JP2003295420A - Method for making planographic printing plate, planographic printing method and planographic printing plate precursor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make a planographic printing plate excellent in printing resistance and ink acceptability from a planographic printing plate precursor excellent in storage stability. <P>SOLUTION: The planographic printing plate is made through a step in which a planographic printing plate precursor having on a hydrophilic support an image forming layer comprising core/shell structure fine particles having a chemically active core and a thermoplastic shell and a hydrophilic polymer is imagewise heated to soften shells, whereby the shells are fusion-bonded to each other and cores are brought into contact with each other or the cores are brought into contact with the hydrophilic support or the hydrophilic polymer to cause chemical bonding, and a step in which the planographic printing plate precursor is processed with an aqueous medium to remove the unheated part of the image forming layer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method of making a lithographic printing plate. In particular, the present invention relates to a lithographic printing plate making method capable of recording an image by scanning exposure of a laser beam based on a digital signal and developing the image by a printing machine.

[0002]

2. Description of the Related Art Generally, a lithographic printing plate comprises an oleophilic image portion that receives ink during the printing process and a hydrophilic non-image portion that receives fountain solution. A conventional lithographic printing plate is prepared by mask-exposing a PS plate having a lipophilic photosensitive resin layer on a hydrophilic support through a lith film, and then dissolving and removing the non-image area with a developing solution. It was normal to do. In recent years, image information is electronically processed as digital information using a computer, accumulated, and output. Therefore, in the image forming processing according to the digital image information, the image is directly formed on the lithographic printing plate precursor by scanning exposure using active radiation having high directivity such as laser light, without passing through the lith film. Is desirable. In this way, the technique of making a printing plate from digital image information without going through the lith film is computer-to-computer
It is called a plate (CTP). When the conventional plate-making method for a printing plate using a PS plate is attempted to be carried out by computer-to-plate (CTP) technology, there is a problem that the wavelength region of laser light and the photosensitive wavelength region of the photosensitive resin do not match.

In addition, in the conventional PS plate, a step (developing process) of dissolving and removing the non-image portion after exposure is indispensable.
Further, a post-treatment step of washing the developed printing plate with water, treating with a rinse solution containing a surfactant, or treating with a desensitizing solution containing gum arabic or a starch derivative was also required. The fact that these additional wet treatments are indispensable has been a major study subject of conventional PS plates. Even if the first half (image forming process) of the plate making process is simplified by the digital process, the effect by the simplification is insufficient in the wet process in which the latter half (developing process) is complicated. Particularly in recent years, consideration of the global environment has become a major concern of the entire industry. In consideration of the environment, it is desirable that the wet post-treatment be simplified, changed to the dry treatment, or even eliminated.

As one of the methods for eliminating the processing step, an exposed printing plate precursor is mounted on a cylinder of a printing machine, and dampening water and ink are supplied while the cylinder is rotated to supply the printing plate precursor. There is a method called on-press development that removes non-image areas. That is, after exposing the printing plate precursor,
This is a method in which it is installed in the printing machine as it is and the processing is completed during the normal printing process. Such a lithographic printing plate precursor suitable for on-press development has a photosensitive layer soluble in dampening water or an ink solvent, and is suitable for development on a printing machine placed in a bright room. It is necessary to have good light room handling.
In the conventional PS version, satisfying such requirements is
It was virtually impossible.

Japanese Patent No. 2938397 discloses a lithographic printing original plate having a hydrophilic support on which a photosensitive layer, in which fine particles of a thermoplastic hydrophobic polymer are dispersed in a hydrophilic binder polymer, is provided. According to the description of the publication, in plate-making, infrared laser exposure is carried out to form an image by coalescing (fusing) the thermoplastic hydrophobic polymer fine particles by heat, and then the plate is mounted on the plate cylinder of the printing machine and wetted. On-press development is possible by supplying water or ink. This lithographic printing plate precursor has a light-sensitive region in the infrared region, and thus has handleability in a bright room. JP-A-2001-277740 describes a lithographic printing plate precursor having a heat-sensitive layer composed of microcapsules containing a compound having a heat-reactive group, and the heat-sensitive layer or its adjacent layer containing a photothermal conversion agent. . The outer wall of the microcapsule is broken by the heat used for plate making. In plate making, the microcapsules are ruptured by the heat of scanning exposure, and the contained compound is reacted to form an image.

[0006]

The image portion formed by the reaction (described in Japanese Patent Laid-Open No. 2001-277740) is superior in printing durability to the image portion formed by heat fusion (described in Japanese Patent 2938397). ing. The purpose of the present invention is to
Without the need for image exposure through a complex lith film,
An object of the present invention is to provide a method of making a planographic printing plate for recording an image. It is also an object of the present invention to provide a lithographic printing method in which an image is recorded and then printed without performing a wet development process. A further object of the present invention is to produce a lithographic printing plate having excellent printing durability from a lithographic printing plate precursor having excellent storage stability. Still another object of the present invention is to provide a lithographic printing plate precursor having high sensitivity and resolution.

[0007]

Means for Solving the Problems The present invention includes the following (1),
A planographic printing plate making method (2), a planographic printing method (3) below and a planographic printing original plate (4) below are provided. (1) A lithographic printing original plate provided with an image forming layer containing a hydrophilic polymer and core / shell structure fine particles having a chemically active core and a thermoplastic shell on a hydrophilic support is imagewise heated. A step of softening the shells to fuse the shells to each other, and bringing the cores into contact with each other, the core and the hydrophilic support, or the core and the hydrophilic polymer to chemically bond either one, and lithographic printing A method of making a lithographic printing plate comprising a step of treating an original plate with an aqueous medium and removing an image-forming layer in an unheated portion. (1a) The plate-making method according to (1), wherein the core is made of a polymer having a chemically active group. (1b) The plate-making method according to (1), wherein the shell is made of a polymer having a softening point of 60 to 200 ° C.

(2) Core / shell structured fine particles having a chemically active core and a thermoplastic shell on a hydrophilic support,
The lithographic printing plate precursor provided with an image forming layer containing a hydrophilic polymer and a photothermal conversion agent is imagewise heated by scanning with a laser beam to soften the shells and fuse the shells together, and the cores together, Core and hydrophilic support,
Alternatively, a lithographic plate comprising a step of bringing the core and a hydrophilic polymer into contact with each other to chemically bond them, and a step of treating the lithographic printing plate precursor with an aqueous medium to remove the image-forming layer in the unheated portion. How to make a printing plate. (2a) The plate-making method according to (2), wherein the core is made of a polymer having a chemically active group. (2b) The plate-making method according to (2), wherein the shell is made of a polymer having a softening point of 60 to 200 ° C.

(3) A lithographic printing original plate having an image forming layer containing a hydrophilic polymer and a core / shell structure fine particle having a chemically active core and a thermoplastic shell is provided on a hydrophilic support as an image. Heating to soften the shells to fuse the shells together, contact the cores, the core and the hydrophilic support, or the core and the hydrophilic polymer, and chemically bond either one, a planographic printing plate. A step of mounting the printing original plate on the printing machine and operating the printing machine, removing the image forming layer in a portion which is not heated by dampening water, ink, or rubbing, thereby making a planographic printing plate, and further A lithographic printing method comprising the steps of supplying a fountain solution and an oil-based ink, and printing with a lithographic printing plate that has been made. (3a) The lithographic printing method as described in (3), wherein the core is made of a polymer having a chemically active group. (3b) The lithographic printing method according to (3), wherein the shell is made of a polymer having a softening point of 60 to 200 ° C. (3c) The lithographic printing method as described in (3), wherein the image forming layer further contains a photothermal conversion agent, and the lithographic printing original plate is imagewise heated by scanning with a laser beam.

(4) Core / shell structure fine particles having a chemically active core and a thermoplastic shell on a hydrophilic support,
An lithographic printing original plate provided with an image forming layer containing a hydrophilic polymer and a photothermal conversion agent, a core made of a polymer having a chemically active group, and a shell made of a polymer having a softening point of 60 to 200 ° C. In the present specification, "chemical activity" means a chemical bond (hydrogen bond,
It means having a functional group (chemically active group) capable of forming a covalent bond, an ionic bond or a coordinate bond. Also,
In the present specification, the softening point is a value measured by the strain gauge method. In the strain gauge method, fine particles of the substance to be measured are sandwiched between a copper plate and a glass plate, the copper plate is heated while pressure is applied from the glass plate side, and the change in pressure with respect to the temperature of the copper plate is measured. , A method of determining the softening point. In the strain gauge method, the temperature at which the pressure starts changing is defined as the softening point.

[0011]

The present invention is characterized by using core / shell structured fine particles having a chemically active core and a thermoplastic shell. The plate-making method in which thermoplastic polymer particles are fused by heat has a problem in printing durability. A polymer having a low softening point that causes heat fusion is generally in a soft state even without heating. Since the polymer was still in a soft state even after heat-sealing, the strength (printing durability) of the hydrophobic coating formed by heat-sealing the polymer was low.

