JP2003291553A - Lithographic printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing original plate which can be printed by mounting in a printer as it is without treating after an exposure, which has a good on-board developability, large strengths in fine halftone dots and fine lines and a high plate wear resistance, and in which a hardness to stain is further improved in printing. <P>SOLUTION: The lithographic printing original plate comprises: a hydrophilic layer containing a hydrophobicity prepared precursor fine particles and a hydrophilic binder polymer; and an image forming layer containing a microcapsule including a hydrophobic substance and a photothermal conversion substance, sequentially formed on a water resisting support. In the original plate, the binder polymer is a composite material of a resin having a bond of connecting at least one atom selected from the group consisting of a metal atom and a semi-metal atom via an oxygen atom and a hydrophilic organic polymer. The hydrophobic substance is a hydrophobic resin having two or more of atomic groups each having 10 kJ/mol or more of aggregation energy contribution in a minimum repeating unit or a hydrophobic compound having 45°C or higher of a phase transfer temperature. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a hydrophilic layer on a support.
Scanning exposure based on digital signals.
After light, it can be developed on a printing press and has high printing durability.
The present invention relates to an original plate for lithographic printing that is difficult to resist. [0002] 2. Description of the Related Art In general, lithographic printing plates are dampened during the printing process.
Hydrophobic (lipophilic) image area that repels water and accepts ink
And a hydrophilic non-image portion that receives the fountain solution. this
Such lithographic printing plates are conventionally oleophilic on a hydrophilic support.
A PS plate provided with a photosensitive resin layer is placed through a lith film.
After the exposure, the photosensitive resin layer in the non-image area is dissolved with a developer.
It was made by removing the solution. [0003] In recent years, image information is electronically transmitted using a computer.
Digitization technology that processes, stores, and outputs subordinately is widely used.
As a result, light with high directivity such as laser light
Scanning according to digitized image information and refilling
Direct image to lithographic printing plate without going through
Computer-to-plate (CTP) technique for forming
Skills have been developed. On the other hand, the production of printing plates using conventional PS plates
The process of dissolving and removing non-image areas after exposure is indispensable.
Yes, usually the developed printing plate was washed with water
Rinse solution containing surfactant, gum arabic, starch
A post-treatment step is also required, which involves treatment with a desensitizing solution containing powder derivatives, etc.
It was important. Such additional wet processing is cumbersome.
Yes, especially to the global environment, which has become a big concern in recent years
Another consideration for conventional technologies that have been desired to be improved.
It is one problem. Therefore, simplification of processing, dry processing or no processing
This is because of the environmental aspects and the process that accompanies the aforementioned digitization.
From the perspective of both further streamlining,
It has come to be strongly desired. That is, image recording
After that, the CTP system can be used for printing without wet processing.
An original printing plate for a stem is desired. One way to eliminate processing steps is to expose
Insert the original plate for printing plate into the cylinder of the printing press,
Supply dampening water and / or ink while rotating the drum
The non-image portion of the printing plate original image forming layer
There is a method called on-press development for removal. That is, mark
After exposing the original plate for printing plate, it is mounted on the printing machine as it is and
In this method, processing is completed in the print preparation process. A CTP flat suitable for such on-press development.
As an original plate for plate printing, for example, Japanese Patent No. 2938397
No., thermoplastic hydrophobic weight in hydrophilic binder polymer
A photosensitive layer in which coalesced fine particles are dispersed is provided on a hydrophilic support.
A lithographic printing plate is described. This gazette includes the lithographic
In printing plates, infrared hydrophobic exposure to thermoplastic hydrophobicity
Image formation by coalescence (fusion) of functional polymer fine particles by heat
After that, attach the plate to the plate cylinder of the printing press, and use fountain solution and / or
Can be developed on-press by supplying ink.
It is listed. Also, JP-A-2001-162961 discloses
Is a microcapsule containing a hydrophobic component on a support.
And image formation containing hydrophilic binder polymer
A heat-sensitive lithographic printing plate with a hydrophilic layer can be developed on-machine.
It is described that. Japanese Patent Application Laid-Open No. 2001-205952 describes support.
On the body, a hydrophilic layer containing a heat-reactive compound, and further
Containing a reaction partner compound of the thermally reactive compound
A lithographic printing plate having is described. This lithographic seal
When printing heat is applied, the hydrophilic layer and the heat-sensitive layer are chemically
Since it adheres by reaction, printing durability is improved. [0010] However, according to the prior art,
The original lithographic printing plate still has printing such as stain resistance and printing durability.
The performance was insufficient. The object of the present invention is to solve this problem.
It is to be decided. That is, it has good on-machine developability.
In addition, the stain resistance in printing has been further improved, and fine halftone dots
Providing lithographic printing original plates with high strength and fine wire strength and high printing durability
There is to do. [0011] [Means for Solving the Problems] On a water resistant support,
Hydrophobized precursor fine particles and hydrophilic binder polymer
A microcapsule containing a hydrophilic layer and a hydrophobic substance
In this order, the image forming layer containing the psel and the photothermal conversion material is added.
A lithographic printing plate having a hydrophilic binder
The remer is selected from the group consisting of metal atoms and metalloid atoms
At least one atom connected via an oxygen atom
A composite of a resin having a bond and a hydrophilic organic polymer
That is, the hydrophobic material has a cohesive energy within the smallest repeating unit.
-Contributing two or more atomic groups with contribution of 10 kJ / mol or more
An original plate for lithographic printing, which is a hydrophobic resin. [0012] 2. The hydrophobic resin is an epoxy resin, a fluororesin.
Enol resin, polyester resin, polyurethane resin,
Melamine resin, polyamide resin, alkyd resin, xyle
Made of styrene resin, urea resin and hydroxystyrene resin
It is at least one resin selected from the group
The lithographic printing original plate as described in 1 above. 3. Hydrophobic precursor fine particles on a water-resistant support
A hydrophilic layer containing particles and a hydrophilic binder polymer,
And microcapsules enclosing hydrophobic substances and photothermal conversion
Lithographic printing having image forming layers containing substances in this order
A hydrophilic binder polymer is used as a metal substrate.
At least one selected from the group consisting of a child and a metalloid atom
Resin having a bond in which two atoms are connected via an oxygen atom
Is a complex of a hydrophilic organic polymer and a hydrophobic substance
Is a hydrophobic compound with a phase transition temperature of 45 ° C or higher
An original plate for lithographic printing. 4). The hydrophobic compound reacts with heat
3. The lithographic stamp as described in 3 above, which has a functional group
Master plate for printing. 5. The hydrophilic organic polymer is
It has a silane coupling group at the terminal represented by the formula (I)
1 to 4 above, wherein the polymer is
The lithographic printing plate according to any one of the above. [0016] [Chemical 1] [In the general formula (I), R¹¹, R¹², R¹³as well as
R¹⁴Are independently hydrogen atoms or carbon atoms of 1 to 8 carbon atoms.
Represents a hydrogen group, m represents 0, 1 or 2, and n represents 1 to 8
Represents an integer. L represents a single bond or an organic linking group, and W represents −
NHCOR¹⁵, -CONH₂, -CON (R¹⁵)₂, -C
OR¹⁵, -OH, -CO₂M or -SO_ThreeM represents here
And R¹⁵Represents an alkyl group having 1 to 8 carbon atoms, M is hydrogen
Atom, alkali metal, alkaline earth metal or onium
Represent. ] 6. The hydrophilic layer is chemically bonded to the surface.
Tables containing combined polymeric compounds having hydrophilic functional groups
1) characterized in that it has a surface graft hydrophilic layer
The lithographic printing plate according to any one of 5 above. 7. Polymer compound having the hydrophilic functional group
Directly at the end of the polymer chain and / or
Other binding polymer compounds chemically bonded to the hydrophilic layer
A linear polymer compound bonded to the hydrophilic layer via
The lithographic printing plate as described in 6 above, wherein the lithographic printing plate is provided. 8. Consisting of metal atoms and metalloid atoms
At least one atom selected from the group via an oxygen atom
A resin having a connected bond is represented by the following general formula (II).
By hydrolysis polycondensation of at least one compound
1 to the above characterized in that it is a resin obtained by
The lithographic printing plate according to any one of 7 above. [0021] Formula (II) (R²⁰)_kM⁰(Y)_Zk [In general formula (II), R²⁰Is a hydrogen atom, hydrocarbon group or compound
Represents a cyclic group, Y represents a reactive group, M⁰Is 3-6 valent
Represents metal or metalloid, z is M⁰Represents the valence of
Represents 0, 1, 2, 3, or 4; However, z-k is 2 or more
It is. ] As a result of intensive studies, the present invention has found that the hydrophilic layer and the image
In a lithographic printing plate having a layer structure having an image forming layer,
Hydrophobic precursors contained in the water layer make the exposed area hydrophilic
Perform selective hydrophobization and / or shape change on the layer surface
Strong adhesion between the hydrophilic layer and the negative image on the image forming layer
When printing, use a hydrophilic layer binder polymer.
At least one selected from metal atoms and metalloid atoms
A tree containing a bond in which two atoms are connected via an oxygen atom
By using a complex of fat and hydrophilic organic polymer
Prevents the hydrophilic layer from degrading and improves the dirt resistance.
It is a thing. [0023] DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
Will be described in detail. In the following, “%” is not particularly specified.
As long as it represents mass%. [Hydrophilic layer] The hydrophilic layer of the present invention is formed before being hydrophobized.
Contains precursor and hydrophilic binder polymer. The hydrophobicity
Precursor is a fine particle of hydrophobic material (single component hydrophobic
Precursor) or a hydrophobic substance in the core and a hydrophilic substance on the outside
Fine particles with a composite structure (hydrophobization precursor of composite structure)
Body), and the hydrophobized precursor is a hydrophilic binder poly
When heat is applied to the hydrophilic layer dispersed in the polymer,
Aqueous substances melt, coalesce, react, exude, diffuse, etc.
The hydrophilic layer surface can be hydrophobized and / or changed in shape
Fine particles. As a single component hydrophobizing precursor, hydrophobic
Low molecular weight organic materials, thermoplastic polymers, thermosetting polymers
Polymers with polymer and thermally reactive functional groups (thermally reactive
At least one selected from polymers)
There are things made as children. Preferred organic low molecular weight compounds are hydrophobic and
Melting point is 300 ° C or lower and boiling point is 100 ° C or higher at normal pressure
A solid or liquid organic compound having a molecular weight of 2000
The following compounds are: In the present invention, as an index of hydrophobicity, 25 ° C.
The solubility in 100 g of water is 2 g or less,
Or the organic / inorganic ratio in the organic conceptual diagram is 0.7 or more
Use the above. Here, the organic conceptual diagram is a compound
Practical and simple to show the degree of organic and inorganic
Scale, “Organic Conceptual Diagram” by Tanaka Yoshio (Sankyo Publishing)
Pp. 1-31 of the company, first published in 1983)
The Such organic low molecular weight compounds include high molecular weight compounds.
Boiling point aliphatic and aromatic hydrocarbons, carboxylic acids, al
Cole, ester, ether, amine and their derivatives
Body, other components for printing ink, plasticizers, etc.
be able to. Specific examples include n-nonane and n-deca.
