day in a vacuum dryer.

  Take 40 g of the above monomer in a 1-liter four-necked flask equipped with a stirrer, nitrogen inlet tube, thermometer, and reflux condenser, add 70 g of methacrylic acid, 200 ml of ethanol and 50 ml of distilled water, and stir on a water bath with stirring. 110 g was added. Under nitrogen atmosphere, the internal temperature was heated to 70 ° C., and 1 g of azobisisobutyronitrile (AIBN) was added at this temperature to initiate polymerization. The mixture was heated and stirred for 6 hours, and then the polymerization system was cooled to room temperature. A part of the sample was taken out, diluted hydrochloric acid was added to adjust the pH to about 3, and this was opened in water to obtain a polymer having the structure shown below.

  100 g of 1,4-dioxane and 23 g of p-chloromethylstyrene were added to the remaining polymer solution from which a part of the polymer was taken out, and stirring was further continued at room temperature for 15 hours. Thereafter, 80 to 90 g of concentrated hydrochloric acid (35 to 37% aqueous solution) was added, and after confirming that the pH of the system was 4 or less, the whole was transferred into 3 liters of distilled water. The precipitated polymer was separated by filtration, washed repeatedly with distilled water, and then dried for one day in a vacuum dryer. Thereby, the target (B) specific polymer (P-1) was obtained with a yield of 90%. It is a polymer having a weight average molecular weight of 90,000 (polystyrene conversion) by molecular weight measurement by gel permeation chromatography, and further supports the structure of (B) specific polymer (P-1) by analysis by proton NMR. there were.

[Synthesis Example 2: (C) Synthesis Example of Specific Monomer (C-5)]
A thirocyanuric acid 89g was suspended in 1.5 liters of methanol, and a 30% aqueous solution in which 84 g of potassium hydroxide was dissolved was gradually added while cooling to obtain a uniform solution. To this, 230 g of p-chloromethylstyrene was gradually added dropwise at room temperature so that the internal temperature did not exceed 40 ° C. Shortly after the addition, the product precipitated, but the stirring was continued, and after stirring for 3 hours, the product was separated by suction filtration. After washing with methanol and drying all day and night in a vacuum dryer, (C) the specific monomer (C-5) was obtained in a yield of 90%.

(Examples 1-5, Comparative Examples 1-4)
[Create support]
The surface treatment shown below was performed using a JIS A 1050 aluminum plate having a thickness shown in Table 3 below and having a width of 1030 mm.

<Surface treatment>
In the surface treatment, the following various treatments (a) to (f) were continuously performed. In addition, after each process and water washing, the liquid was drained with the nip roller.

(A) The aluminum plate was etched at a caustic soda concentration of 26 mass%, an aluminum ion concentration of 6.5 mass%, and a temperature of 70 ° C. to dissolve the aluminum plate at 5 g / m ² . Thereafter, it was washed with water.
(B) A desmut treatment by spraying was performed with a 1% by mass aqueous solution of nitric acid having a temperature of 30 ° C. (including 0.5% by mass of aluminum ions), and then washed with water.

(C) An electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass aqueous nitric acid solution (including 0.5% by mass aluminum ions and 0.007% by mass ammonium ions) at a temperature of 30 ° C. The AC power source was subjected to an electrochemical surface roughening treatment using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 2 msec until the current value reached a peak from zero and a duty ratio of 1: 1. Ferrite was used for the auxiliary anode. The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 250 C / cm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Thereafter, it was washed with water.

(D) The aluminum plate was spray-etched at 35 ° C. with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass to dissolve the aluminum plate by 0.2 g / m ² , The removal of the smut component mainly composed of aluminum hydroxide generated during chemical roughening and the edge portion of the generated pit were dissolved to smooth the edge portion. Thereafter, it was washed with water.
(E) A desmut treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid having a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), and then washing with water by spraying.

(F) Anodization was performed for 50 seconds at a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions), a temperature of 33 ° C., and a current density of 5 (A / dm ² ). Thereafter, it was washed with water. The mass of the anodic oxide film at this time was 2.7 g / m ² .

  The surface roughness Ra, surface area ratio ΔS, and steepness a45 of the aluminum support thus obtained were Ra = 0.27 (measuring instrument: Surfcom manufactured by Tokyo Seimitsu Co., Ltd., stylus tip diameter 2 microns), respectively. Meter), ΔS = 75%, a45 = 44% (measuring instrument: SPA300 / SPI3800N manufactured by Seiko Instruments Inc.).

[Formation of negative recording layer]
Next, the following recording layer coating solution is prepared, applied to the aluminum support subjected to the above surface treatment so that the thickness after drying becomes 1.4 μm, and dried in a dryer at 70 ° C. for 5 minutes. The specific lithographic printing plate precursors [CTP-1] to [CTP-5] were obtained.

<Recording layer coating solution>
-(A) Radical generator (BC-6) 2.5 parts by mass-(B) Specific polymer (P-1) 10.0 parts by mass-(C) Specific monomer (C-5) 3.5 parts by mass -(D) Infrared absorber (S-4) 0.5 mass part-Dioxane 70.0 mass part-Cyclohexane 20.0 mass part

  The components (A) to (D) used in the recording layer coating liquid are those described as the specific examples described above.