According to the present invention, when the core / shell structured fine particles having the chemically active core and the thermoplastic shell are used, the image area is formed by both the chemical bonding of the core and the thermal fusion of the shell. Therefore, a lithographic printing plate having the advantages of both the heat-fusion type plate making method and the heat-reactive type plate making method can be made. Also, the thermoplastic shell is
It also has the function of isolating the chemically active core and preventing the reaction of the core during storage of the lithographic printing plate precursor (the same function as the wall of the microcapsule). Unlike the microcapsules, the core / shell structure fine particles used in the present invention have a shell
Not only isolation of the core, but also actively involved in image formation. In the prior art, core / shell structured fine particles have been proposed (described in EP514145A1 and JP-A-2000-141895). However, these core / shell structured particles are an improvement over the conventional thermoplastic polymer particles (structure with soft core and hard shell), in which the core does not form chemical bonds.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION [Basic configuration of lithographic printing original plate] FIG.
FIG. 1 is a schematic sectional view showing a basic configuration of a preferable lithographic printing original plate. In the lithographic printing original plate shown in FIG. 1, an image forming layer (2) is provided on a hydrophilic support (1). In the image forming layer (2), the core / shell structure fine particles (21) and the photothermal conversion agent (22) are dispersed in the hydrophilic polymer (23). The core / shell structured fine particles (21) are composed of a chemically active core (21c) and a thermoplastic shell (21s).

[Chemically Active Core] A chemically active substance is used for the core of the fine particles. In imaging, the core is chemically bound to either another core, the hydrophilic polymer and the hydrophilic support. Chemical bonds are hydrogen bonds,
It is either an ionic bond, a coordinate bond or a covalent bond. The chemical bond is preferably a bond formed without external energy (eg, thermal energy, light energy).

In the case of hydrogen bonding, the chemically active core has one of a hydrogen (proton) donating group and a hydrogen accepting group, and the other core, either the hydrophilic polymer or the hydrophilic support, has the other. Have The chemically active core may have both hydrogen donating groups and hydrogen accepting groups. Examples of the hydrogen donating group include a hydroxyl group (—OH), a carboxyl group (—COOH), a primary amino group (—NH ₂ ), a secondary amino group (—NRH) and an imino group = NH). Examples of hydrogen-accepting groups include carbonyl groups (> C =
O), ether groups (-O-) and tertiary amino groups (-N)
R ₂ ) is included. As a combination of a hydrogen donating group and a hydrogen accepting group, a hydroxyl group-tertiary amino group, a carboxyl group-tertiary amino group and a hydroxyl group-ether group are preferable. Hydroxyl group-tertiary amino group and carboxyl group-tertiary amino group are more preferable, and phenolic hydroxyl group-tertiary amino group in nitrogen-containing heterocycle and carboxyl group-tertiary amino group in nitrogen-containing heterocycle are the most preferable. preferable.

In the case of ionic bonding, the chemically active core has one of the anionic and cationic groups and the other core, either the hydrophilic polymer or the hydrophilic support, has the other. The chemically active core may have both anionic and cationic groups. Examples of anionic groups include sulfonates, carboxylates and phosphonates. Examples of the cationic group include an ammonium group, an iodonium group, a sulfonium group and a phosphonium group.

In the case of a coordinate bond, the chemically active core has a functional group that functions as a ligand, the hydrophilic support is an aluminum support, and the functional group that functions as a ligand is aluminum. It is preferable to form a complex. Examples of functional groups that function as ligands include primary amino groups, secondary amino groups, tertiary amino groups, ammonium groups, pyridinium groups, phosphonic acid groups and salts thereof, boric acid groups and salts thereof, acetoacetyl groups. , Phenolic hydroxyl group,
It includes epoxy groups and siloxane groups. Functional groups that function as ligands include ammonium groups, pyridinium groups, phosphonic acid groups and salts thereof, boric acid groups and salts thereof, acetoacetyl groups, phenolic hydroxyl groups,
Epoxy groups and siloxane groups are preferred, and ammonium groups, acetoacetyl groups, phenolic hydroxyl groups and epoxy groups are more preferred.

In the case of a covalent bond, the chemically active core has one of the chemical reaction components described below as a functional group, and the other core, the hydrophilic polymer or the hydrophilic support has the other as a functional group. Have The chemically active core may have both groups.

(A) Reaction of Active Ester with Group Containing Active Hydrogen Examples of the active ester include N-hydroxyphthalimide ester, N-hydroxysuccinimide ester, p-
Nitrophenyl ester, p- chlorophenyl ester, p- methoxycarbonylphenyl ester, p- sulfonium phenyl ester and HCH (OCH ₃₎
COOCH ₃ is included. Examples of groups containing active hydrogen include:
Included are hydroxyl, primary amino groups, secondary amino groups, thiols, hydrazinos, hydrazides and amides.

(B) Reaction of an acid anhydride with a group containing active hydrogen (C) Reaction of an acid halide with a group containing active hydrogen

(D) Reaction of a group capable of leaving by a nucleophilic reaction and a nucleophilic group: Examples of the group capable of leaving by a nucleophilic reaction include a halogen atom, an alkylsulfonyloxy group, an arylsulfonyloxy group and an azido group. Is included. Examples of nucleophilic groups include hydroxyl, amino, thiol, hydrazino, hydrazide, amide, sulfide and phosphino.

(E) Condensation reaction of a heterocyclic group having an unsaturated bond in the ring and a carbonyl group: Examples of the heterocyclic ring having an unsaturated bond in the ring include N-alkylindole, N-alkylpyrrole and N -Alkyl imidazoles, furans and oxazoles are included.

(F) Condensation reaction of heterocyclic group having unsaturated bond in ring with acetal group (G) Phenol group having active hydrogen at ortho position and phenol group having hydroxymethyl group at ortho position or para position Condensation reaction with (H) a condensation reaction between a phenol group having an active hydrogen at the ortho position and an aniline group having a hydroxymethyl group at the ortho position or the para position.

(I) Condensation reaction of carboxyl group and N-methylol group (J) Condensation reaction of carboxyl group and N-alkoxymethyl group (K) Condensation reaction of carboxyl group and carboxyl group (L) Carboxyl group Condensation reaction with a group containing active hydrogen (M) Condensation reaction between a group containing active hydrogen and an N-methylol group

(N) Condensation reaction of group containing active hydrogen with N-alkoxymethyl group (O) Condensation reaction of carbonyl group with hydrazide (P) Group containing primary amino, hydrazino, ketimine or ester and active hydrogen atom Condensation reaction with (Q) Reaction of diazo group with active methylene group

(R) Reaction of cyclic ether group with nucleophilic group Examples of cyclic ether groups include epoxy, oxetane and tetrahydrofuran. Examples of nucleophilic groups include hydroxyl, amino, carboxyl, thiol, hydrazino, hydrazide, amide, sulfide and phosphino.

(S) Reaction of Vinyl Ether with Hydroxyl or Carboxyl (T) Diels-Alder Reaction of Diene with Dienophile (U) Michael Addition Reaction of Enone with Nucleophilic Group Examples of enone include acryloyl and methacryloyl. included. Examples of nucleophilic groups are hydroxyl, amino,
Includes carboxyl, thiol, hydrazino, hydrazide, amide, sulfide and phosphino. (V) Reaction of isocyanate with a group containing active hydrogen Examples of the group containing active hydrogen include hydroxyl, primary amino group, secondary amino group, thiol, hydrazino, hydrazide and amide.

Preferred reactions are: (A) a reaction between an active ester and a group containing active hydrogen, (D) a reaction between a group capable of leaving by a nucleophilic reaction and a nucleophilic group, and (E) an unsaturated group in the ring. Condensation reaction between a heterocyclic group having a bond and a carbonyl group, (F) condensation reaction between a heterocyclic group having an unsaturated bond in the ring and an acetal group, (G) a phenol group having an active hydrogen at the ortho position and an ortho group Reaction with a phenol group having a hydroxymethyl group at the or-position or para position, (H) a condensation reaction between a phenol group having an active hydrogen at the ortho position and an aniline group having a hydroxymethyl group at the ortho position or the para position, (I )
A condensation reaction between a carboxyl group and an N-methylol group,
(J) Condensation reaction of carboxyl group and N-alkoxymethyl group, (M) Condensation reaction of group containing active hydrogen with N-methylol group, (N) Group containing active hydrogen and N-alkoxymethyl group Condensation reaction, condensation reaction of (O) carbonyl group with hydrazide, reaction of (Q) diazo group with active methylene group, reaction of (R) cyclic ether group with nucleophilic group,
(D) Diels-Alder reaction of diene and dienophile, and (V) reaction of isocyanate with a group containing active hydrogen.

Further preferred reactions are: (A) a reaction between an active ester and a group containing active hydrogen; (D) a reaction between a group leaving by a nucleophilic reaction and a nucleophilic group; A condensation reaction between a heterocyclic group having a saturated bond and a carbonyl group,
(F) Condensation reaction of heterocyclic group having unsaturated bond in ring with acetal group, (I) Condensation reaction of carboxyl group with N-methylol group, (J) Carboxyl group with N-alkoxymethyl group Condensation reaction, condensation reaction of (M) group containing active hydrogen with N-methylol group, condensation reaction of group containing (N) active hydrogen with N-alkoxymethyl group, condensation of (O) carbonyl group with hydrazide And the Diels-Alder reaction of the (T) diene with the dienophile. The most preferable reaction is (A) a reaction between an active ester and a group containing active hydrogen, (I) a condensation reaction between a carboxyl group and an N-methylol group, and (J) a condensation reaction between a carboxyl group and an N-alkoxymethyl group. , (M) a condensation reaction of a group containing active hydrogen with an N-methylol group, (N) a condensation reaction of a group containing active hydrogen with an N-alkoxymethyl group, (O)
Condensation reaction of carbonyl group and hydrazide, and (T)
It is a Diels-Alder reaction between a diene and a dienophile.