N-hexadecane, octadecane, eicosane, potassium
Proic acid, capric acid, stearic acid, oleic acid, dopamine
Decyl alcohol, octyl alcohol, n-octade
Sil alcohol, 2-octanol, lauryl alcohol
, Lauryl methyl ether, stearyl methyl ether
, Stearylamide, linseed oil, soybean oil, poppy oil, sacrificial oil
Oils and fats such as flower oil, tributyl phosphate, tric acid phosphate
Resyl, dibutyl phthalate, butyl laurate, lid
Plasticizers such as dioctyl oxalate, carnauba wax,
Star wax, microcrystalline wax, para
Fin wax, shellac wax, palm wax, beeswax
Which waxes, low molecular weight polyethylene, silver behenate,
Such as calcium stearate and magnesium palmitate.
Examples of long-chain fatty acid metal salts and other fine particle dispersions
It is done. Examples of organic polymer compounds include thermoplastic polymers.
Polymer, thermosetting polymer, poly having thermoreactive functional group
And the like. Fine particles (fine particles) of these polymers
(Also called child polymer or polymer fine particles)
When obtained, the fine particles melt or react to coalesce.
By converting the hydrophilic layer surface to hydrophobic,
The surface shape can be changed. These fine particles are in the image forming layer.
These can be used alone or in combination of two or more. Thermoplastic polymer granules used in the present invention
As a child, it is insoluble in water and has a glass transition point of 50 ° C to 1 ° C.
Thermophysical properties in the range of 80 ° C, and the average particle size of resin fine particles is
The thing of 0.005-2.0 micrometers is preferable. More preferred
The glass transition point is 60 ° C to 160 ° C, and the average particle size is
0.01 to 1.5 μm. Form these fine particles
The mass average molecular weight (Mw) of the resin is preferably 3 × 1
0^Three~ 1x10⁶And more preferably 5 × 10^Three~ 8
× 10^FiveIt is. Resins with physical properties in this range
By using the effect of the present invention, that is, hydrophilicity
(Stain resistance in printing) and better adhesion to the image area
The above is obtained well. As such a resin, for example, Yuji Harasaki
"Latest binder technical handbook" etc. General Technology Center Co., Ltd.
(Published in 1985), Koichi Nakamura “Binder for recording materials
Practical technology "CMC Co., Ltd. (1985), Chubu
Business Development Center Publishing Department “Synthesis and design of acrylic resin
And New Application Development "(published in 1985), Research Dis
As described in closure No. 33303 (January 1992)
Each resin is mentioned. Specific examples include olefin polymers and copolymers.
Body (eg, polyethylene, polypropylene, polyiso
Butylene, ethylene-vinyl acetate copolymer, ethylene
Acrylate copolymer, ethylene-methacrylate copolymer
Polymer, ethylene-methacrylic acid copolymer, cycloalkene
Copolymer, vinylcycloalkane copolymer, etc.), chloride
Vinyl polymers and copolymers (eg, polyvinyl chloride,
Vinyl chloride-vinyl acetate copolymer, etc.), vinylidene chloride
Copolymer, vinyl alkanoate polymer and copolymer, al
Allyl citrate polymers and copolymers, styrene and its derivatives
Conductor polymers and copolymers (eg butadiene-
Tylene copolymer, isobutylene-styrene copolymer,
Tylene-methacrylate copolymer, styrene-acrylate
-Copolymer), acrylonitrile copolymer, methacrylate
Lilonitrile copolymer, alkyl vinyl ether copolymer
, Acrylic acid ester polymer and copolymer, methacrylate
Luric acid ester polymers and copolymers, Itacon Sanges
Terpolymers and copolymers, maleic anhydride copolymers, polymers
Kurylamide copolymer, methacrylamide copolymer,
Enol resin, alkyd resin, polycarbonate resin,
Ketone resin, polyester resin, hydroxyl group and carboxy
Group-modified polyester resin, butyral resin, polyvinyl chloride
Ruacetal resin, urethane resin, rosin resin, hydrogenated
Rosin resin, petroleum resin, hydrogenated petroleum resin, malein
Acid resin, terpene resin, hydrogenated terpene resin, cyclized rubber
-Methacrylic acid ester copolymer, cyclized rubber-Akkuk
Rylate copolymer, heterocycle containing no nitrogen atom
Containing a copolymer (for example, a furan ring as a heterocyclic ring,
Tetrahydrofuran ring, thiophene ring, dioxane ring,
Dioxofuran ring, lactone ring, benzofuran ring, ben
Zothiophene ring, 1,3-dioxetane ring, etc.), Epoxy
And the like. These resins may be used alone or in combination of two or more.
A combination of the above may be used. The formation of fine particles of these thermoplastic polymers
Polymerization granulation reaction (emulsification) using each corresponding resin monomer
Polymerization, suspension polymerization, etc.)
Or a method of making fine particles by a dry mechanical method, or
A solution of the resin in a water-immiscible solvent with milk in the aqueous phase.
Conventionally known methods can be used, such as a method of dispersing and dispersing
The Specifically, for example, "the latest technology of polymer fine particles and
Application development "CMC Co., Ltd. (published in 1997)
Material design for new powders "Techno System (1988)
Etc.). Thermosetting polymer fine particles used in the present invention
As a child, a resin having a phenol skeleton, a urea resin
(Eg urea induction such as urea or methoxymethylated urea
Resin body with aldehydes such as formaldehyde
Melamine resin (for example, melamine or
Derivatives of aldehydes with aldehydes such as formaldehyde
Resin), alkyd resin, unsaturated polyester
Resin, polyurethane resin, epoxy resin, etc.
The As a resin having a suitable phenol skeleton
For example, phenol, cresol, etc.
Phenol resinized with aldehydes such as dehydride
Resin, hydroxystyrene resin, N- (p-hydroxy
Phenol skeleton such as phenyl) methacrylamide
Methacrylamide or acrylamide resin, and p
-Phenols such as hydroxyphenyl methacrylate
Methacrylate or acrylate resin with skeleton
I can make it. Of these, particularly preferred
Resin having an enol skeleton, melamine resin, urea resin and
And epoxy resin. The fine particles of the thermosetting polymer are the same as those described above.
It can be performed in the same way as the fine particles of thermoplastic resin.
it can. The polymer having a heat-reactive functional group used in the present invention.
As the thermoreactive functional group of the polymer particles, a polymerization reaction is performed.
Ethylenically unsaturated groups (eg acryloyl groups, meta
Acryloyl group, vinyl group, allyl group, etc.)
Isocyanate group to be performed or block body thereof and
A functional group having an active hydrogen atom as a reaction partner (for example,
Amino group, hydroxyl group, carboxyl group, etc.)
An epoxy group that undergoes an addition reaction and its reaction partner
Amino group, carboxyl group or hydroxyl group, condensed
Carboxyl group and hydroxyl group or
Amino group, acid anhydride and amino group that perform ring-opening addition reaction
Or a hydroxyl group. Only
If a chemical bond is formed, what kind of reaction is performed
It may be a functional group. Introduction of these functional groups into fine polymer particles
May be performed at the time of polymerization, or a polymer reaction may be performed after the polymerization.
May be used. When introduced during polymerization, these functional groups
Emulsion polymerization or suspension polymerization of monomers having
Is preferred. Specific examples of monomers having such functional groups
Examples include allyl methacrylate, allyl acrylate
, Vinyl methacrylate, vinyl acrylate, grease
Sidyl methacrylate, glycidyl acrylate, 2-
Vinyloxyethyl methacrylate, 2-isocyanate
Totoethyl methacrylate or its alcohol
Block isocyanate, 2-isocyanate ethyl
Acrylate or alcohol
Ic isocyanate, 2-aminoethyl methacrylate
2-aminoethyl acrylate, 4-aminomethyl
Styrene, 4-vinyloxystyrene, 2-hydroxy
Ethyl methacrylate, 2-hydroxyethyl acrylate
, Acrylic acid, methacrylic acid, maleic anhydride, 2
Functional acrylate, bifunctional methacrylate, or special
Paragraph No. [00] in the specification of Kakai 2001-293971
18] to [0035] and the like.
Although it can, it is not limited to these. In the emulsion polymerization or suspension polymerization,
It has a thermally reactive functional group that can be copolymerized with the above monomers.
Monomers may coexist. With such monomers
For example, styrene, alkyl acrylate, acrylic
Rukylemethacrylate, acrylonitrile, vinyl acetate
But do not have a thermally reactive functional group.
The monomer is not limited to these as long as it is a good monomer. When introduction of heat-reactive functional group after polymerization
Examples of the polymer reaction used in the method include WO96-34.
The polymer reaction described in No. 316 can be exemplified. Polymers having these thermally reactive functional groups
The solidification temperature of the fine particles is preferably 70 ° C. or higher.
Considering qualitative properties, 100 ° C. or higher is more preferable. Further, the resin fine particles of the hydrophobizing precursor are prepared.
Self-water dispersion with a fine resin particle surface having a hydrophilic surface
Hydrophobic resin fine particles. Suitable self-water dispersible hydrophobic resin fine particles
(1) The lipophilic resin structure and hydrophilicity in the molecule
And a raw material resin having a structural part having a group.
221137 and JP-A-5-66600
Such as emulsifiers and protective colloids.
Resin fine particles dispersed in water, and (2) core / shell
It has a structure, the core part is lipophilic resin, the shell part is hydrophilic
Fine particles composed of resin composed of components, and (3) hydrophobic
Encapsulating the active substance and protecting its surface with hydrophilic wall material
Examples include microcapsule fine particles. These self-water dispersible hydrophobic resin fine particles
Is easily and uniformly dispersed in the coating dispersion for forming the hydrophilic layer.
In the hydrophilic layer film formed after coating, the particles
Exist uniformly dispersed without agglomeration. this child
As a result, the effects of the present invention are further improved. (1) single resin fine particles, or
In the fine particles having a composite structure as in (2) and (3),
The resin component exhibiting hydrophilicity includes the following hydrophilic components in the polymer component:
Bond directly to the polymer main chain or in the side chain
It is contained in the substituent component. As the hydrophilic group, -OH group, -COOH
Group, -SH group, -SO_ThreeH group, -PO_ThreeH₂Group, -OPO_Three
H group, -P (= O) (OH) (R⁰¹) Group, -OP (= O) (OH)
(R⁰¹) Group, -N (R⁰¹) CO (R⁰¹) Group, -N (R⁰¹) SO
₂(R⁰¹) Group, -CON (R⁰²) (R⁰³) Group, -SO₂N (R⁰²)
(R⁰³) Group, -SO₂NHSO₂(R⁰¹) Group, -N (R⁰²) (R
⁰³) Groups, 5-6 membered compounds containing at least one nitrogen atom
Forms a condensed ring structure with a heterocyclic group or a 5- to 6-membered heterocyclic ring
And heterocyclic groups and cationic groups. These hydrophilic
One or more sex groups are contained in the repeating unit constituting the group.
May be included. The hydrophilic resin is a copolymer.
In some cases, it may contain more than one copolymer component.
Yes. Here, the substituent (R⁰¹) May be substituted
C1-C12 aliphatic group or ring member which may be substituted
Represents an aryl group of formula 6-14. (R⁰²) And (R⁰³)
Each may be the same or different, hydrogen atom,
Good C1-C18 aliphatic group, carbon that may be substituted
Represents an aryl group of formula 6-14. (R⁰²) And (R^{0 Three})
And may form a ring, in which case (R⁰²) And (R⁰³)
Represents an atomic group forming a ring. Substituent (R⁰¹) Aliphatic group having 1 to 12 carbon atoms
As a straight or branched chain having 1 to 12 carbon atoms.