[Evaluation of photosensitivity (sensitivity) of lithographic printing plate precursor]
Specific lithographic printing plate precursors [CTP-1] to [CTP-5] obtained as described above were subjected to a 50% flat screen image with a resolution of 175 lpi on a Trendsetter 3244VX manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser. Was exposed by changing the outer drum rotation speed at 150 rpm and the output in the range of 0 to 8 W by 0.15 logE. The exposure was performed under conditions of 25 ° C. and 50% RH.
After the exposure, development was performed at 30 ° C. for 10 seconds with a developer in which 6% by mass of sodium metasilicate was dissolved. When the minimum exposure energy at which the flat screen image of the lithographic printing plate obtained by development shows 50% was determined as the sensitivity of the lithographic printing plate precursor, all the specific lithographic printing plate precursors showed a high sensitivity of 175 mJ / cm ^2. It was.

[Create slip sheet]
[Interleaf 1]
Bleached kraft pulp was beaten and 0.4% by mass of rosin sizing agent was added to the paper stock diluted to a concentration of 4%, and aluminum sulfate was added until the pH reached 5.0. The paper stock was coated with 3.0% by weight of a paper strength agent mainly composed of starch, and paper was made. Beck smoothness of the surface in contact with the outermost surface on the negative recording layer side was 60 seconds, and the density was 0.8 g / cm. ³ and interleaf 1 having a water content of 6.0% and a basis weight of 38 g / m ² was prepared. The main points of the specifications of the slip sheet 1 are shown in Table 2.

[Interleaf 2]
As interleaving paper 2, Beck smoothness of the surface in contact with the outermost surface on the negative recording layer side made from the raw material of 100% hardwood bleached kraft pulp using the same sizing agent and fixing agent, density about 500 seconds, density Paper having 0.8 g / cm ³ , moisture 4.5%, pH 5.5 and basis weight 30 g / m ² was used. The main points of the specifications of the slip sheet 2 are shown in Table 2.

[Preparation of lithographic printing plate precursor laminate]
The obtained specific lithographic printing plate precursors [CTP-1] to [CTP-5] and the slip sheet 1 or the slip sheet 2 are combined and stacked alternately as shown in Table 3 below. To 5 and lithographic printing plate precursor laminates in Comparative Examples 1 to 4 were produced. In the obtained lithographic printing plate precursor laminate, the dynamic friction coefficient of the negative recording layer with respect to the interleaf was measured by the method presented in JIS P 8147. The results are also shown in Table 3.

[Evaluation of lithographic printing plate precursor laminate]
(Scratch resistance)
The prepared laminate was piled up to a height of 1 m, vibrated for 10 minutes, then exposed and developed, and the state of occurrence of scratches was evaluated visually. The following criteria are used as the evaluation scale. The exposure and development conditions are as described above except that the output during exposure is fixed at 6 W. The evaluation results are shown in Table 3.
○: Scratches are not seen △: Slightly scratches are seen ×: Scratches are sufficiently understood

(Evaluation of dirt on images)
The specific planographic printing plate precursor subjected to the above scratch resistance evaluation was subsequently printed using a commercially available oil-based ink on a Heidelberg printing press Heidel SOR-M. At this time, whether or not the non-image portion of the printed matter was stained was visually observed and used as an index of the stain property of the image. The evaluation results are shown in Table 3.
○: Dirt is not seen △: Dirt is slightly seen ×: Dirt is sufficiently understood

(Evaluation of handleability)
At the time of evaluation of the smearing property of the image, the frequency of occurrence of a nick (folding of the plate) when the specific lithographic printing plate precursor was mounted on a printing machine was measured and used as an index of handling property. The evaluation is a three-stage evaluation shown below, where 2 is a practically acceptable lower limit and 1 is a practically unusable level. The evaluation results are shown in Table 3.
3: No nick generated when the 100th version is installed 2: One nick generated when the 100th version is installed 1: Two or more nicks generated when the 100th version is installed

As is apparent from Table 3, the lithographic printing plate precursor laminates of the present invention in Examples 1 to 5 were found to be excellent in all of scratch resistance, image stain resistance, and handleability.
On the other hand, it was found that Comparative Example 1 was inferior in all of scratch resistance, image stain, and handleability, and had a practical problem. Moreover, although Comparative Examples 2-4 did not have a problem in handleability, it turned out that scratch resistance and image stain | pollution | contamination are inferior and it is a level which has a problem practically.

It is a schematic block diagram which shows an example of the DRM interference wave measuring apparatus for measuring the melt | dissolution behavior of a negative recording layer. It is a schematic block diagram which shows an example of the measuring method of the electrostatic capacitance used in evaluating the permeability to the negative recording layer of a developing solution.

Claims (2)

  On the support (A) a compound that generates a radical by light or heat, (B) a polymer having a phenyl group substituted with a vinyl group on the side chain, and (C) two or more phenyl groups substituted with a vinyl group A lithographic printing plate precursor laminate comprising: a lithographic printing plate precursor provided with a negative recording layer containing a monomer having (D) an infrared absorber; and an interleaving paper.   The lithographic printing plate precursor laminate according to claim 1, wherein the support is an aluminum support, and the thickness of the aluminum support is 0.25 mm to 0.55 mm.

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