The core is composed of a compound having a chemically active functional group as described above. The core is preferably a polymer having a chemically active functional group, more preferably a polymer having a chemically active functional group in its side chain. The main chain of the polymer is hydrocarbon (polyolefin), polyester, polyamide, polyimide,
It is preferably selected from polyureas, polyurethanes, polyethers and combinations thereof. A hydrocarbon backbone is especially preferred. The chemically active functional group can be directly attached to the main chain. However, the chemically active functional group is preferably bonded to the main chain via a linking group.

The main chain of the polymer may have a substituent in addition to the chemically active functional group. Examples of the substituent include a halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, sulfo, cyano, a monovalent aliphatic group,
Monovalent aromatic group, monovalent heterocyclic group, -OR, -CO-
R, -NH-R, -N (-R) ₂ , -N ⁺ (-R) ₃ ,
-CO-OR, -O-CO-R, -CO-NH-R,
-CO-N (-R) ₂ and -NH-CO-R are included. Each R is a monovalent aliphatic group, a monovalent aromatic group or a monovalent heterocyclic group. When the substituent includes plural Rs, the plural Rs may be different from each other. Carboxyl and sulfo may have a hydrogen atom dissociated or may be in a salt state. A plurality of substituents on the main chain may combine to form an aliphatic ring or a heterocycle. The ring formed may have a spiro bond relationship with the main chain.
The ring formed may have a substituent. Examples of the substituent include oxo (═O) in addition to the above-mentioned main chain substituent. Further, a plurality of substituents on the main chain may be bonded to each other to form a crosslinked structure.

The aliphatic group may have a cyclic structure or a branched structure. The aliphatic group may have an unsaturated bond. The aliphatic group preferably has 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms.
It is more preferably from 1 to 20, even more preferably from 1 to 15, and most preferably from 1 to 12. The aliphatic group may have a substituent. Examples of the substituent of the aliphatic group include a halogen atom (F, C
1, Br, I), hydroxyl, carboxyl, sulfo, cyano, monovalent aromatic group, monovalent heterocyclic group, —O—
R, -CO-R, -NH-R, -N (-R) ₂ , -N ^+.
(-R) ₃ , -CO-O-R, -O-CO-R, -CO
-NH-R, -CO-N (-R) ₂ and -NH-CO
-R is included. Each R is a monovalent aliphatic group, a monovalent aromatic group or a monovalent heterocyclic group. Carboxyl and sulfo, even if the hydrogen atom is dissociated,
It may be in a salt state.

The aromatic group preferably has a benzene ring or a naphthalene ring. The aromatic group may have a substituent. Examples of the substituent of the aromatic group include halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, sulfo, cyano, monovalent aliphatic group, monovalent aromatic group, monovalent heterocycle. Group, -OR, -CO-R, -NH-
R, -N (-R) ₂ , -N ⁺ (-R) ₃ , -CO-O-
R, -O-CO-R, -CO-NH-R, -CO-N
(-R) ₂ and -NH-CO-R are included. R above
Are respectively a monovalent aliphatic group, a monovalent aromatic group or a monovalent heterocyclic group. Carboxyl and sulfo are
The hydrogen atom may be dissociated or may be in a salt state. The heterocyclic group preferably has a 3-membered ring to a 7-membered ring. The heterocycle may have an unsaturated bond. Examples of the heterocycle include a piperidine ring and a piperazine ring. The heterocyclic group may have a substituent. The substituent of the heterocyclic group is the same as the substituent of the aromatic group.

When the polymer has a hydrocarbon main chain, it preferably has a repeating unit containing a chemically active functional group represented by the following formula (I).

[0035]

[Chemical 1]

In the formula (I), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, carboxyl or an alkoxycarbonyl group having 2 to 11 carbon atoms. R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, carboxyl or an alkoxycarbonyl group having 2 to 7 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms More preferably, it is a carboxyl or an alkoxycarbonyl group having 2 to 4 carbon atoms, further preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
Most preferably, it is a hydrogen atom or methyl.

In the formula (I), L ¹ is a single bond or a divalent linking group. L ¹ is an aliphatic group, an aromatic group, a heterocyclic group, —O—, —S—, —CO—, —CS—, —NH.
More preferably, it is a divalent linking group consisting of-and a combination thereof. The definitions and examples of the aliphatic group, aromatic group and heterocyclic group are as described above. In formula (I), X is a chemically active functional group.

As the polymer used for the core, a homopolymer consisting only of repeating units containing a chemically active functional group can be used. Further, a copolymer composed of two or more kinds of repeating units containing a chemically active functional group can be used. A copolymer of a repeating unit containing a chemically active functional group and a repeating unit containing no chemically active functional group can also be used. Below, the example of the repeating unit which comprises a polymer is shown.

[0039]

[Chemical 2]

[0040]

[Chemical 3]

[0041]

[Chemical 4]

[0042]

[Chemical 5]

[0043]

[Chemical 6]

[0044]

[Chemical 7]

[0045]

[Chemical 8]

[0046]

[Chemical 9]

[0047]

[Chemical 10]

[0048]

[Chemical 11]

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054]

[Chemical 17]

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

[0061]

[Chemical formula 24]

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

[0064]

[Chemical 27]

[0065]

[Chemical 28]

[0066]

[Chemical 29]

[0067]

[Chemical 30]

[0068]

[Chemical 31]

[0069]

[Chemical 32]

[0070]

[Chemical 33]

[0071]

[Chemical 34]

[0072]

[Chemical 35]

[0073]

[Chemical 36]

[0074]

[Chemical 37]

[0075]

[Chemical 38]

[0076]

[Chemical Formula 39]

[0077]

[Chemical 40]

[0078]

[Chemical 41]

[0079]

[Chemical 42]

[0080]

[Chemical 43]

[0081]

[Chemical 44]

[0082]

[Chemical formula 45]

[0083]

[Chemical formula 46]

[0084]

[Chemical 47]

[0085]

[Chemical 48]

[0086]

[Chemical 49]

[0087]

[Chemical 50]

[0088]

[Chemical 51]

[0089]

[Chemical 52]

[0090]

[Chemical 53]

[0091]

[Chemical 54]

[0092]

[Chemical 55]

[0093]

[Chemical 56]

[0094]

[Chemical 57]

[0095]

[Chemical 58]

[0096]

[Chemical 59]

[0097]

[Chemical 60]

[0098]

[Chemical formula 61]

[0099]

[Chemical formula 62]

[0100]

[Chemical formula 63]

[0101]

[Chemical 64]

[0102]

[Chemical 65]

[0103]

[Chemical formula 66]

[0104]

[Chemical formula 67]

[0105]

[Chemical 68]

[0106]

[Chemical 69]

[0107]

[Chemical 70]

[0108]

[Chemical 71]

[0109]

[Chemical 72]

[0110]

[Chemical formula 73]

[0111]

[Chemical 74]

When a repeating unit containing a chemically active functional group and a repeating unit containing no chemically active functional group are combined, a repeating unit containing a chemically active functional group / a chemically active repeating unit The molar ratio of the repeating units not containing such a functional group is preferably 0.1 / 99.9 to 99.8 / 0.2, and 0.2 / 9.
More preferably 9.8 to 99/1, and 0.5
More preferably, it is /99.5 to 95/5,
It is still more preferably 1/99 to 80/20, and most preferably 2/98 to 49/51. The following are examples of copolymers. The numbers in parentheses correspond to the exemplary numbers of the repeating units. The ratio of repeating units is a molar ratio (%).

CP-1: − (9) ₂₅ − − (201) ₇₅ − CP-2: − (4) ₃₀ − − (102) ₇₀ − CP-3: − (8) ₂₅ − − (19) ₇₅ - CP-4: - (8 ) 50 - - (201) 50 - CP-5: - (17) 20 - - (20) 80 - CP-6: - (8) 50 - - (17) 50 - CP _{-7: - (8) 50 -} - (21) 50 - CP-8: - (8) 50 - - (22) 50 - CP-9: - (23) 60 - - (136) 40 - CP-10 : - (8) ₂₀ - - (135) ₈₀ -

CP-11: − (24) ₂₀ − − (243) ₈₀ − CP-12: − (1) ₃₀ − − (201) ₇₀ − CP-13: − (26) ₃₀ − − (201) ₇₀ - CP-14: - (27 ) 30 - - (201) 70 - CP-15: - (34) 95 - - (35) 5 - CP-16 :-( 102) 40 - - (209) 60 - CP _{-17 :-( 101) 80 - - (} 103) 20 - CP-18: - (9) 25 - - (201) 75 - CP-19: - (40) 50 - - (248) 50 - CP-20 :-( 41) _50- (201) _50-

CP-21 :-( 243) ₈₀ --- (248) ₂₀ -CP-22 :-( 104) ₈₀ --- (211) ₂₀ -CP-23 :-( 43) ₃₀ --- (201) ₇₀ -CP-24 :-( 44) _30- (202) ₇₀ -CP-25 :-( 48) _50- (110) ₅₀ -CP-26 :-( 50) _50- (51) ₅₀ -CP -27:-(52) ₂₀ --(201) ₈₀ -CP-28:-(53) ₂₅ --(120) ₇₅ -CP-29:-(54) ₂₅ --(101) ₇₅ -CP-30 : - (1) ₂₀ - - (201) ₈₀ -