Alkyl group (for example, methyl group, ethyl group, propyl group,
Butyl, pentyl, hexyl, heptyl, oct
Til, nonyl, decyl, undecyl, dodecyl
Group, etc.), C2-C12 linear or branched al
Kenyl group (eg, vinyl group, propenyl group, butenyl
Group, pentenyl group, hexenyl group, octenyl group,
Nyl group, dodecenyl group, etc.), straight chain having 2 to 12 carbon atoms
Or branched alkynyl groups (e.g., ethynyl groups, prop
Lopinyl, butynyl, pentynyl, hexynyl
Group, octynyl group, decynyl group, dodecynyl group, etc.), charcoal
An alicyclic group having a prime number of 5 to 10 (for example, a cyclopentyl group,
Cyclohexyl, cyclooctyl, cyclodecyl
Group, cyclohexenyl group, cyclooctenyl group, trisyl group
Clodecyl group, tricyclodecenyl group, isobornyl
Group, adamantyl group, etc.). Substituent (R⁰²) Aliphatic group having 1 to 18 carbon atoms
As a straight-chain or branched chain having 1 to 18 carbon atoms.
Alkyl group (for example, methyl group, ethyl group, propyl group,
Butyl, pentyl, hexyl, heptyl, oct
Til, nonyl, decyl, undecyl, dodecyl
Group, tridecyl group, tetradecyl group, hexadecyl group,
Octadecyl group, etc.), straight chain having 2 to 18 carbon atoms or
Branched alkenyl groups (eg vinyl groups, propenyls)
Group, butenyl group, pentenyl group, hexenyl group, octet
Nyl, decenyl, dodecenyl, tetradecenyl
Group, hexadecenyl group, octadecenyl group, etc.), carbon number
2-18 linear or branched alkynyl groups (eg
For example, ethynyl group, propynyl group, butynyl group, pentini group
Group, hexynyl group, octynyl group, decynyl group, dodeyl group
Sinyl group, octadecynyl group, etc.), C5-C10 fat
Cyclic groups (eg, cyclopentyl, cyclohexyl)
Group, cyclooctyl group, cyclodecyl group, cyclohexe
Nyl, cyclooctenyl, tricyclodecyl,
Licyclodecenyl group, isobornyl group, adamantyl group
Etc.). Substituent (R⁰¹) ~ (R⁰³) Having 6 to 14 carbon atoms
Examples of the aryl group include a phenyl group and naphthyl.
Group, dihydronaphthyl group, tetranyl group, indenyl
Group, indanyl group, benzocyclobutenyl group, benzosi
Examples include a chloroheptenyl group and an anthranyl group. These hydrocarbon groups may be substituted.
Examples of the substituent include those exemplified as the hydrophilic group.
Group, cyano group, halogen atom (fluorine atom, chlorine atom,
Bromine atom, iodine atom), -OR⁰⁴Group, -SR⁰⁴Group,-
COOR⁰⁴Group, -OCOR⁰⁴Group, -SO₂R⁰⁴Group, -C
OR⁰⁴Group, -NHCONHR⁰⁴Group, -Si (R⁰⁵)
(R⁰⁶) (R⁰⁷) Group, alkyl group, alkenyl group, alkini
Group, alicyclic group, aryl group, heterocyclic group, etc.
The It should be noted that the substituent (R⁰⁴) ~ (R⁰⁷)
(R⁰¹) Represents the same content. Alkyl group, alkenyl
As the group, alkynyl group, alicyclic group, and aryl group,
(R ⁰¹) Having the same contents as each substituent. As the heterocyclic group, an oxygen atom, a sulfur atom,
Contains at least one atom selected from nitrogen atoms
5-membered or 6-membered heterocyclic groups, and these heterocyclic groups
Examples thereof include a heterocyclic group having a polycyclic structure. these
The heterocyclic group may have a substituent, and as a substituent
Is the same as the substituent which can be substituted for the hydrocarbon group.
Is mentioned. As specific examples of the heterocyclic group, for example,
Tetrahydrofuran, dihydrofuran, pyrrole, pyro
Phosphorus, pyrrolidine, pyrazole, pyrazoline, pyrazoli
Gin, imidazole, imidazoline, imidazolidine,
Triazole, triazoline, triazolidine, tetra
Sol, tetrazoline, tetrazolidine, thiophene,
Dihydrothiophene, Tetrahydrothiophene, Isoo
Xazole, isoxazoline, isoxazolidine,
Oxazole, oxazoline, oxazolidine, isothi
Azole, isothiazoline, isothiazolidine, thiazo
, Thiazoline, thiazolidine, pyridine, hydropyr
Lysine, piperidine, pyridazine, hydropyridazine,
Pyrimidine, pyrazine, piperazine, pyran, hydropi
Orchid, thiopyran, hydrothiopyran, oxazine,
Ruphorin, azepine, hydroazepine, azocine, aze
Syn, diazepine, diazocine, hydrodiazocine, di
Azonin, diazecin, Oxepin, hydrooxepin, oxosi
, Oxonine, oxesin, thiepine, thiocin,
Dorithiocin, thionine, thiecin, dithiepine, dithi
Osin, dithionine, dithiecin, oxazepine, thia
Zepin, oxathiepine, hydrooxathiepin, o
Xathiocin, hydrooxathiocin, isoindo
, Indoline, indole, isoindoline, carba
Sol, indazole, benzimidazole, hydrobe
Nzoimidazole, benzotriazole, isobenzof
Orchid, dibenzofuran, hydrobenzofuran, benzoo
Xazole, benzothiophene, benzodithiol,
Drobenzoxazole, benzoisoxazole,
Nzothiazole, benzoisothiazole, benzoxa
Thiol, quinoline, isoquinoline, acridine, phen
Nanthridine, quinazoline, phenazine, benzopyra
, Xanthene, benzothiopyran, hydrobenzopyra
, Benzoxazine, benzothiazine, thioxanthate
Phenoxazine, phenothiazine, benzoazepi
, Benzodiazepine, pyrrolidine, quinolidine, quino
Lydidine, indolizine, pyrrolizidine, purine, iso
Chroman, chroman, bipyridine, bithiophene, quinu
Heterocycles derived from heterocycles such as klysine and piperazine
Groups. The cationic group as the hydrophilic group is onium.
A group forming a salt, wherein -N⁺(R⁰⁸)_Three, -S
⁺(R⁰⁹)₂, -J⁺(R⁰⁹), -P⁺(R⁰⁹)_ThreeIs mentioned
The Here, the substituent (R⁰⁸) Is a hydrogen atom, carbonized
Represents a hydrogen group or a heterocyclic group, and the three to be substituted are the same
May be different. Substituent (R⁰⁹) Is a hydrocarbon group or
Represents a heterocyclic group, the same when 2 or 3 are substituted
But it can be different. Substituent (R⁰⁸) ~ (R⁰⁹) With hydrocarbon groups
Thus, preferably, it may be substituted with 1 to 12 carbon atoms.
Straight or branched alkyl groups {eg methyl
Group, ethyl group, propyl group, butyl group, pentyl group,
Xyl, heptyl, octyl, nonyl, decyl
Groups, dodecyl groups, etc .; groups that can be substituted with these groups
Is a halogen atom (chlorine atom, fluorine atom, bromine atom
Child), hydroxy group, thiol group, carboxy group, sulfur
E group, cyano group, epoxy group, -OR 'group (R' is carbon
Hydride group, for example, methyl group, ethyl group, propyl group,
Butyl, hexyl, heptyl, octyl, dec
Group, propenyl group, butenyl group, hexenyl group, octyl group
Tenenyl group, 2-hydroxyethyl group, 3-chloropropylene
Group, 2-cyanoethyl group, N, N-dimethylamino group
Til group, 2-bromoethyl group, 2- (2-methoxyethyl)
E) Oxyethyl group, 2-methoxycarbonylethyl
Group, 3-carboxypropyl group, benzyl group, etc.
-OCOR 'group, -COOR' group, -COR '
The group -N (R ") (R") (R "is a hydrogen atom or
Represents the same content as R ', each may be the same or different
-NHCONHR 'group, -NHCOOR' group,-
Si (R ')_ThreeGroup, —CONHR ″ group, —NHCOR ′
Groups and the like. These substituents are duplicated in the alkyl group.
Number may be substituted)}, C 2-12 straight chain which may be substituted
Or a branched alkenyl group (eg, vinyl group, propylene group)
Nyl, butenyl, pentenyl, hexenyl,
Octenyl, decenyl, dodecenyl, etc.
The group substituted with the above is substituted with the above alkyl group
The same content as the group, or multiple substitutions
Or an optionally substituted aralkyl having 7 to 14 carbon atoms.
Kill group (for example, benzyl group, phenethyl group, 3-phen
Nylpropyl, naphthylmethyl, 2-naphthylethyl
A group substituted by these groups includes the above-mentioned al
And the same content as the group substituted with the kill group,
More than one may be substituted), C5-C10 optionally substituted alicyclic
Group (for example, cyclopentyl group, cyclohexyl group, 2
-Cyclohexylethyl group, 2-cyclopentylethyl
Group, norbornyl group, adamantyl group, etc.
The group to be substituted is the same as the substituent of the alkyl group.
Content may be included, or multiple substitutions may be made) C6-C12 optionally substituted aryl
Group (for example, phenyl group, naphthyl group, as substituent)
Has the same content as the group substituted with the alkyl group.
And a plurality of them may be substituted). Substituent (R⁰⁸) ~ (R⁰⁹) As a heterocyclic group
Is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
A condensed ring containing at least one atom selected from
Good heterocyclic groups (for example, heterocyclic rings include pyran ring,
Ring, thiophene ring, morpholine ring, pyrrole ring, thia
Zole ring, oxazole ring, pyridine ring, piperidine
Ring, pyrrolidone ring, benzothiazole ring, benzoxa
Sol ring, quinoline ring, tetrahydrofuran ring, etc.
It may contain a substituent. As the substituent, the alkyl
Examples of the same content as the substituent in the group
May be replaced). Next, in the lipophilic part of the self-water-dispersed resin fine particles,
explain about. As a resin containing a lipophilic part, water
Insoluble in the glass transition point of the resin at 50 ° C to 180 ° C.
Any can be used. Specifically, the heat
Same as exemplified for plastic resin fine particles and thermosetting resin fine particles
Can be mentioned. Preferably, (meth) acrylate resin,
Styrene resin, vinyl ester resin, epoxy resin, resin
Resin resin, phenol resin, vinyl ether resin, vinyl resin
Nilketone resin, olefin resin, substituted (meth) acrylic
Luamide copolymer resin and the like. Monomer corresponding to the polymer component of each of these resins
As a specific example of the body, for example, JP 2001-47755 A
Example of paragraph numbers [0086] to [0090]
The compounds shown are mentioned. The same resin contains a hydrophilic component and a lipophilic component.
The self-water-dispersible hydrophobic resin contains a hydrophilic group-containing monomer and
Synthesize a lipophilic monomer with a polymerization reaction or
A hydrophilic group is introduced into an oil-based resin by a conventionally known polymer reaction.