CP-31 :-( 13) _30- (201) ₇₀ -CP-32 :-( 56) _50- (110) ₅₀ -CP-33 :-( 57) _80- (201) ₂₀ -CP-34 :-( 58) _50- (201) ₅₀ -CP-35 :-( 59) _50- (104) ₅₀ -CP-36 :-( 60) _50- (61) ₅₀ -CP _{-37: - (62) 50 -} - (201) 50 - CP-38: - (51) 20 - - (63) 80 - CP-39: - (40) 50 - - (110) 50 - CP-40 :-( 64) _30- (201) _70-

CP-41 :-( 65) _80- (201) ₂₀ -CP-42 :-( 66) _50- (104) ₅₀ -CP-43 :-( 67) _50- (68) ₅₀ -CP-44 :-( 8) _80- (109) ₂₀ -CP-45 :-( 69) _80- (70) ₂₀ -CP-46 :-( 71) _50- (110) ₅₀ -CP -47:-(72) ₈₀ --(201) ₂₀ -CP-48:-(61) ₅₀ --(73) ₅₀ -CP-49:-(76) ₂₀ --(201) ₈₀ -CP-50 _{: - (75) 25 - -} (201) 75 - CP-51: - (77) 20 - - (201) 80 -

The polymer used for the core can be synthesized by a polymerization reaction (radical polymerization reaction) of a monomer (generally an ethylenically unsaturated monomer) corresponding to the above repeating unit. The chemically active functional group may be introduced after the synthesis of the backbone polymer. The polymer used for the core may have a crosslinked structure. The crosslinked structure can be introduced into the polymer by using a polyfunctional monomer (for example, a monomer having two or more ethylenically unsaturated groups). Examples of polyfunctional monomers include ethylene glycol dimethacrylate and divinylbenzene. The crosslinked polymer used for the core preferably has a softening temperature of 80 to 200 ° C. The polymerization is preferably an emulsion polymerization reaction. In the emulsion polymerization reaction, core fine particles can be formed simultaneously with the synthesis of the polymer. For the emulsion polymerization reaction, reaction conditions generally used for producing latex may be adopted. In order to form homogeneous fine particles, it is preferable to use a surfactant in the emulsion polymerization reaction. Surfactants include anionic surfactants, cationic surfactants,
It is classified into nonionic surfactants and amphoteric surfactants.

Examples of the anionic surfactant include carboxylate (eg, potassium laurate, sodium oleate), sulfate ester (eg, sodium octyl sulfate, and the like).
Sodium dodecyl sulphate), sulphonates (eg sodium dodecylbenzene sulphonate, sodium dioctyl sulphosuccinate) and phosphate ester salts (eg sodium lauryl phosphate). The anionic surfactant may have a nonionic hydrophilic group in addition to the anionic group. Examples of anionic surfactants having a nonionic hydrophilic group include polyethylene glycol sulfate ester salts (eg, 2,4,6-tri (sec-butyl) phenyl polyethylene glycol ether sodium sulfate, dodecyl polyethylene glycol ether sodium sulfate, Octyl polyethylene glycol ether sodium sulfate, heptadecyl sodium polyethylene glycol ether sulfate, polyethylene glycol polypropylene glycol polyethylene glycol ether ammonium sulfate), polyethylene glycol sulfonate (eg p
-(1,1,3,3-Tetramethylbutyl) phenyl polyethylene glycol sulfonate sodium, dodecyl polyethylene glycol ether sulfosuccinate disodium) and polyethylene glycol phosphate (eg, dodecyl polyethylene glycol ester phosphate, di (dodecyl polyethylene) Glycol ester) phosphate) are included.

Examples of the cationic surfactant include amine salts (eg, laurylamine sulfate, stearylamine sulfate), pyridinium salts (eg, cetylpyridinium chloride) and quaternary ammonium salts (eg, lauryltrimethylammonium chloride). , Lauroylaminopropyldimethylhydroxyethylammonium perchlorate). The cationic surfactant may have a nonionic hydrophilic group in addition to the cationic group. Examples of the cationic surfactant having a nonionic hydrophilic group include:
Included are polyethylene glycol quaternary ammonium salts (eg, methylheptadecyl di (polyethylene glycol) ammonium chloride).

Examples of the nonionic surfactant include sorbitan ester (eg, sorbitan monolaurate, sorbitan monostearate), polyethylene glycol ether (eg, polyethylene glycol dodecyl ether, polyethylene glycol tridecyl ether, polyethylene glycol hexadecyl ether). , Polyethylene glycol octadecyl ether, polyethylene glycol octadecenyl ether, polyethylene glycol nonyl phenyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol poly (trimethylene) glycol ether, polyethylene glycol polypropylene glycol ethynyl ether, polyethylene glycol p- (1-isobutyl) -3-Methylbutyl) phenyle Ether, polyethylene glycol
2,4,6-tri (sec-butyl) phenyl ether,
2,4,7,9-Tetramethyl-decane-5-yn-
4,7-di (polyethylene glycol) ether), polyethylene glycol ester (eg, polyethylene glycol laurate, polyethylene glycol stearate, polyethylene glycol oleate, polyethylene glycol distearate), sorbitan monoester tri (polyethylene glycol) ether ( Example, sorbitan-6-laurate-2,3,4-tri (polyethylene glycol) ether, sorbitan-6-stearate-2,3,4-tri (polyethylene glycol) ether, polyethylene glycol amine (eg, di (polyethylene Glycol) dodecylamine, di (polyethylene glycol) octadecylamine), sorbitol polyethylene glycol ether (eg, sorbitol-1,
2,3,4-Tetra (polyethylene glycol stearate) -5,6-di (polyethylene glycol) ether) and polyethylene glycol amide (eg, N, N)
-Di (polyethylene glycol) laurylamide, N,
N-di (polyethylene glycol) stearylylamide).

The amphoteric surfactant has an anionic group and a cationic group. Examples of amphoteric surfactants include bedaine esters (eg, dimethyllaurylbedine).

Nonionic surfactants, anionic surfactants having a nonionic group and cationic surfactants having a nonionic group are preferred. You may use together 2 or more types of surfactant. The amount of the surfactant used is preferably 0.01 to 10% by mass of the total amount of the monomers. It is preferable to use a polymerization initiator (chain transfer agent) for the polymerization reaction. The amount of the polymerization initiator used is preferably 0.05 to 10% by mass of the total amount of the monomers.

The average particle size of the core fine particles is 12 to 150.
nm is preferable, and 16 to 125 nm is more preferable. The particle size distribution is preferably as uniform as possible. The polymer forming the core fine particles preferably has a softening temperature of 80 to 200 ° C, more preferably 90 to 150 ° C.

[Thermoplastic Shell] The shell of the fine particles is preferably made of a polymer, more preferably a hydrophobic polymer. The shell polymer is preferably substantially non-crosslinked. The term “substantially not crosslinked” means that the proportion of repeating units containing a crosslinked structure is less than 0.1% in terms of molar ratio. Further, it is preferable that the shell polymer is substantially free of chemically active functional groups. "Substantially free of functional groups" also means that the proportion of repeating units containing chemically active functional groups is less than 0.1% in molar ratio.

The shell polymer preferably has a softening point of 60 to 150 ° C., more preferably 80 to 130 ° C. The main chain of the shell polymer is preferably selected from hydrocarbon (polyolefin), polyester, polyamide, polyimide, polyurea, polyurethane, polyether and combinations thereof. A hydrocarbon backbone is especially preferred.

The main chain of the shell polymer can have a substituent within a range that the entire polymer is hydrophobic.
Examples of the substituent include a halogen atom (F, Cl, Br,
I), cyano, monovalent aliphatic group, monovalent aromatic group, monovalent heterocyclic group, -OR, -CO-R, -NH-R, -N.
(-R) ₂ , -N ⁺ (-R) ₃ , -CO-OR, -O
-CO-R, -CO-NH-R, -CO-N (-R) ₂
And -NH-CO-R are included. Each R is a monovalent aliphatic group, a monovalent aromatic group or a monovalent heterocyclic group. When the substituent includes plural Rs, the plural Rs may be different from each other. The carboxyl, sulfo, sulfate ester group, phosphono and phosphate ester group may have hydrogen atoms dissociated or may be in a salt state. A plurality of substituents on the main chain may combine to form an aliphatic ring or a heterocycle. The ring formed may have a spiro bond relationship with the main chain. The ring formed may have a substituent. Examples of the substituent include oxo (═O) in addition to the above-mentioned main chain substituent.

When the shell polymer has a hydrocarbon main chain, the shell polymer preferably has a repeating unit represented by the following formula (II).

[0129]

[Chemical 75]

In the formula (II), R ² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, carboxyl or an alkoxycarbonyl group having 2 to 11 carbon atoms. R ² is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, carboxyl or an alkoxycarbonyl group having 2 to 7 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. More preferably, it is a carboxyl or an alkoxycarbonyl group having 2 to 4 carbon atoms, further preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
Most preferably, it is a hydrogen atom or methyl. In formula (II), L ² is —O— or —N (—R ⁴ ).
− In formula (II), R ³ and R ⁴ are each independently an aliphatic group, an aromatic group or a heterocyclic group. The definitions and examples of the aliphatic group, aromatic group and heterocyclic group are as described in the core of the fine particles.

Examples of the repeating units of the shell polymer include the repeating units (101) to
The same as (140) and (201) to (252). As the shell polymer, a copolymer composed of two or more kinds of repeating units can also be used. Below, the example of the copolymer which consists of two types of repeating units is shown. The numbers in parentheses correspond to the exemplary numbers of the repeating units described for the core of microparticles. The ratio of repeating units is a molar ratio (%).

[0132] _{CP-101 :-( 102) 70 -} - (110) 30 - CP-102 :-( 102) 80 - - (104) 20 - CP-103 :-( 102) 60 - - (112) 40 _{- CP-104 :-( 102) 95} - - (140) 5 - CP-105 :-( 102) 50 - - (201) 50 - CP-106 :-( 102) 90 - - (212) 10 - CP _{-107 :-( 102) 80 - - (} 207) 20 - CP-108 :-( 201) 90 - - (101) 10 - CP-109 :-( 201) 80 - - (104) 20 - CP-110 :-( 201) ₈₀ - - (110) ₂₀ -

[0133] _{CP-111 :-( 201) 90 -} - (112) 10 - CP-112 :-( 201) 90 - - (139) 10 - CP-113 :-( 201) 95 - - (126) 5 -CP-114 :-( 201) ₈₀ --- (204) ₂₀ -CP-115 :-( 201) ₈₀ --- (203) ₂₀ -CP-116 :-( 201) ₅₀ --- (207) ₅₀ -CP -117 :-( 209) _80- (104) ₂₀ -CP-118 :-( 209) _70- (106) ₃₀ -CP-119 :-( 209) _70- (112) ₃₀ -CP-120 :-( 209) ₈₀ - - (207) ₂₀ -

The shell polymer can be synthesized by a polymerization reaction (radical polymerization reaction) of a monomer (generally an ethylenically unsaturated monomer) corresponding to the above repeating unit. The shell can be directly formed on the core fine particles by a polymerization reaction. In order to form uniform fine particles, it is preferable to use a surfactant in the shell formation as in the core formation. Preferred surfactants are the same as those described in the core formation. You may use together 2 or more types of surfactant. The amount of the surfactant used is preferably 0.01 to 10% by mass of the total amount of the monomers. It is preferable to use a polymerization initiator (chain transfer agent) for the polymerization reaction. The amount of the polymerization initiator used is preferably 0.05 to 10% by mass of the total amount of the monomers. The shell polymer preferably has a softening temperature of 60 to 180 ° C, more preferably 70 to 140 ° C. It is also preferable that the shell polymer has a softening temperature lower than the softening temperature of the polymer forming the core fine particles.

The average particle size of the core / shell structure fine particles is 6
It is preferably 0 to 300 nm, and 80 to 25
More preferably, it is 0 nm. The particle size distribution is preferably as uniform as possible. The core / shell mass ratio is preferably 0.01 to 5,
It is more preferably 0.03 to 4. You may mix and use 2 or more types of core / shell structure fine particles.
The core / shell structure fine particles are contained in the image forming layer in an amount of 20 to 99.
It is preferably contained by mass%, more preferably 50 to 95% by mass, and most preferably 60 to 90% by mass.

[Hydrophilic Polymer] It is preferable that the hydrophilic polymer functions as a binder for the core / shell structure fine particles in the image forming layer. The hydrophilic group of the hydrophilic polymer is preferably hydroxyl, carboxyl or amino. As the hydrophilic polymer, various natural or semi-synthetic polymers or synthetic polymers can be used. Examples of natural or semi-synthetic polymers include polysaccharides (eg, gum arabic, starch derivatives, carboxymethyl cellulose, its sodium salt, cellulose acetate,
Sodium alginate) or proteins (eg casein, gelatin) can be used.

Examples of synthetic polymers having hydroxyl as a hydrophilic group include polyhydroxyethyl methacrylate, polyhydroxyethyl acrylate, polyhydroxypropyl methacrylate, polyhydroxypropyl acrylate, polyhydroxybutyl methacrylate, polyhydroxybutyl acrylate, polyallyl alcohol. , Polyvinyl alcohol and poly-N-methylol acrylamide. Examples of synthetic polymers having a carboxyl as a hydrophilic group include polymaleic acid, polyacrylic acid, polymethacrylic acid and salts thereof. Examples of synthetic polymers having other hydrophilic groups (eg, amino, many ether bonds, hydrophilic heterocyclic groups, amide bonds, sulfo) include polyethylene glycol, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, polyacrylamide, Included are polymethacrylamide and poly (2-acrylamido-2-methylpropanesulfonic acid) and its salts.

A copolymer having two or more kinds of repeating units of the hydrophilic synthetic polymer may be used. A copolymer containing a repeating unit of a hydrophilic synthetic polymer and a repeating unit of a hydrophobic synthetic polymer (eg, polyvinyl acetate, polystyrene) may be used. Examples of copolymers include vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers and vinyl alcohol-vinyl acetate copolymers (partially saponified polymers of polyvinyl acetate). When a vinyl alcohol-vinyl acetate copolymer is synthesized by partial saponification of polyvinyl acetate, the saponification degree is preferably 60% by mass or more, and 80% by mass.
It is more preferable that the above is satisfied. The hydrophilic polymer is
Gum arabic, carboxymethyl cellulose, polyacrylic acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, poly (2-acrylamido-2-methylpropanesulfonic acid) and saponification degree of 60% by mass.
The above polyvinyl alcohol is preferable, carboxymethyl cellulose, polyacrylic acid, polymethacrylic acid,
Polyacrylamide and polymethacrylamide are more preferred. You may use together two or more types of hydrophilic polymers.

The hydrophilic polymer may have a crosslinked structure. The crosslinked structure is preferably introduced into the hydrophilic polymer by using a crosslinking agent. Examples of the cross-linking agent include aldehyde (eg, glyoxal), aldehyde resin (eg, melamine formaldehyde resin, urea formaldehyde resin), methylol compound (eg, N-methylol urea, N).
-Methylol melamine, methylolated polyamide resin), active vinyl compound (eg, divinyl sulfone, bis (β-hydroxyethyl sulfonic acid)), epoxy compound (eg, epichlorohydrin, polyethylene glycol diglycidyl ether, polyamide / polyamine / epichlorohydride) Phosphorus adduct, polyamide epichlorohydrin resin), ester (eg, monochloroacetic acid ester, thioglycolic acid ester), polycarboxylic acid (eg, polyacrylic acid, methyl vinyl ether / maleic acid copolymer), inorganic acid (eg. , Boric acid), titanyl sulfate,
Included are metal salts (eg, copper salts, aluminum salts, tin salts, vanadium salts, chromium salts) and modified polyamide polyimide resins. In addition to the cross-linking agent, a cross-linking catalyst (eg, ammonium chloride, silane coupling agent, titanate coupling agent) may be used. The hydrophilic polymer is contained in the image forming layer in an amount of preferably 2 to 40% by mass, more preferably 3 to 30% by mass.

[Photothermal Conversion Agent] The image forming layer preferably contains a photothermal conversion agent. The photothermal conversion agent is a substance having a function of absorbing light, converting light energy into heat energy, and generating heat. The photothermal conversion agent can be present inside the core / shell structured fine particles. The photothermal conversion agent may be added outside the fine particles (in the hydrophilic binder).
The wavelength of light absorbed by the photothermal conversion agent (maximum absorption wavelength) is 7
It is particularly preferable that it is at least 00 nm (infrared light). Pigments, dyes or fine metal particles capable of absorbing infrared light can be preferably used as the photothermal conversion agent.

For infrared absorbing pigments, the Color Index (CI) handbook, "Latest pigment handbook" (edited by Japan Pigment Technology Association, published in 1977), "Latest pigment application technology" (C
MC Publishing, 1986, "Printing Ink Technology" (CM
C Publishing, published in 1984). A particularly preferred infrared absorbing pigment is carbon black. When the infrared absorbing pigment is added to the inside of the core / shell structure fine particles, the pigment can be subjected to a hydrophobizing (lipophilicizing) treatment. As the hydrophobic treatment, there is a method of coating the surface of the pigment with a lipophilic resin. When the infrared absorbing pigment is dispersed in the hydrophilic polymer, the pigment can be subjected to a hydrophilic treatment. As the hydrophilic treatment, a method of coating the surface of the pigment with a hydrophilic resin, a method of attaching a surfactant to the surface of the pigment, or a reactive substance (eg, silica sol, alumina sol, silane coupling agent, epoxy compound, isocyanate) A method of binding a compound) to the pigment surface can be adopted. The particle size of the pigment is preferably 0.01 to 1 μm,
More preferably, it is 0.01 to 0.5 μm.
When the pigment is dispersed in the hydrophilic polymer, a known dispersion technique used in ink production or toner production can be applied.

Regarding infrared absorbing dyes, "Dye Handbook" edited by the Society of Synthetic Organic Chemistry, published in 1970, "Chemical Industry" 19
May 1986 issue P. 45-51 "near infrared absorbing dye",
"Development of 90's functional dyes and market trends" Chapter 2 2.3
See (1990) CMC. Preferred infrared absorbing dyes are azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, and naphthoquinone dyes (JP-A-58-1127).
No. 93, No. 58-224793, No. 59-48187.
No. 59-73996, No. 60-52940, No. 60-63744), anthraquinone dye, phthalocyanine dye (JP-A-11-235883), squarylium dye (JP-A-58-112).
792), pyrylium dye (US Pat. No. 388)
1924 and 4283475, each specification, JP-A-5
7-142645, 58-181051, 58.
-220143, 59-41363, 59-8
No. 4248, No. 59-84249, No. 59-1460.
63, 59-146061, JP-B-51351
4 and 5-19702), carbonium dyes, quinoneimine dyes and methine dyes (Japanese Patent Application Laid-Open No. Sho 5).
8-173696, 58-181690, 58
No. 194595).