The method of entering. As the polymer reaction, Koji Tsuruta (ed.) “High
Molecular Functional Materials Series II, Polymer Synthesis and Reaction
(2) ”Chapter 7, Kyoritsu Publishing Co., Ltd. (1991)
The methods described in the review can be used. Lipophilic in the raw resin molecule used in the phase inversion emulsification method
In some cases, the polymerizable resin portion may be the above polymerizable monomer.
Copolymers of monomers and polymerizable unsaturated group-containing oligomers
There may be. Such polymerizable unsaturated group-containing oligomers
For example, vinyl-modified polyester, vinyl
Modified polyurethane, vinyl modified epoxy resin, vinyl modified
Can be mentioned. Vinyl base
In the case of the polymer reaction, the method described in the above-mentioned book is used.
The These monomers and polymerizable unsaturated groups are contained.
At least one selected from oligomers and the hydrophilic group
By phase inversion emulsification method.
A raw material resin of self-water dispersible resin fine particles is obtained. this
The raw material resin has a weight average molecular weight of 500 to 500,000,
The number average molecular weight is preferably 200-60000
Yes. Further, the heat-reactive sensor having the same contents as described above.
It can also have groups. In addition to the above, the self component used in the present invention
As the dispersible resin fine particles, urethane resin, for example,
Urethane resin die disclosed in Japanese Patent Laid-Open No. 1-287183
It is a sparging or epoxy resin, for example,
Sho 53-1228, 55-3481 or 55-
Various epoxy compounds as described in No. 9433
Can be mentioned. Further, the above-mentioned hydrophobic organic low in the fine particles.
Molecular compounds can also be accommodated. Hydrophobic organic compounds
Encapsulation in resin fine particles is hydrophobic during the synthesis of resin fine particles.
Phase-inversion emulsification by adding it in an organic solvent in which a functionalized resin is dissolved
Can be done. Self-dispersible hydrophobized resin fine particles as described above
The solidification temperature is preferably 70 ° C or higher, but the stability over time
Considering 100 ° C. or higher is more preferable. Self of core-shell structure used in the present invention
Water-dispersible resin fine particles are emulsified (including phase inversion emulsification) or separated.
Hydrophobic heavy that softens or melts under the action of heat obtained by dispersion polymerization
A hydrophilic polymer around the fine particles of coalescence
Core-shell type composite fine particles with polymer layers
Is a different phase structure fine particle, simply called core-shell type fine particle.
The The polymerized layer of hydrophilic polymer forms the core particle (sheet
Of the core particles by adding a hydrophilic monomer to the dispersion of
This is carried out by polymerizing a hydrophilic monomer on the surface. The lipophilic resin part constituting the core part is
At least one selected from thermoplastic resins and thermosetting resins
It consists of two resins. The hydrophilic resin forming the shell phase is
At least one hydrophilic group selected from the above-mentioned hydrophilic groups
In addition to resins having silica, silica fine particles and alumina fine particles
A sol-like fine particle dispersion with extremely high hydrophilicity
Agglomerated and adhered to the surface of fine particles, or sol-gel conversion product
Formed by quality (for example, (semi) metal-containing resin described later)
It may be a hydrophilic gel. In addition, for example, JP-A-5-9431
Various epoxy resins with a core-shell structure as described in
Is also suitable as the self-water dispersible resin fine particles of the present invention. Self-water dispersible resin having the above core-shell structure
Even in the case of fine particles, the resin fine particles by phase inversion emulsification described above
In the same way as above, a hydrophilic compound is adsorbed on the resin surface,
A hydrophobic organic compound can be encapsulated in the resin.
Suitable compounds for adsorption or encapsulation include phase inversion emulsification.
And the same compounds as described in the resin fine particles. Average of hydrophobized resin fine particles used in the present invention
The particle size is preferably 0.01 to 20 μm, but among them
0.05 to 2.0 μm is more preferable, in particular 0.1 to
1.0 μm is optimal. Within this range, good resolution and
Longevity stability is obtained. Microcapsule fine particles (hereinafter simply referred to as My
Is called hydrophobic capsule)
Small organic molecules mentioned in the section on single-component hydrophobized precursors
It may be a compound, but it must be a compound having a thermally reactive group.
And the microcapsule via the thermally reactive group
A structure that can react with each other may be used, or in the image forming layer
As other additives, hydrophilic resins or low-molecular compounds described later are used.
If contained, the structure can react with them.
Yes. In addition, two or more types of microcapsules can be thermally reacted with each other.
Each with a reactive thermoreactive group.
It is also good as a structure that allows reaction between the pursels
Yes. The microcapsule of the present invention has a thermally reactive group.
It has a structure in which the compound is encapsulated in a microcapsule
Or, it is a structure that is contained in the outer wall of the microcapsule.
At the same time as encapsulating in microcapsules
The structure may be included in the outer wall of the black capsule. As such a thermally reactive group, a polymerization reaction is carried out.
Ethylenically unsaturated groups (eg acryloyl groups, meta
Acryloyl group, vinyl group, allyl group, etc.)
Isocyanate group to be performed or block body thereof and
A functional group having an active hydrogen atom as a reaction partner (for example,
Amino group, hydroxy group, carboxy group, etc.)
Epoxy group for the addition reaction and its reaction partner amino
Group, carboxy group or hydroxy group, condensation reaction
Carboxy group and hydroxy group or amino group, ring-opening addition reaction
Acid anhydride and amino group or hydroxy group, thermal decomposition
And diazonium groups that react with hydroxy groups, etc.
Can be mentioned. However, no chemical bond is formed
Any functional group capable of performing any reaction may be used. Examples of the compound having a thermally reactive group include
Ethylenically unsaturated group described in 2001-293971
Compound (polymerizable monomer, prepolymer, oligomer)
Compounds well known as, for example, trimethylo
Lepropane diacrylate, trimethylol proppant
Triacrylate of reacrylate and pentaerythritol
Of salt, tetraacrylate, dipentaerythritol
Diacrylate, pentaacrylate, etc. and allyl on the side chain
Group-containing polymers such as allyl methacrylate and polymers
Copolymer of alkyl methacrylate), epoxy compound,
Isocyanate compounds, amines, alcohol and pheno
Carboxylic acids and acid anhydrides, JP 2001-30
The heat-reactive group described in No. 5723 is protected,
Compounds that are deprotected by solution (eg phenol bromide)
Tolylene diisocyanate, etc.), JP 2002-0
No. 02135 and Japanese Patent Application Laid-Open No. 2002-046361
Epoxy resin (for example, manufactured by Yuka Shell Epoxy Co., Ltd.)
Epicoat 1001, Epicoat 1003, Epicor
Epoxy resin such as G1004, Nobola made by Sumitomo Chemical Co., Ltd.
Epoxy resin, Methacrylic acid / Glymethacrylic acid
Pheno such as zirc copolymer) and thermosetting novolac resin
Resin, JP-A-2002-029162, and JP-A-200
The compound having a vinyloxy group described in No. 2-036745
Examples include compounds and polymers. Preferred microcaps used in the present invention
Cell wall material is polyurea, polyurethane, polyester
, Polycarbonate, polyamide, and mixtures thereof
In particular, polyurea and polyurethane are preferred.
Good. On the outer wall of the microcapsule, as described above,
A compound having a thermally reactive group may be introduced. As a compound containing a compound having a thermally reactive group
As a method of microencapsulation, for example, JP-A-2
Paragraph No. [003 in the specification of 001-293971
6] is appropriately selected from the various methods cited in
You can. However, it is not limited. The microcapsules of the present invention are disclosed in JP-A-200.
Like a microcapsule described in 1-272740
The outer wall may be broken by heat used for image formation.
Of the microcapsules described in 2001-277742
As can be seen, the outer wall cannot be broken by the heat used for image formation.
Yes. In the case of microcapsules where the outer wall is not broken by heat,
As described in Kai 2001-277742, the outer wall is
Dimensionally cross-linked and the outer wall is swollen with microcapsule dispersion solvent
By adding the solvent to be removed.
It is used in the wall or on the microcapsule surface. The hydrophilic binder polymer of the present invention contains gold
Metal atoms and / or metalloid atoms are connected via oxygen atoms
(Hereinafter referred to as “(semi) metal-containing resin”)
And a hydrophilic organic polymer)
It is. (Semi) metal-containing tree as hydrophilic organic polymer
Hydrophilic organic polymer having groups capable of forming hydrogen bonds with fats
-(A) and a silane at the terminal represented by the following general formula (I)
Hydrophilic organic polymer (B) having a coupling group
I can get lost. Of these, the hydrophilic organic polymer (B) is particularly preferred.
Good. [0089] [Chemical 2] [In the general formula (I), R¹¹, R¹², R¹³as well as
R¹⁴Are independently hydrogen atoms or carbon atoms of 1 to 8 carbon atoms.
Represents a hydrogen group, m represents 0, 1 or 2, and n represents 1 to 8
Represents an integer. L represents a single bond or an organic linking group, and W represents −
NHCOR¹⁵, -CONH₂, -CON (R¹⁵)₂, -C
OR¹⁵, -OH, -CO₂M or -SO_ThreeM represents here
And R¹⁵Represents an alkyl group having 1 to 8 carbon atoms, M is hydrogen
Atom, alkali metal, alkaline earth metal or onium
Represent. ] "(Semi) metal-containing resin and hydrophilic organic polymer"
"Composite with-" includes sol-like substances and gel-like substances
Use for meaning. (Semi) metal-containing resin is "oxygen atom-metal
Mainly bonds consisting of `` atom or metalloid atom-oxygen atom ''
Represents the polymer contained. Where (semi) metal-containing trees
Even if fat contains both metal atoms and metalloid atoms
Good. Preferably, a resin containing only metalloid atoms, semi-metal
It is a resin containing metal atoms and metal atoms. The (semi) metal-containing resin has the following general formula (II)
Obtained by hydrolysis polycondensation of the compound represented by
Preferably it is a remer. Where hydrolysis polycondensation
Means that the reactive group is hydrolyzed under acidic or basic conditions.
It is a reaction that repeats decomposition and condensation and polymerizes. [0093] Formula (II) (R²⁰)_kM⁰(Y)_Zk [In the general formula (II), R²⁰Is a hydrogen atom, carbonized
Represents a hydrogen group or a heterocyclic group, Y represents a reactive group, M⁰
Represents a trivalent to hexavalent metal or metalloid, and z represents M⁰The valence of
And k represents 0, 1, 2, 3, or 4. However, z-
k is 2 or more. ] The above compounds may be used alone or in combination of two or more.