For infrared absorbing dyes, US Pat.
It is also described in each specification of 6993 and 5156938 and JP-A-10-268512. A commercially available infrared absorbing dye (for example, Epolite III-178, Epolite III-130, Epolite III-125, manufactured by Eporin) may be used. Methine dyes are more preferred, and cyanine dyes (UK Patent 434875, US Patent 497
No. 3572, JP-A-58-125246,
59-84356, 59-216146, 6
0-78787). The cyanine dye is defined by the following formula. Bo-Le = Bs In the above formula, Bs is a basic nucleus; Bo is an onium body of a basic nucleus; and Le is a methine chain composed of an odd number of methines. In the case of infrared absorbing dye, L
e is preferably a methine chain composed of 7 methines.

When the infrared absorbing dye is added to the hydrophilic polymer of the image forming layer, it is preferable to use a hydrophilic dye. Examples of hydrophilic infrared absorbing dyes are shown below.

[0145]

[Chemical 76]

[0146]

[Chemical 77]

[0147]

[Chemical 78]

[0148]

[Chemical 79]

[0149]

[Chemical 80]

[0150]

[Chemical 81]

When the infrared absorbing dye is added to the core / shell structure fine particles, it is preferable to use a relatively hydrophobic dye. Examples of hydrophobic infrared absorbing dyes are shown below.

[0152]

[Chemical formula 82]

[0153]

[Chemical 83]

[0154]

[Chemical 84]

[0155]

[Chemical 85]

[0156]

[Chemical 86]

The metal generally has a self-heating property.
Therefore, metals with absorption in the infrared, visible or ultraviolet region,
In particular, a metal having absorption in the infrared region has a light-heat conversion function. The metal forming the metal fine particles is preferably heat-sealed by light irradiation. Specifically, the melting point is 100.
It is preferably 0 ° C. or lower. As the metal constituting the metal fine particles, Si, Al, Ti, V, Cr, Mn, F
e, Co, Ni, Cu, Zn, Y, Zr, Mo, Ag,
Au, Pt, Pd, Rh, In, Sn, W, Te, P
b, Ge, Re, Sb and alloys thereof are preferred,
Re, Sb, Te, Ag, Au, Cu, Ge, Pb and Sn are more preferable, and Ag, Au, Cu, Sb and Ge are more preferable.
And Pb are more preferred, and Ag, Au and Cu are most preferred.

In the case of an alloy, a low melting point metal (eg Re, S
b, Te, Au, Ag, Cu, Ge, Pb, Sn),
Metals with high self-heating properties (eg Ti, Cr, Fe, Co,
Ni, W, Ge) can also be combined. It is also possible to use fine particles of a metal (eg, Ag, Pt, Pd) having a large light absorption and fine particles of another metal in combination. The metal fine particles are preferably dispersed in the hydrophilic polymer by subjecting the surface to hydrophilic treatment.
As the surface hydrophilic treatment, means such as surface treatment with a hydrophilic substance (eg, surfactant), surface chemical reaction with the hydrophilic substance, or formation of a hydrophilic polymer film can be adopted. A method such as providing a protective colloid hydrophilic polymer film can be used. A surface chemical reaction with a hydrophilic substance is preferred, and a surface silicate treatment is most preferred.
In the surface silicate treatment of iron fine particles, the surface can be made sufficiently hydrophilic by a method of immersing the iron fine particles in an aqueous sodium silicate (3%) solution at 70 ° C. for 30 seconds. Other metal fine particles can be subjected to surface silicate treatment in the same manner. Metal oxide particles or metal sulfide particles may be used instead of the metal particles. The particle size of the fine particles is preferably 10 μm or less, and is 0.0
It is more preferably from 03 to 5 μm, and 0.01
Most preferably from 3 to 3 μm.

[Other Optional Components of Image Forming Layer] A colorant may be added to the image forming layer for the purpose of distinguishing the image area and the non-image area after image formation. As the colorant, a dye or pigment having a large absorption in the visible region is used. Examples of colorants are Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60.
3, Oil Black BY, Oil Black BS, Oil Black T-505 (above Orient Chemical Industry Co., Ltd.)
Made), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42)
535), ethyl violet, rhodamine B (CI1
45170B), Malachite Green (CI4200
0) and methylene blue (CI52015). Regarding the dyes used as the colorant, see JP-A-6-61.
It is described in JP-A-2-293247. Inorganic pigments such as titanium oxide can also be used as colorants. The addition amount of the colorant is preferably 0.01 to 10% by mass of the image forming layer.

The image-forming layer contains a nonionic surfactant (JP-A-62-25174) in order to enhance the stability of on-press development.
No. 0, JP-A-3-208514) or an amphoteric surfactant (JP-A-59-121044, JP-A-4-13149). Examples of nonionic surfactants include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride and polyoxyethylene nonyl phenyl ether. Examples of amphoteric surfactants include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-
Alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-
An N, N-betaine type surfactant (Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.) is included. The nonionic surfactant and the amphoteric surfactant are contained in the image forming layer in an amount of 0.05 to 15% by mass.
It is preferably contained, and more preferably 0.1 to 5% by mass.

A plasticizer may be added to impart flexibility to the image forming layer. Examples of plasticizers include polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate and tetrahydrofurfuryl oleate. .

[Formation of Image-Forming Layer] The image-forming layer is prepared by dissolving, dispersing or emulsifying each component in a suitable liquid medium to prepare a coating solution, coating the solution on a hydrophilic support, and drying it. It can be formed by removing the liquid medium.
Examples of the liquid medium used for the coating liquid include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2.
-Propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N,
N-dimethylformamide, tetramethylurea, N-
Includes methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyl lactone, toluene and water. Two or more kinds of liquids may be mixed and used. The total solid content concentration of the coating liquid is preferably 1 to 50% by mass.

A surfactant may be added to the coating solution to improve the coating property. Fluorine-based surfactants (described in JP-A-62-170950) are particularly preferable. The addition amount of the surfactant is preferably 0.01 to 1% by mass with respect to the solid content of the coating liquid, and is 0.05
To 0.5 mass% is more preferable. The dry coating amount of the image forming layer is preferably 0.5 to 5.0 g / m ² .

[Hydrophilic support] As the hydrophilic support,
A metal plate, a plastic film or paper can be used. Specifically, a surface-treated aluminum plate,
Hydrophilic treated plastic film or water treated paper is preferred. More specifically, an anodized aluminum plate, a polyethylene terephthalate film provided with a hydrophilic layer, or a polyethylene-laminated paper is preferable.

Anodized aluminum plates are particularly preferred. The aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of a foreign element. Examples of foreign elements contained in aluminum alloys are:
Includes silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The ratio of the foreign element is preferably 10% by mass or less. You may use the aluminum plate for commercial printing plates. The thickness of the aluminum plate is preferably 0.05 to 0.6 mm, more preferably 0.1 to 0.4 mm, and most preferably 0.15 to 0.3 mm.

The surface of the aluminum plate is preferably roughened. The roughening treatment can be performed by a mechanical method, an electrochemical method or a chemical method. As the mechanical method, a ball polishing method, a brush polishing method, a blast polishing method or a buff polishing method can be adopted. As the electrochemical method, a method of performing alternating current or direct current in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid can be adopted. An electrolytic surface-roughening method using a mixed acid (described in JP-A-54-63902) can also be used. As a chemical method, a method of immersing an aluminum plate in a saturated aqueous solution of an aluminum salt of mineral acid (described in JP-A-54-31187) is suitable. The roughening treatment is preferably performed so that the center line average roughness (Ra) of the surface of the aluminum plate is 0.2 to 1.0 μm. The roughened aluminum plate is subjected to alkali etching treatment if necessary. An aqueous solution of potassium hydroxide or sodium hydroxide is generally used as the alkaline treatment liquid. After the alkali etching treatment, it is preferable to further perform a neutralization treatment.

The anodizing treatment of the aluminum plate is carried out in order to enhance the abrasion resistance of the support. As the electrolyte used for the anodizing treatment, various electrolytes forming a porous oxide film can be used. Generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used as the electrolyte. The anodizing treatment conditions are generally such that the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5.
To 60 A / dm ² , voltage of 1 to 100 V, and
The electrolysis time is in the range of 10 seconds to 5 minutes. The amount of oxide film formed by anodizing treatment is 1.0 to 5.0 g /
It is preferably m ² and is 1.5 to 4.0 g / m ^2.
Is more preferable.

[Water-soluble overcoat layer] A water-soluble overcoat layer may be provided on the image-forming layer to prevent the surface of the image-forming layer from being contaminated by a lipophilic substance. The water-soluble overcoat layer is composed of a material that can be easily removed during printing. For that purpose, it is preferable to form the water-soluble overcoat layer from a water-soluble organic polymer. Examples of water-soluble organic polymers include polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, alkali metal salts or amine salts thereof, polymethacrylic acid, alkali metal salts or amine salts thereof, polyacrylamide, polyhydroxyethyl acrylate, polyvinyl. Pyrrolidone, polyvinyl methyl ether, poly-2-acrylamido-2-methyl-1-propanesulfonic acid, its alkali metal salts or amine salts, gum arabic, cellulose ether (eg, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose), dextrin and Included are derivatives thereof (eg, white dextrin, enzyme-degraded etherified dextrin pullulan).
A copolymer having two or more kinds of repeating units of water-soluble organic polymer may be used. Examples of copolymers include vinyl alcohol-vinyl acetate copolymers (partially saponified polymers of polyvinyl acetate) and vinyl methyl ether-maleic anhydride copolymers. When a vinyl alcohol-vinyl acetate copolymer is synthesized by partial saponification of polyvinyl acetate, the saponification degree is preferably 65% by mass or more. You may use together two or more types of water-soluble organic polymers.

The above photothermal conversion agent may be added to the overcoat layer. The photothermal conversion agent added to the overcoat layer is preferably water-soluble. A nonionic surfactant (eg, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl ether) can be added to the coating solution for the overcoat layer. The coating amount of the overcoat layer is preferably 0.1 to 2.0 g / m ² .

[Image-like heating step] The lithographic printing original plate is imagewise heated to form an image. Directly, the lithographic printing plate precursor can be imagewise heated by the thermal recording head. In that case, the photothermal conversion agent is unnecessary. However, since the thermal recording head generally has a low image resolution, it is desirable to use a photothermal conversion agent to convert light energy by image exposure into heat energy. Generally, the exposure device used for image exposure has higher resolution than the thermal recording head. The exposure method includes exposure through an original (original) which is analog data and scanning exposure corresponding to original data (usually digital data). For exposure through the original, a xenon discharge lamp or an infrared lamp is used as a light source. If a high-power light source such as a xenon discharge lamp is used, short-time flash exposure is possible.

For scanning exposure, it is general to use a laser, especially an infrared laser. Infrared wavelength is 70
It is preferably 0 to 1200 nm. Infrared
Solid-state high-power infrared laser (for example, semiconductor laser,
YAG laser) is preferred. Laser output is 100m
W or more is preferable. To reduce the exposure time, it is preferable to use a multi-beam laser device. Also, 1
The exposure time per pixel is preferably within 20 μsec. The light energy applied is 10 to 500 mJ /
It is preferably cm ² . Heating is preferably carried out at a temperature at which both the shell and core soften. The heating temperature is preferably 10 ° C. or more higher than the higher one of the softening temperature of the shell and the softening temperature of the core,
It is more preferable that the temperature is 20 ° C. or higher.

[Plate-making and printing process] The planographic printing plate precursor image-wise heated can be made into a plate by developing with water or a suitable aqueous solution as a developing solution. However, even if the development process is not performed, the planographic printing plate can be continuously printed by simply mounting the planographic printing plate precursor heated in an image form on the printing machine and printing with ink and fountain solution in the usual procedure. Can be carried out. That is, when the lithographic printing plate precursor is mounted on the printing machine and the printing machine is operated, the image forming layer in the portion heated by dampening water, ink, or rubbing can be removed. If a printing machine having a laser exposure device (described in Japanese Patent No. 2938398) is used,
After mounting the lithographic printing plate on the press cylinder,
It is also possible to perform exposure with a laser installed in a printing machine, and then apply dampening water or ink to perform on-machine development (exposure to printing are continuously processed).

[0173]

EXAMPLES [Example 1] (Preparation of core / shell structure fine particles) In a 1-liter three-necked flask, 29.6% by mass of the following anionic surfactant was added.
An aqueous solution of 4.8 g and distilled water of 540 g were added, and the mixture was stirred under a nitrogen stream at 50 ° C. at 250 rpm for 30 minutes. A solution of 0.462 g of potassium peroxodisulfate, 0.178 g of sodium bisulfite and 5.13 mL of a 1M sodium hydrogen carbonate aqueous solution mixed therein to make 30 mL with distilled water, and 71.08 g of glycidyl methacrylate were mixed.
It dripped over time. After the completion of dropping, potassium peroxodisulfate 0.231 g and sodium hydrogen sulfite 0.089
g, 10 mL of distilled water and 2.56 mL of a 1 M sodium hydrogencarbonate aqueous solution were added, and then 3
Stirring was continued for a while to prepare core fine particles. The average particle size of the obtained core fine particles was 100 nm. The softening temperature of the polymer forming the core fine particles was 85 ° C.

[0174]

[Chemical 87]

The reaction mixture thus obtained was treated under a nitrogen stream at 50
After stirring at 250 rpm for 30 minutes at 250 rpm, potassium peroxodisulfate 0.127 g, sodium hydrogen sulfite 0.048 g, 1M sodium hydrogen carbonate aqueous solution 1.4 m
A solution prepared by mixing L with 30 mL of distilled water and 23.53 g of methyl methacrylate were added dropwise over 3 hours. After the dropping was completed, potassium peroxodisulfate was further added.
127 g, distilled water 10 g, sodium hydrogen sulfite 0.0
After adding a solution in which 48 g and 1.4 mL of a 1 M sodium hydrogen carbonate aqueous solution were mixed, stirring was continued as it was. After 3 hours, the reaction mixture was cooled to room temperature and filtered through a glass filter to remove aggregates. The solid content concentration was adjusted to 10% by weight with distilled water to prepare core / shell structure fine particles. The average particle diameter of the obtained core / shell structured fine particles was 110 nm. The core / shell mass ratio is 3.02, and the softening temperature of the shell polymer is 1
It was 30 ° C.

(Preparation of Aluminum Support) Al99.
5% or more, Fe 0.30%, Si 0.10%, Ti 0.
JIS-A-1050 containing 02% and Cu 0.013%
The molten alloy was cleaned and cast into an aluminum plate. For the cleaning treatment, degassing treatment was performed to remove unnecessary gas such as hydrogen in the molten metal, and ceramic tube filter treatment was performed. The casting method was a DC casting method. The solidified ingot with a thickness of 500 mm is ground by 10 mm from the surface,
A homogenizing treatment was performed at 550 ° C. for 10 hours so that the intermetallic compound did not become coarse. Then, after hot rolling at 400 ° C. and intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, cold rolling was performed to obtain an aluminum rolled plate having a plate pressure of 0.30 mm. The center line average surface roughness Ra after cold rolling is 0.2 by controlling the roughness of the rolling roll.
It was controlled to μm. Then, a tension leveler was applied to improve the flatness.

Next, a surface treatment was carried out to obtain a support for a lithographic printing plate. First, in order to remove the rolling oil on the surface of the aluminum plate, it is treated with a 10 mass% sodium aluminate solution at 50 ° C
Was degreased for 30 seconds, neutralized with a 30% by mass aqueous sulfuric acid solution at 50 ° C. for 30 seconds, and smut-removed.
Next, in order to improve the adhesion between the support and the image-forming layer and to impart water retention to the non-image area, the surface of the support was roughened, that is, a so-called graining treatment was performed. An aqueous solution containing 1% by mass of nitric acid and 0.5% by mass of aluminum nitrate was added to 45
While maintaining the temperature at ℃, while flowing the aluminum web in the aqueous solution, the anode side electricity quantity of 240 C / dm with an alternating waveform with a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect power supply cell.
Electrolytic graining was performed by giving ² . Then 10%
Etching treatment was performed with an aqueous solution of sodium aluminate at 50 ° C. for 30 seconds, neutralization was performed with an aqueous solution of 30 mass% sulfuric acid at 50 ° C. for 30 seconds, and smut removal treatment was performed.

Further improved abrasion resistance, chemical resistance and water retention
To form an oxide film on the support by anodization.
I made it. 20% by mass aqueous solution of sulfuric acid as an electrolyte at 35 ° C
Indirectly while carrying the aluminum web through the electrolyte.
14 A / dm depending on the power supply cell ²Electrolysis with direct current of
2.5 g / m²The anodic oxide film of was prepared. this
In order to ensure hydrophilicity as a non-image area on the post-printing plate,
Kate processing was performed. Treatment is No. 3 sodium silicate 1.5%
Keeping the aqueous solution at 70 ℃, the contact time of aluminum web is 15 seconds
And then washed with water. The adhesion amount of Si is 1
0 mg / m ²Met. R of the support made by the above
a (center line surface roughness) was 0.25 μm.

(Preparation of lithographic printing original plate) An aluminum support was coated with an image forming layer coating solution having the following composition and dried at 60 ° C. for 3 minutes. The coating weight after drying was 0.6 g / m ² . In this way, a lithographic printing original plate was produced.

[0180] ────────────────────────────────────   Composition of coating liquid for image forming layer ────────────────────────────────────   Fine particles with core / shell structure (solid content conversion) 0.99 g   Infrared absorbing dye (IR-10) 0.12g   Polyacrylic acid with a molecular weight of 25,000 0.09g   10% by mass aqueous solution of fluorine-based surfactant 0.10 g ────────────────────────────────────

(Evaluation of lithographic printing original plate) The obtained lithographic printing original plate was used as a trend setter 3244VFS manufactured by Creo Co. equipped with a water-cooled 40W infrared semiconductor laser to rotate the outer surface drum at 100 rpm and plate energy at 200 mJ /.
Exposure was performed under the conditions of cm ² and resolution of 2400 dpi. It is mounted on a SOR-M printer manufactured by Heidelberg without developing, and commercially available additives (IF201 (2.5%) Fuji Photo Film Co., Ltd., IF202 (0.75%) Fuji Photo Film Co., Ltd. Printing) using a commercially available black ink (GEOS-G ink, manufactured by Dainippon Ink and Chemicals, Inc.) as usual, and printing until a good printed matter is obtained. The number of printed sheets (printing) and the number of sheets (printing endurance) from which a good printed matter was obtained were evaluated. Separately, wrap the obtained lithographic printing plate precursor with aluminum kraft paper and
After left in a constant temperature and humidity warehouse at 0 ° C. and a relative humidity of 40% for 3 days, it was exposed and printed under the same conditions as above. As in the case immediately after the above production, the number of prints until a good printed matter was obtained (printing) and the number of good printed matters obtained (printing durability) were evaluated. The results are shown in Table 2.