It is used for the production of (semi) metal-containing resins. The (semi) metal represented by the general formula (II)
The compound will be described in detail. R in general formula (II)²⁰
Preferred hydrocarbon groups and heterocyclic groups of
Convertible group (R⁰⁸). The reactive group Y is preferably hydroxy
Group, halogen atom (fluorine atom, chlorine atom, bromine atom or
Represents an iodine atom), -OR^{twenty one}Group, -OCOR^{twenty two}Group,
-CH (COR^{twenty three}) (COR^{twenty four}) Group, —CH (COR^{twenty three})
(COOR^{twenty four}) Group or -N (R^{twenty five}) (R²⁶) Represents a group. -OR^{twenty one}In the group R^{twenty one}Is C1-C1
0 aliphatic group which may be substituted (for example, methyl group, eth
Til, propyl, butyl, pentyl, hexyl
Group, heptyl group, octyl group, nonyl group, decyl group,
Lopenyl, butenyl, heptenyl, hexenyl
Group, octenyl group, decenyl group, 2-hydroxyethyl
Group, 2-hydroxypropyl group, 2-methoxyethyl
Group, 2- (methoxyethyloxy) ethyl group, 2-
(N, N-diethylamino) ethyl group, 2-methoxy group
Lopyl group, 2-cyanoethyl group, 3-methyloxypro
Pyr group, 2-chloroethyl group, cyclohexyl group, cycl
Lopentyl, cyclooctyl, chlorocyclohexyl
Group, methoxycyclohexyl group, benzyl group, phene
Til, dimethoxybenzyl, methylbenzyl, butyl
A lomobenzyl group, etc.). -OCOR^{twenty two}In the group R^{twenty two}Is R^{twenty one}When
The same aliphatic group or 6 to 12 carbon atoms may be substituted
An aromatic group (the aromatic group includes R²⁰Aryl group in
And the same as those exemplified in the above. -CH (COR^{twenty three}) (COR^{twenty four}) Group and -C
H (COR^{twenty three}) (COOR^{twenty four}) In the group R^{twenty three}Is carbon number
1-4 alkyl groups (eg, methyl, ethyl,
Propyl, butyl, etc.) or aryl groups (eg
Nyl group, tolyl group, xylyl group, etc.), R^{twenty four}Is carbon
A number 1-6 alkyl group (for example, a methyl group, an ethyl group,
Propyl group, butyl group, pentyl group, hexyl group, etc.),
Aralkyl group having 7 to 12 carbon atoms (for example, benzyl group,
Phenethyl group, phenylpropyl group, methylbenzyl
Group, methoxybenzyl group, carboxybenzyl group, black
Robenzyl group etc.) or aryl group (eg phenyl
Group, tolyl group, xylyl group, mesityl group, methoxyphene
Nyl, chlorophenyl, carboxyphenyl, di
Represents an ethoxyphenyl group or the like. In addition, -N (R^{twenty five}) (R²⁶R)
^{twenty five}And R²⁶May be the same or different from each other,
Preferably a hydrogen atom or a C1-C10 substituent
A good aliphatic group (eg -OR^{twenty one}R of group^{twenty one}the same as
Of the contents of). More preferably,
R^{twenty five}And R²⁶The total number of carbon atoms is 12 or less. (Semi) metal M⁰Preferably transition gold
Genus, rare earth metals, metals of group III-V of the periodic table
The More preferably, Al, Si, Sn, Ge, Ti, Z
r and the like, more preferably Al, Si, Sn, T
i, Zr and the like. Si is particularly preferable. (Semi) metal compound represented by the general formula (II)
Specific examples of the following include the following:
It is not limited. Methyltrichlorosilane, methyltribro
Musilane, methyltrimethoxysilane, methyltrieth
Xysilane, methyltriisopropoxysilane, methyl
Tri-t-butoxysilane, ethyltrichlorosilane,
Tiltribromsilane, ethyltrimethoxysilane,
Tiltlyethoxysilane, Ethyltriisopropoxy
Lan, ethyltri-t-butoxysilane, n-propylto
Lichlorosilane, n-propyltribromosilane, n-
Propyltrimethoxysilane, n-propyltriethoxy
Sisilane, n-propyltriisopropoxysilane, n
-Propyltri-t-butoxysilane, n-hexyltri
Chlorosilane, n-hexyltribromosilane, n-he
Xyltrimethoxysilane, n-hexyltriethoxy
Silane, n-hexyltriisopropoxysilane, n-
Hexyltri-t-butoxysilane, n-decyltrichloro
Rusilane, n-decyltribromosilane, n-decylto
Limethoxysilane, n-decyltriethoxysilane, n
-Decyltriisopropoxysilane, n-decyltri-t
-Butoxysilane, n-octadecyltrichlorosila
N-octadecyltribromosilane, n-octade
Siltrimethoxysilane, n-octadecyltriethoxy
Sisilane, n-octadecyltriisopropoxysila
N-octadecyltri-t-butoxysilane, phenyl
Lutrichlorosilane, phenyltribromosilane,
Nyltrimethoxysilane, phenyltriethoxysila
, Phenyltriisopropoxysilane, phenyltri
t-butoxysilane, Tetrachlorosilane, tetrabromosila
Tetramethoxysilane, Tetraethoxysilane, Te
Trisopropoxysilane, tetrabutoxysilane, di
Methoxydiethoxysilane, dimethyldichlorosilane,
Dimethyldibromosilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diphenyldichlorosila
, Diphenyldibromosilane, diphenyldimethoxy
Silane, diphenyldiethoxysilane, phenylmethyl
Dichlorosilane, phenylmethyldibromosilane, phenoxy
Nylmethyldimethoxysilane, phenylmethyldiethoxy
Sisilane, triethoxyhydrosilane, tribromohydride
Rosilane, trimethoxyhydrosilane, isopropoxy
Hydrosilane, tri-t-butoxyhydrosilane, vinyl
Trichlorosilane, vinyltribromosilane, vinylto
Limethoxysilane, vinyltriethoxysilane, vinyl
Triisopropoxysilane, vinyl tri-t-butoxy
Lan, trifluoropropyltrichlorosilane, trif
Fluoropropyltribromosilane, trifluoropropiyl
Rutrimethoxysilane, trifluoropropyltrieth
Xysilane, trifluoropropyltriisopropoxy
Silane, trifluoropropyltri-t-butoxysila
, Γ-Glycidoxypropylmethyl dimethoxy
Sisilane, γ-glycidoxypropylmethyldiethoxy
Silane, γ-glycidoxypropyltrimethoxysila
Γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyl triisopropoxysilane, γ
-Glycidoxypropyltri-t-butoxysilane, γ-
Methacryloxypropylmethyldimethoxysilane, γ
-Methacryloxypropylmethyldiethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ
-Methacryloxypropyl triisopropoxysila
Γ-methacryloxypropyltri-t-butoxy
Lan, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, γ-amino
Propyltrimethoxysilane, γ-aminopropyltri
Ethoxysilane, γ-aminopropyltriisopropoxy
Sisilane, γ-aminopropyltri-t-butoxysila
Γ-mercaptopropylmethyldimethoxysilane,
γ-mercaptopropylmethyldiethoxysilane, γ-
Mercaptopropyltrimethoxysilane, γ-mercap
Topropyltriethoxysilane, γ-mercaptopropi
Lutriisopropoxysilane, γ-mercaptopropyl
Tri-t-butoxine run, β- (3,4-epoxy
Rohexyl) ethyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltriethoxysila
, Ti (OR)_Four(Where R is an alkyl group
(For example, methyl group, ethyl group, propyl group, butyl
Group, pentyl group, hexyl group, etc.)), TiC
l_Four, Zn (OR)₂, Zn (CH_ThreeCOCHCOC
H_Three)₂, Sn (OR)_Four, Sn (CH_ThreeCOCHCOCH_Three)
_Four, Sn (OCOR)_Four, SnCl_Four, Zr (OR)_Four, Zr
(CH_ThreeCOCHCOCH_Three)_Four, Al (OR)_Three, Al
(CH_ThreeCOCHCOCH_Three)_Three. Next, the (semi) metal-containing resin and composite are mixed.
The hydrophilic organic polymer to be formed will be described. The hydrophilic organic polymer (A) of the present invention is
A group capable of forming a hydrogen bond with a (semi) metal-containing resin (hereinafter,
Also referred to as a specific linking group). With this particular linking group
Preferably, an amide bond (carboxylic acid amide bond) is used.
And sulfonamide bonds), urethane bonds and
At least one bond selected from ureido bonds and water
An acid group can be mentioned. As useful hydrophilic organic polymers (A),
At least one specific linking group as described above, repeating unit component
Contained in the main chain and / or side chain of polymer
Can be mentioned. Preferably, the repeating unit component
-N (R⁰) CO-, -N (R⁰) SO₂-,-
At least selected from NHCONH- and -NHCOO-
1 type of bond is present in the main chain and / or side chain of the polymer
And / or components containing —OH groups
It is. The polymer main chain contains the specific linking group of the present invention.
The polymer having -N (R ⁰CO) bond or
-N (R⁰) SO₂-Amide resin having a bond, -NHC
Ureido resin having ONH-bond, -NHCOO-bond
And urethane resin containing a combination. During the amide bond or sulfonamide bond
R⁰Represents a hydrogen atom or an organic residue,
R in the general formula (II)²⁰Hydrocarbon groups and compounds in
The thing of the same content as a unicyclic group is mentioned. Diamines and dimers used for the production of amide resins
Used for carboxylic acids or disulfonic acids, ureido resins
Used for diisocyanates and urethane resins
Examples of diols include “Polymer Day” edited by the Society of Polymer Science
Tahand Book -Basics- "Chapter I Publishing Co., Ltd. (1)
986), Shinzo Yamashita, Tosuke Kaneko, “Crosslinking Agent Handbook”
Compounds described in “Ku” published by Taiseisha (1981)
Can be used. Further, other polymers having an amide bond
Containing repeating units represented by the following general formula (III)
N-acylated form of polyalkyleneimine or
Includes polyvinylpyrrolidone and its derivatives. [0115] [Chemical Formula 3] In the formula (III), Z¹Is -CO-, -SO₂−
Or -CS- is represented. R³¹Is R in formula (I)¹¹Same as
Represents content. r¹Is a hydrogen atom or having 1 to 6 carbon atoms
An alkyl group (for example, a methyl group, an ethyl group, a propyl group,
Butyl group, pentyl group, hexyl group, etc.). r¹Is
It may be the same or different. p represents an integer of 2 or 3. The repeating unit represented by the general formula (III)
Among the polymers contained, Z¹Represents -CO-, and p represents
2 represents an oxa group that may have a substituent.
Obtained by ring-opening polymerization of zolin in the presence of a catalyst.
The Examples of the catalyst include dimethyl sulfate and p-tolue.
Sulfate esters such as sulfonic acid alkyl esters
Sulfonic acid esters; alkyl iodides (eg methyl iodide)
Al) Halogenated alkyl such as Friedel Crafts
Metal fluoride in the medium; sulfuric acid, hydrogen iodide, p-tolu
Acids such as enesulfonic acid, and these acids and oxazolines
Oxazolinium salts that are salts with Na
This polymer may be a homopolymer, copolymer
It may be a body. Also this polymer to other polymers
May be a grafted copolymer. As specific examples of oxazoline, for example,
2-oxazoline, 2-methyl-2-oxazoline, 2
-Ethyl-2-oxazoline, 2-propyl-2-oxy
Sazoline, 2-isopropyl-2-oxazoline, 2-
Butyl-2-oxazoline, 2-dichloromethyl-2-
Oxazoline, 2-trichloromethyl-2-oxazoly
2-pentafluoroethyl-2-oxazoline, 2
-Phenyl-2-oxazoline, 2-methoxycarboni
Ruethyl-2-oxazoline, 2- (4-methylpheny
L) -2-oxazoline, 2- (4-chlorophenyl)
-2-oxazoline and the like. Preferred oxa
Zolin includes 2-oxazoline, 2-methyl-2-oxy
Contains sazoline, 2-ethyl-2-oxazoline, etc.
The One or two such oxazoline polymers
It can be used above. The repeating unit represented by the general formula (III)
Other polymers that have oxazoline
And thiazoline, 4,5-dihydro-1,3-oxazine
Or similar with 4,5-dihydro-1,3-thiazine
Can get to. N-acylated form of polyalkylenimine and
Is obtained by polymer reaction with carboxylic acid halides.
Ru-N (CO-R³¹) -Containing carboxylic acid amide,
-N obtained by polymer reaction with sulfonyl halides
(SO₂-R³¹) -Containing sulfonamide (wherein
R³¹Is R in the above formula (III)³¹Is synonymous with
I can get lost. In addition, the specific side chain of the present invention is not attached to the side chain of the polymer.
As a polymer containing a combined group, at least one kind
Contains a component having a specific bonding group as a main component
Can be mentioned. Examples of such components include a
Kurylamide, methacrylamide, crotonamide, vinyl
Nyl acetic acid amide or the following compounds are mentioned. However,
The present invention is not limited to these. The symbols in the following structural formulas are as follows:
Represents content. a¹: -H or -CH_Three T⁰: -H, -CH_Three,-(CH₂)₂OCH_ThreeOr-(CH
₂)₂N (CH_Three)₂ L⁰: -C_xH_{2x + 1},-(CH₂)₂OCH_Three,-(CH₂)₂N
(CH_Three)₂, Benzyl or-(CH₂)_xOH L¹: -H, L⁰Or-(CH₂)₂CONH₂ x: an integer from 1 to 4 y: 0 or 1 z: 0, 1 or 2 [0123] [Formula 4] [0124] [Chemical formula 5]On the other hand, a hydrophilic organic polymer containing a hydroxyl group and
Natural water-soluble polymer, semi-synthetic water-soluble polymer, synthetic
Any polymer can be used, specifically supervised by Fujio Kotake
"Dai Organic Chemistry 19, Natural Polymer Compound I" published by Asakura Shoten
(1960), Management Development Center Publishing Department, “Highly water-soluble
"Molecular and Water Dispersible Resin Comprehensive Technical Data" Management Development Center
Published by the publisher (1981), Shinji Nagatomo “New water-soluble polymer”
-Application and Market "published by CMC Co., Ltd. (1988)
) "Development of functional cellulose" CMC Co., Ltd.
Publications (1985) and the like can be mentioned. For example, as natural and semi-synthetic polymers
Cellulose, cellulose derivatives (cellulose esthetics
Cellulose: cellulose nitrate, cellulose sulfate, cellulose acetate
, Cellulose propionate, cellulose succinate, dairy
Acid cellulose, cellulose acetate succinate, acetic acid butyrate cell
Loose, cellulose acetate phthalate, etc., cellulose ether
Methyl cellulose, ethyl cellulose, cyanoe
Chill cellulose, carboxymethyl cellulose, hydro
Xylethylcellulose, hydroxypropyl cellulose
, Ethyl hydroxyethyl cellulose, hydroxy
Lopylmethylcellulose, carboxymethylhydroxy
Ethyl cellulose), starch, starch derivatives (acids)
Starch, esterified starch; nitric acid, sulfuric acid, phosphorus
Esters such as acid, acetic acid, propionic acid, butyric acid, succinic acid
, Etherified starches; methylated, ethylated,
Anoethylation, hydroxyalkylation, carboxymethyl
Derivatives), alginic acid, pectin, carragina
Gum, tamarind gum, natural gums (gum arabic, gua
-Gum, locust bean gum, tragagant gum, ki
Santangham etc.), pullulan, dextran, casei
And gelatin, chitin, chitosan and the like. Examples of synthetic polymers include polyvinyl polymers.
Lucol, polyalkylene glycol (polyethylene glycol)
Recall, polypropylene glycol, (ethylene glycol
Coal / propylene glycol) copolymers), allyl
Alcohol copolymers, polymers containing at least one hydroxyl group
Polymerization of crylate or methacrylate
Body or copolymer (as ester substituent, for example 2
-Hydroxyethyl group, 3-hydroxypropyl group,
2,3-dihydroxypropyl group, 3-hydroxy-2
-Hydroxymethyl-2-methylpropyl group, 3-hydride
Loxy-2,2-di (hydroxymethyl) propyl group,
Polyoxyethylene group, polyoxypropylene group,
Etc.), acrylamide containing at least one hydroxyl group
Or an N-substituted polymer or copolymer of methacrylamide
Polymer (as N-substituent, for example, monomethylol
Group, 2-hydroxyethyl group, 3-hydroxypropyl
Group, 1,1-bis (hydroxymethyl) ethyl group, 2,
3,4,5,6-pentahydroxypentyl group, etc.)
Is mentioned. However, as a synthetic polymer, repeated simple
Contains at least one hydroxyl group in the side chain substituent at the position
If it is a thing, it will not specifically limit. Hydrophilic organic polymers having the above specific binding groups
The weight average molecular weight of the remer (A) is preferably 10^Three~
10⁶, More preferably 10^Three~ 4x10^FiveIt is. Next, the powder represented by the general formula (I) of the present invention is used.
Hydrophilic organic polymer having a silane coupling group at the end
(B) will be described. This organic polymer (B)
Japanese Patent Application No. 2001-175952 including synthesis method in detail
Has been described. In the general formula (I), R¹¹, R¹²,
R¹³And R¹⁴Each independently represents a hydrogen atom or 8 carbon atoms.
The following hydrocarbon groups are represented. Hydrocarbon groups include alkyl
Group, aryl group, etc.
The lower linear, branched or cyclic alkyl groups are preferred. This
These hydrocarbon groups may further have a substituent. Ingredients
Physically, methyl group, ethyl group, propyl group, butyl
Group, pentyl group, hexyl group, heptyl group, octyl
Group, isopropyl group, isobutyl group, s-butyl group, t
-Butyl group, isopentyl group, neopentyl group, 1-
Tylbutyl group, isohexyl group, 2-ethylhexyl
Group, 2-methylhexyl group, cyclopentyl group, etc.
It is done. R¹¹, R¹², R¹³And R¹⁴The effect and availability
From the viewpoint of easiness, preferably a hydrogen atom and methyl, respectively
Group or ethyl group. L represents a single bond or an organic linking group. here
And when L represents an organic linking group, L is not a non-metallic atom.
A polyvalent linking group, specifically 1 to 60
Carbon atom, 0 to 10 nitrogen atoms, 0 or
Up to 50 oxygen atoms, 1 to 100 hydrogen atoms
Consists of atoms and 0 to 20 sulfur atoms
Is. More specific linking groups include the following structural units:
List the ranks or combinations of these
You can. [0132] [Chemical 6] W is -NHCOR.¹⁵, -CON
H₂, -CON (R¹⁵)₂, -COR¹⁵, -OH, -CO
₂M or -SO_ThreeM, where R¹⁵1 to 1 carbon atoms
8 represents a linear, branched or cyclic alkyl group. Also,
-CON (R¹⁵)₂Multiple R¹⁵If you have
R¹⁵May be the same or different and R¹⁵Ties together
May be combined to form a ring, and the formed ring is
Contains heteroatoms such as oxygen, sulfur and nitrogen
It may be a heterocyclic ring. R¹⁵Has further substituents
As the substituent that can be introduced here,
R¹¹, R¹², R¹³And R ¹⁴Can be introduced when is an alkyl group
Can be mentioned as well
The R¹⁵Specifically, methyl group, eth
Til, propyl, butyl, pentyl, hexyl
Group, heptyl group, octyl group, isopropyl group, isobutyl group
Tyl group, s-butyl group, t-butyl group, isopentyl
Group, neopentyl group, 1-methylbutyl group, isohexyl
Group, 2-ethylhexyl group, 2-methylhexyl group,
Preferred examples include a cyclopentyl group. Specific examples of W are more preferable.
As: -NHCOCH_Three, -CONH₂, -COO
H, -SO_Three ^-NMe_Four ⁺And a morpholino group. M is a hydrogen atom; lithium,
Alkali metals such as sodium and potassium; calcium,
Alkaline earth metals such as barium or ammonium,
Examples include oniums such as iodonium and sulfonium.
The Hydrophilic organic polymer represented by general formula (I)
-The molecular weight of (B) is preferably the weight average molecular weight (Mw).
Or 200 to 100,000, more preferably 300 to
50000, more preferably 500-20000
The Hydrophilic organic polymer (B) suitable for the present invention
Specific examples of these are shown below, but the present invention is limited thereto.
It is not a thing. [0139] [Chemical 7](Semi) A composite of a metal-containing resin and an organic polymer
In forming a coalescence, the organic polymer may be used alone
Two or more kinds may be used in combination. Also (semi) metal
The ratio of contained resin and organic polymer can be selected within a wide range
But preferably (semi) metal-containing resin / organic polymer quality
10/90 to 90/10 by weight ratio, more preferably 20 /
80-80 / 20. In this range, the hydrophilic layer
Excellent film strength and water resistance against dampening water during printing
The Binder polymer containing the composite of the present invention
Produced by hydrolysis polycondensation of the (semi) metal compound
(Semi) metal-containing resin hydroxy group and hydrophilic organic
The specific bonding group in the polymer is due to hydrogen bonding action, etc.
To form more uniform organic / inorganic hybrid and phase separation
It becomes microscopically homogeneous without. (Semi) metal-containing resin
If a hydrocarbon group is present, it is attributed to the hydrocarbon group.
To further improve the affinity with hydrophilic organic polymers.
It is estimated that. The composite of the present invention is excellent in film formability.
ing. The composite of the present invention comprises the above (semi) metal compound.
Hydrolyzed polycondensed and mixed with hydrophilic organic polymer
Or the presence of a hydrophilic organic polymer
Below, hydrolytic polycondensation of the (semi) metal compound
More manufactured. Preferably, the presence of a hydrophilic organic polymer
In the present, the (semi) metal compound is converted into a known sol-gel method.
The organic / inorganic of the present invention by hydrolytic polycondensation
A polymer composite can be obtained. Generated organic / nothing
In the polymer composite, the hydrophilic organic polymer is
(Semi) gel produced by hydrolysis polycondensation of metal compounds
Matrix (ie inorganic (semi) metal oxide tertiary
Uniformly distributed in the original fine network structure). Furthermore, it is represented by the general formula (II).
Promotes (semi) metal compound hydrolysis and co-condensation reactions
Therefore, it is preferable to use an acidic catalyst or a basic catalyst in combination.
That's right. The catalyst is an acid or basic compound as it is.
Or dissolved in water or alcohol.
(Hereinafter referred to as acidic catalyst and basic catalyst, respectively)
U). There is no particular limitation on the concentration at that time.
However, when the concentration is high, the hydrolysis and polycondensation rates are fast.
Tend to be. However, use a concentrated basic catalyst.
Salt may form in the sol solution.
The concentration of the basic catalyst should be 1N (concentration in aqueous solution) or less.
Good. The kind of acidic catalyst or basic catalyst is particularly limited.
If you need to use a dense catalyst
Is not likely to remain in the catalyst grains after sintering.
A catalyst composed of elements is preferable. Specifically, acidic catalyst
As hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid,
Sulfuric acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, formic acid,
Carboxylic acid such as acetic acid, R of structural formula RCOOH is other element
Or substituted carboxylic acid substituted by a substituent, benzene
As a basic catalyst such as sulfonic acid such as sulfonic acid
Ammonia base such as aqueous ammonia, ethylamine
And amines such as aniline and aniline. The hydrophilic layer of the present invention comprises beryllium and magnesi.