[Example 2] (Preparation of lithographic printing plate precursor) The same as Example 1 except that a mixture of styrene / 4-vinylpyridine (mixing molar ratio: 75/25) was used in place of glycidyl methacrylate. To prepare core / shell structured fine particles. The average particle diameter of the core fine particles is 80 nm, the average particle diameter of the core / shell structured fine particles is 100 nm, and the mass ratio of the core / shell is 1.05.
Met. Using the prepared core / shell structure fine particles,
A lithographic printing original plate was prepared in the same manner as in Example 1.

(Evaluation of lithographic printing original plate) The obtained lithographic printing original plate was subjected to plate making and printing in the same manner as in Example 1 and evaluated.
The results are shown in Table 2.

[Example 3] (Preparation of lithographic printing plate precursor) Same as Example 1 except that a mixture of methyl methacrylate / acetoacetoxyethyl methacrylate (mixing molar ratio: 70/30) was used instead of glycidyl methacrylate. Thus, core / shell structured fine particles were prepared. The average particle size of the core particles is 60n
m, the average particle diameter of the core / shell structure fine particles is 90 nm,
The core / shell mass ratio was 0.42. A lithographic printing original plate was produced in the same manner as in Example 1 using the prepared core / shell structured fine particles.

(Evaluation of lithographic printing original plate) The obtained lithographic printing original plate was subjected to plate making and printing in the same manner as in Example 1 and evaluated.
The results are shown in Table 2.

[Examples 4 to 6] (Preparation of lithographic printing plate precursor) A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that the core / shell structured fine particles shown in Table 1 were prepared and used.

[0187]

[Table 1] Table 1 ──────────────────────────────────── Lithographic printing Average of constituent polymer of fine particles Particle size (nm) Softening temperature (℃) Core / Che master (core / shell) Core Overall core Shell mass ratio ───────────────────────── ──────────── Example 1 10/102 100 110 85 85 130 3.02 Example 2 CP1 / 102 80 100 100 110 130 1.1 Example 3 CP2 / 102 60 90 90 80 130 0. 4 Example 4 CP49 / CP101 80 90 90 95 85 2.4 Example 5 CP50 / CP101 70 90 110 110 85 0.9 Example 6 CP51 / CP101 60 80 80 100 85 0.7 ──────────── ──────────────────────── ──

(Note) 10: polyglycidyl methacrylate 102: polymethyl methacrylate CP1: styrene / 4-vinylpyridine copolymer (copolymerization molar ratio: 75/25) CP2: methyl methacrylate / acetoacetoxyethyl methacrylate copolymer (copolymerization molar ratio) : 70/3
0) CP49: Styrene / 2-vinylpyridine copolymer (copolymerization molar ratio: 80/20) CP50: Styrene / N- (isobutoxymethyl) acrylamide copolymer (copolymerization molar ratio: 75/25) CP51: Styrene / p- Vinylbenzyl acetoacetate copolymer (copolymerization molar ratio: 80/20) CP101: methyl methacrylate / butyl methacrylate copolymer (copolymerization molar ratio: 70/30)

(Evaluation of lithographic printing original plate) The obtained lithographic printing original plate was subjected to plate making and printing in the same manner as in Example 1.
The results are shown in Table 2.

Comparative Example 1 (Preparation of Comparative Fine Particles) In a 1-liter three-necked flask,
29.6% by mass of the anionic surfactant used in Example 1
An aqueous solution of 4.8 g and distilled water of 540 g were added, and the mixture was stirred under a nitrogen stream at 50 ° C. at 250 rpm for 30 minutes. A solution of 0.462 g of potassium peroxodisulfate, 0.178 g of sodium bisulfite and 5.13 mL of 1M sodium hydrogen carbonate solution and 30 mL of distilled water, and 71.08 g of glycidyl methacrylate were added dropwise thereto over 3 hours. . After completion of dropping, 0.231 g of potassium peroxodisulfate, 0.089 g of sodium hydrogen sulfite, 10 mL of distilled water, 1M aqueous solution of sodium hydrogencarbonate 2.56.
After adding a solution in which mL was mixed, stirring was continued as it was for 3 hours to prepare fine particles. The particle size of the obtained fine particles is
It was 100 nm. In addition, 2 g of the obtained fine particle aqueous solution
After adding 1 g of saturated saline solution to the above, the resin and the aqueous solution were separated by a centrifuge, and the supernatant was removed, followed by drying under reduced pressure.
A powder resin was obtained. The softening temperature of the powder resin measured by the strain gauge method was 85 ° C.

(Preparation of lithographic printing original plate) Using the prepared core / shell structured fine particles, a lithographic printing original plate was prepared in the same manner as in Example 1.

(Evaluation of lithographic printing original plate) The obtained lithographic printing original plate was subjected to plate making and printing in the same manner as in Example 1 and evaluated.
The results are shown in Table 2.

[0193]

[Table 2] Table 2 ──────────────────────────────────── Planographic printing Fine particle composition Polymer printing Evaluation (immediately after manufacturing) Printing evaluation (after storage) Original plate (core / shell) Imprinted number of printed sheets Number of printed sheets of durable print ──────────────────────── ───────────── Example 1 10/102 10 sheets 25,000 sheets 10 sheets 25,000 sheets Example 2 CP1 / 102 10 sheets 20 thousand sheets 10 sheets 2. 0000 sheets Example 3 CP2 / 102 10 sheets 25,000 sheets 10 sheets 25,000 sheets Example 4 CP49 / CP101 10 sheets 30 thousand sheets 10 sheets 3.0 million sheets Example 5 CP50 / CP101 10 Sheets 35,000 sheets 10 sheets 35,000 sheets Example 6 CP51 / CP101 10 sheets 3 million sheets 10 sheets 3 million sheets Comparative example 1 10 (non-core / sheet) 30 sheets 15,000 sheets 300 sheets 15,000 sheets ─────────────────────────────────── ──

(Note) 10: Polyglycidyl methacrylate 102: Polymethyl methacrylate CP1: Styrene / 4-vinylpyridine copolymer (copolymerization molar ratio: 75/25) CP2: Methyl methacrylate / acetoacetoxyethyl methacrylate copolymer (copolymerization molar ratio) : 70/3
0) CP49: Styrene / 2-vinylpyridine copolymer (copolymerization molar ratio: 80/20) CP50: Styrene / N- (isobutoxymethyl) acrylamide copolymer (copolymerization molar ratio: 75/25) CP51: Styrene / p- Vinylbenzyl acetoacetate copolymer (copolymerization molar ratio: 80/20) CP101: methyl methacrylate / butyl methacrylate copolymer (copolymerization molar ratio: 70/30)

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing a basic configuration of a preferable lithographic printing plate precursor.

[Explanation of symbols]

1 Hydrophilic support 2 Image forming layer 21 core / shell structured particles 21c core 21s shell 22 Photothermal conversion agent 23 Hydrophilic polymer

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA01 AA02 AA11 AA12 AB03                       AC08 AD01 BJ03 CC11 DA36                       FA10                 2H084 AA14 AE05 BB02 BB04 CC05                 2H096 AA06 BA01 EA04 EA23 GA08                 2H114 AA04 AA23 BA01 BA10 DA21                       DA41 EA02 FA06

Claims (4)

[Claims] 1. A lithographic printing plate precursor having an image-forming layer comprising a hydrophilic polymer and a core / shell structure fine particle having a chemically active core and a thermoplastic shell, and an image forming layer provided on the hydrophilic support. Heating, softening the shells and fusing the shells together, contacting the cores, the core and the hydrophilic support, or the core and the hydrophilic polymer, and chemically bonding any of them, and A method for making a lithographic printing plate comprising a step of treating an lithographic printing plate precursor with an aqueous medium to remove an image forming layer in a non-heated portion. 2. A lithographic printing plate precursor on which a hydrophilic support is provided with an image forming layer containing core / shell structure fine particles having a chemically active core and a thermoplastic shell, a hydrophilic polymer and a photothermal conversion agent. Imagewise heating by scanning with a laser beam to soften the shells to fuse the shells together, and to bring the cores into contact with each other, the core and the hydrophilic support, or the core and the hydrophilic polymer. A method of making a lithographic printing plate, comprising the steps of chemically bonding the lithographic printing plate and the step of treating the lithographic printing plate precursor with an aqueous medium to remove the image forming layer in the unheated portion. 3. A lithographic printing original plate having an image-forming layer comprising a hydrophilic polymer and a core / shell structured fine particle having a chemically active core and a thermoplastic shell, and an image-forming layer on a hydrophilic support. A step of heating and softening the shells to fuse the shells together, and contacting the cores, the core and the hydrophilic support, or the core and the hydrophilic polymer to chemically bond either one, lithographic printing The original plate is attached to the printing machine and the printing machine is operated to remove the image forming layer in the unheated portion by dampening water, ink, or rubbing.
A lithographic printing method comprising the steps of making a lithographic printing plate as described above, and further supplying dampening water and an oil-based ink and printing with the lithographic printing plate thus made. 4. An image forming layer containing a core / shell structure fine particle having a chemically active core and a thermoplastic shell, a hydrophilic polymer and a photothermal conversion agent is provided on a hydrophilic support, and the core is chemically formed. A lithographic printing original plate comprising a polymer having a chemically active group and a shell having a softening point of 60 to 200 ° C.