Um, aluminum, silicon, titanium, boron, germany
Um, tin, zirconium, iron, vanadium, antimony
Of at least one element selected from
Can contain oxide or hydroxide colloids
The Of these oxides or hydroxides of these elements, particularly preferred
Preferred are aluminum, silicon, titanium and zirconium
An oxide or hydroxide of an element selected from
The The particle size of the colloid is 5 to 100 nm.
Preferably, 5 to 50 nm is more preferable. These rollers
For id dispersions, purchase commercial products such as Nissan Chemical Industries, Ltd.
You can also [0148] The colloid described above is composed of (semi) metal-containing resin
Coexisting in the production of composites with aqueous organic polymers
Added to the hydrophilic layer as a component of the hydrophilic binder preparation
You can also In addition, the hydrophilic layer has a further improved film strength.
In order to achieve this, a cross-linking agent may be added. As a crosslinking agent,
Mention may be made of compounds usually used as crosslinking agents.
The Specifically, Shinzo Yamashita, Tosuke Kaneko “Crosslinking agent hand
Book, published by Taiseisha (1981), edited by the Society of Polymer Science, Japan
Child Data Handbook, Basics "Baifukan (1986)
Etc. can be used. For example, ammonium chloride, metal ions,
Organic peroxides, polyisocyanate compounds (eg
Louisene diisocyanate, diphenylmethane diisocyanate
Anato, triphenylmethane triisocyanate, poly
Limethylene phenyl isocyanate, hexamethylene di
Isocyanate, isophorone diisocyanate, polymer
Polyisocyanates, etc.), polyol compounds (eg
1,4-butanediol, polyoxypropylene group
Recall, polyoxyethylene glycol, 1,1,1
-Trimethylolpropane, etc.), polyamine compounds
(For example, ethylenediamine, γ-hydroxypropyl
Ethylenediamine, phenylenediamine, hexamethyl
Range amine, N-aminoethylpiperazine, modified fat
Group polyamines), polyepoxy group-containing compounds and
Poxy resin (for example, “New Epoxy Resin” written by Hiroshi Kakiuchi
Tsujido (published in 1985), edited by Kuniyuki Hashimoto “Epoxy resin”
Compounds described in Nikkan Kogyo Shimbun (1969)
), Melamine resin (for example, edited by Ichiro Miwa and Hideo Matsunaga)
"Yulia Melamine Resin" Nikkan Kogyo Shimbun (1969)
Etc.), poly (meth) crelay
Compounds (for example, Nobu Okawara, Takeo Saegusa, Toshinobu Higashimura)
"Oligomer" Kodan (1976), Eizo Omori "machine"
Performance Acrylic Resin ”Techno System (published in 1985)
Etc.). In the hydrophilic layer of the present invention, light energy is converted into heat energy.
Adds photothermal conversion material for efficient conversion to energy
it can. The photothermal conversion material that can be used in the present invention is particularly limited.
There is no limit, absorbing light such as ultraviolet rays, visible rays, infrared rays, etc.
Any substance that can be converted to heat can be used. Especially preferred
What is new is that infrared rays with a wavelength of 760nm to 1200nm
Dyes, pigments or metals that absorb effectively. As a preferred dye, for example, JP-A-5
No. 8-125246, JP 59-84356, JP
Sho 60-78787, JP-A-10-268512,
Cyanine described in U.S. Pat. No. 4,973,572
Dye, JP-A-58-173696, JP-A-58-18
1690, Japanese Patent Laid-Open No. 58-194595, etc.
Methine dyes, JP 58-112793 A, JP
Sho 58-224793, JP-A 59-48187,
JP 59-73996, JP 60-52940
And naphths described in JP-A-60-63744
Toquinone dyes, described in JP-A No. 58-112792, etc.
Squarilium dyes, British Patent 434,875
Cyanine dyes described in No. In the vicinity of US Pat. No. 5,156,938
Infrared absorption sensitizer, described in US Pat. No. 3,881,924
Substituted arylbenzo (thio) pyrylium salts,
7-142645 (US Pat. No. 4,327,169)
No.), trimethine thiapyrylium salt, JP-A 58-
181051, 582-22014, 59-4
1363, 59-84248, 59-8424
No. 9, No. 59-146063, No. 59-146061
JP-A 59-
Cyanine dye described in US Pat. No. 216146, US Pat. No. 4,2
Pentamethine thiopyrylium salt described in 83,475
No. 5-13514, 5-19702
Pyryllium compounds disclosed in US Pat. No. 4,7
Described in Formulas 56, 993 as formulas (I) and (II)
And near infrared absorbing dyes. Special
Among these, cyanine dyes and squarily are preferable.
Dyes, pyrylium salts, nickel thiolate complexes
It is done. As the pigment, commercially available pigments and color inks are used.
Dex (CI) Handbook, "Latest Pigment Handbook" (Japanese face
Japan Technology Association, published in 1977), “Latest Pigment Applied Technology”
(CMC Publishing, 1986), “Printing Ink Technology” C
Uses pigments described in MC Publishing, 1984)
it can. Specifically, insoluble azo pigments, azo lake faces
Materials, condensed azo pigments, chelate azo pigments, phthalocyanines
Pigments, anthraquinone pigments, perylene and perinone
Pigment, thioindigo pigment, quinacridone pigment, di
Oxazine pigments, isoindolinone pigments, quinophthalates
Ron pigment, dyed lake pigment, azine pigment, nitroso
Pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic pigment,
-Bon black or the like can be used. Pigment is not surface treated
It may be used for any known surface treatment.
Yes. Among these pigments, carbon black is preferable.
It is. As the metal fine particles, Japanese Patent Application Laid-Open No. 2001-20.
The metal fine particles described in 5952 are preferred. Specifically
Is preferably Ag, Au, Cu, Sb, Ge and Pb
Ag, Au and Cu are more preferable. The above photothermal conversion substance is a hydrophilic binder polymer.
It may be contained in the matrix formed by the limer.
In a hydrophobized precursor, i.e. a single component polymer
Microparticles, core-shell microparticle cores and microcapsules
In a hydrophobic substance. former
In this case, a water-soluble or hydrophilic photothermal conversion substance is preferred.
In the latter case, a lipophilic photothermal conversion substance is preferred. These dyes or pigments have a hydrophilic layer solid content.
0.01 to 50%, preferably 0.1 to 10% of dye,
Is particularly preferably 0.5 to 10%, especially in the case of pigments.
Preferably it can be used at a rate of 3.1 to 10%
The The amount of metal fine particles added is 10% or more of the total solid content of the hydrophilic layer.
Above is preferred. The hydrophilic layer of the present invention has a dispersion stability of the hydrophilic layer.
To improve the performance, coating performance, on-machine developability, printing performance, etc.
In addition to nonionic and anionic surfactants,
Cationic interface as described in 195356
Activators, fluorine-containing surfactants, and JP-A-59-121
No. 044 and JP-A-4-13149.
Amphoteric surfactants can be added. Addition amount is parent
0.05 to 5% of aqueous layer solid content is preferable. The aqueous coating solution is preferably an aqueous solvent.
Furthermore, for uniform liquefaction by suppressing precipitation when adjusting the coating liquid
A water-soluble solvent is used in combination. As the water-soluble solvent,
(Methanol, ethanol, propyl alcohol)
, Ethylene glycol, diethylene glycol, pro
Pyrene glycol, dipropylene glycol, ethylene
Glycol monomethyl ether, propylene glycol
Monomethyl ether, ethylene glycol monoethyl ester
Ether), ethers (tetrahydrofuran, ethyl)
Glycol dimethyl ether, propylene glycol
Dimethyl ether, tetrahydropyran, etc.), ketone
(Acetone, Methyl ethyl ketone, Acetylacetone
Etc.), esters (methyl acetate, ethylene glycol
No acetate, etc.), amides (formamide, N-methyl)
Ruformamide, pyrrolidone, N-methylpyrrolidone
Etc.), etc., and even if one or more are used in combination
Good. The hydrophilic layer of the present invention is a parent layer in which necessary components are dissolved.
Prepare an aqueous layer coating solution and apply a conventionally known coating on the water-resistant support.
Apply and dry using any of the cloth methods.
Be filmed. The thickness of the formed hydrophilic layer is 0.2 to 10 g /
m²Is preferable, and more preferably 0.5 to 8 g / m.²In
The Within this range, a uniform film with sufficient strength is produced. In the present invention, the hydrophilic layer surface has a parent.
A polymer compound having an aqueous functional group is chemically bonded.
Can have a surface graft hydrophilic layer. this
The surface graft hydrophilic layer is a thin layer covering the hydrophilic layer surface.
A hydrophilic layer is formed. Provide surface graft hydrophilic layer
Without impairing the adhesion with the image forming layer.
The water retention of the hydrophilic layer can be improved. In the surface graft hydrophilic layer, at least 1
The end of a polymer compound having two hydrophilic functional groups is
High molecular compound for bonding directly or other to the hydrophilic layer of the printing plate
(Hereinafter, this high molecular compound for bonding is referred to as “main polymerization”.
Chemical bonds), sometimes referred to as “compounds”.
ing. Hydrophilic functional group constituting the graft part
The polymer compound having
It is preferable that the polymer be a polymer. With hydrophilic functional groups
An amide group, a carboxy group, a sulfo group, phosphoric acid,
Phosphonic acid or amino groups or salts thereof, 2-tri
Methylaminoethyl (meth) acrylate or its halo
Examples include hydrogenates. These hydrophilic functional groups have the above-mentioned graft part.
At least one contained in the polymer compound constituting
For example, with the hydrophilic layer of the linear polymer compound
When having a hydrophilic functional group at the terminal opposite to the binding part,
Linear polymer is a polymerization component or co-polymerization of hydrophilic monomer
The case where it contains as a part is mentioned. Hydrophilicity that can be used in the present invention
The monomer has the above hydrophilic functional group.
If it is, it will not specifically limit. Particularly useful hydrophilic modules
Examples of nomers include (meth) acrylic acid or its alkyl
Potassium metal salt or amine salt, itaconic acid or its alcohol
Potassium metal salt or amine salt, 2-hydroxyethyl
(Meth) acrylate, (meth) acrylamide, N-
Monomethylol (meth) acrylamide, N-dimethylo
(Meth) acrylamide or allylamine or
Its hydrohalide, 3-vinylpropionic acid or
Alkali metal salt or amine salt, vinyl sulfone
Acids or alkali metal salts or amine salts thereof, vinyls
Tylenesulfonic acid or its alkali metal salt or amino acid
Salt, 2-sulfoethylene (meth) acrylate or
Is 3-sulfopropylene (meth) acrylate or its
Alkali metal salt or amine salt, polyoxyethylene
Glycol mono (meth) acrylate or 2-act
Rilamido-2-methylpropanesulfonic acid or its amide
Lucari metal salt or amine salt, acid phosphooxy
Polyoxyethylene glycol mono (meth) acrylate
Or allylamine or its hydrohalide
Can be mentioned. The surface graft hydrophilic layer of the present invention is generally
Easy to manufacture using means called surface graft polymerization
can do. Graft polymerization is active on polymer chains
Give another seed, polymerize another monomer, thereby starting
A method of synthesizing graft (grafting) polymers, especially
When the polymer chain that gives the active species forms a solid surface
Is called surface graft polymerization. Surface graph of the present invention
The hydrophilic layer is surface graft polymerization on the hydrophilic layer surface.
Can be easily obtained. A surface graph for realizing the hydrophilic layer of the present invention.
As the photopolymerization method, all known methods described in the literature are used.
Can be used, for example, new polymer experiments 10,
Edited by Polymer Society of Japan, 1994, published by Kyoritsu Shuppan Co., Ltd., P135
Photograft polymerization, plasma irradiation graft polymerization
Surface graft polymerization method, adsorption technology handbook NTS Ltd., bamboo
Supervision, published in 1999.2, p203, p695, gamma rays,
Examples include radiation-induced graft polymerization methods such as electron beams.
The Further, as a specific method of the photograft polymerization method,
Described in JP-A-10-296895 and JP-A-11-119413
The method can be used. Create the surface graft hydrophilic layer of the present invention
In addition to these, at the end of the polymer compound chain
Trialkoxysilyl group, isocyanate group, amino
Reactive functional groups such as groups, hydroxyl groups and carboxy groups
And the coupling between the lithographic printing plate and the hydrophilic layer surface functional group.
Examples of the forming method include a forming reaction. Further, it is chemically bonded to the hydrophilic layer surface.
A main polymer compound and the end of the polymer chain on the main polymer compound
Linear polymers with hydrophilic functional groups attached at the ends
When producing a hydrophilic hydrophilic layer comprising a compound,
Functional group capable of coupling reaction with functional group on the surface of water layer
Giving to the side chain of polymer compound, hydrophilic as graft chain
Graft type incorporating polymer chains with functional groups
A polymer compound is synthesized, and this polymer and hydrophilic layer surface functional group
Can be formed by a coupling reaction. Or
Specific examples of such trunk polymer compounds will be described later (half).
A hydrophilic organic polymer that forms a composite with a metal-containing resin;
Can be mentioned. The above photo-graft polymerization method, plasma irradiation group
Raft polymerization, radiation-induced graft polymerization, coupling
Plasma irradiation grafting from the viewpoint of manufacturing suitability
The polymerization method and radiation-induced graft polymerization method are particularly excellent. Specifically, plasma irradiation graft polymerization.
Method and radiation irradiation graft polymerization method.
And Y.Ikada et al., Macromolecules vol.19, pag
e 1804 (1986) etc.
The Treatment of hydrophilic layer surface with plasma or electron beam
And generate radicals on the surface, and then its active surface
Reacting with a monomer having a hydrophilic functional group
Can get more. The film thickness of the surface graft hydrophilic layer of the present invention is favorable.
Preferably 0.01 ~ 10g / m²Range and better
Preferably 0.1-5g / m²Range. Within this range
With this, the effects of the present invention are fully exerted, and further excellent printing durability is achieved.
In addition to being obtained, the fine line reproducibility of the printed matter is also good,
preferable. [Image forming layer] The image forming layer of the present invention comprises
Microcapsules enclosing aqueous substances and photothermal conversion substances
contains. The hydrophobic substance aggregates within the smallest repeating unit
Two atomic groups with an energy contribution of 10 kJ / mol or more
Hydrophobic resin having the above or a phase transition temperature of 45 ° C. or higher
It is a hydrophobic compound. The above hydrophobic resin is disclosed in JP-A-2002-00.
As described in No. 2135, the minimum repeat unit of the structure
The contribution value of the cohesive energy by Fendors is 10k.
Hydrophobic resin having two or more atomic groups of J / mol or more
It is characterized by being. Contribution of cohesive energy of atomic groups
For the cohesive energy contribution value by Fendors
For example, D.W.Krevelen, Properties of Polymers, 3rd.
Edition, Elsevier (1997), p. 189-200
It is listed. Aggregation energy of 10 kJ / mol or more
Specific examples of the atomic group having
Group, cyano group, phenyl group, carbonyl group, carboxy group
Sil group, urethane bond, urea bond, ureido bond,
Ether bond, ester bond, amide bond, etc.
The As a specific example of the above hydrophobic resin,
Resin, phenol resin, polyester resin, polyurea
Tan resin, melamine resin, polyamide resin, alkyd tree
Fat, xylene resin, urea resin, hydroxystyrene resin
Is mentioned. Released from microcapsules by heat
The mechanical strength of the image area created by the hydrophobic resin
In the case of a resin with a large energy, it becomes large and further resistance is increased.
It is estimated that it contributes to improvement of printability. As the hydrophobic resin, laser writing is possible.
The one that plasticizes once when the heat rises and hardens when cooled
preferable. Furthermore, it is more preferable if the resin is crosslinked by heat.
That's right. From this, heat of epoxy groups, methylol groups, etc.
A resin having a reactive group is preferred. Has a thermally reactive group
Hydrophobic resin was generated by chemical decomposition of the capsule wall material
Compound, binder resin, dispersion resin, or other additions
Perform crosslinking reaction or self-crosslinking reaction with
Yeah. The hydrophobicity suitable for the image forming layer of the present invention.
Examples of the compound include a monomer having a phase transition temperature of 45 ° C. or higher.
Low molecular weight compounds, oligomers, polymers, resins, etc.
A high molecular compound can be mentioned. Hydrophobic compound phase
If the transition temperature is high, on-machine storage of the planographic printing plate
Degradability of developability hardly occurs. Among the above hydrophobic compounds, a thermally reactive group is present.
The compound which has is more preferable. As a suitable thermally reactive group
Is the same thermally reactive group as described in the hydrophilic layer section.
Can. Hydrophobic compounds having thermally reactive groups are
Image strength is improved by thermal reaction, and high printing durability can be realized.
The As specific examples of the hydrophobic low molecular weight compounds,
Tris (acryloyloxyethyl) isocyanurate
(Mp53 ° C), tris (methacryloyloxye)
Chill) isocyanurate (mp 81 ° C.), pentaerythris
Litol tetraacrylate (mp50 ° C), bisphete
Nord A dimethacrylate (mp62 ° C), neo-plier
Luglycol diacrylate (mp70 ° C), trimethyl
Roll propane acrylate benzoate (Kyoeisha)
Gaku Co., Ltd. BA-134, mp45 ° C.)
The Others such as Shinzo Yamashita and Tosuke Kaneko “Crosslinking agent
Book "published by Taiseisha (1981),
Thermally reactive compounds with melting points or glass transition temperatures of 45 ° C or higher
Can be used. As specific examples of the hydrophobic polymer compound,
Polystyrene resin (Tg 100 ° C), polymethyl
Tacrylate (Tg 105 ° C), polyacrylonitrile
(Tg 105 ° C), polyethyl methacrylate resin (T
g65 ° C.), polyester resin, for example, manufactured by Toyobo Co., Ltd.
Byron 200 (Tg 67 ° C.) and the like can be mentioned. As a suitable hydrophobic resin having a heat-reactive group
For example, an epoxy resin that is a thermosetting resin, such as
1002 (Tg 51 ° C.), Epicoat 1004 (6
0 ° C), novolac type phenolic resin, for example, Crezo
Lunovolac resin (m-cresol / p-cresol
Molar ratio 60/40, weight average molecular weight 6600, Tg1
03 ° C), acrylates or
Tacrylate resin, for example allyl methacrylate / meta
Crylic acid copolymer (molar ratio 80/20, weight average molecular weight
15000 (Tg62 ° C.) and the like. Among such hydrophobic compounds, the phase transition temperature
A compound having a degree of 55 ° C. or higher is more preferable, and the phase transition temperature is
More preferred is a compound of 60 ° C. or higher. Hydrophobic compounds
The phase transition temperature of the product is preferably 170 ° C. or less, more preferably
Or 150 ° C. or lower. Particularly good images within this range
Formation is obtained. Microencapsulation of the above hydrophobic material
Using the same methods and wall materials as described in the description of the hydrophilic layer.
It can be carried out. The average particle size of the above microcapsules is
0.01-20 μm is preferable, but 0.05-
2.0 μm is more preferable, and 0.10 to 1.0 μm is particularly preferable.
Is preferred. Amount of microcapsules added to the image forming layer
Is preferably at least 50% of the solid content of the image forming layer in terms of solid content.
60% or more is more preferable. Photothermal conversion contained in the image forming layer of the present invention
Suitable materials are the same as those described in the section of the hydrophilic layer.
Can be cited as a thing. Photothermal conversion material is hydrophilic
As in the case of the layer, in the hydrophilic matrix of the image forming layer
Water-soluble or hydrophilic photothermal conversion substance
Is preferably contained in the hydrophobic material of the microcapsule.
In this case, a lipophilic photothermal conversion substance is preferable. The image forming layer of the present invention has improved on-press developability.
Add hydrophilic resin for strength of film and image forming layer
be able to. The hydrophilic resin is not three-dimensionally cross-linked
Those having a good on-press developability are preferred. Examples of hydrophilic resins include hydroxyl.
Group, carboxyl group, hydroxyethyl group, hydroxy
Propyl group, amino group, aminoethyl group, aminopropyl
Those having a hydrophilic group such as
Good. As specific examples of hydrophilic resins, Arabico
, Casein, gelatin, soya gum, starch and its derivatives
Body, hydroxyethyl cellulose, hydroxypropyl
Cellulose, methylcellulose, carboxymethyl cell
Cellulose such as loin and its salts and cellulose acetate
Source derivatives, alginic acid and its alkali metal salts, al
Potassium earth metal salt or ammonium salt, water-soluble urethane tree
Fat, water-soluble polyester resin, vinyl acetate-maleic acid
Copolymers, styrene-maleic acid copolymers,
Riacrylic acids and their salts, polymethacrylic acids and
And salts thereof, hydroxyethyl methacrylate homo
Polymers and copolymers, hydroxyethyl acrylate
Homopolymers and copolymers of hydroxypropyl
Methacrylate homopolymers and copolymers, hydro
Homopolymers and copolymers of xylpropyl acrylate
-Hydroxybutyl methacrylate homopolymer and
And copolymers of hydroxybutyl acrylate
Limers and copolymers, polyethylene oxides, poly
(Propylene oxide), polyvinyl alcohol (P
VA), and a degree of hydrolysis of at least 60%, preferably
Preferably at least 80% hydrolyzed polyvinyl acetate
, Polyvinyl formal, polyvinyl butyral,
Homopolymer of polyvinylpyrrolidone and acrylamide
And copolymers, homopolymers of methacrylamide and
Polymer, homopolymer of N-methylolacrylamide
And copolymers, 2-acrylamido-2-methylpropyl
Examples include lopansulfonic acid and its salts. Another hydrophilic resin suitable for the present invention is a parent resin.
Mention may be made of aqueous graft polymers. Hydrophilic
The raft polymer is a monomer having a hydrophilic group (below
Is also called a hydrophilic monomer) as a polymerization component
Graft polymer having polymer or copolymer as side chain
-Represents. Copolymerization of hydrophilic monomers in side chain copolymers
The proportion is preferably 50 mol% or more, more preferably 8
It is 0 mol% or more. Main chain is formed from hydrophilic monomer
Even formed from hydrophobic monomers
In addition, hydrophilic monomers and hydrophobic monomers
-It may be formed from both. Examples of the hydrophilic group include carboxy.
Sil group and its salt, carboxylic anhydride group, sulfonic acid group
And salts thereof, amide groups, polyethyleneoxy groups, etc.
It is done. As a monomer used for the side chain, the above hydrophilic
Any monomer having a functional group can be used, but is preferred.
Or acrylic acid, methacrylic acid, maleic anhydride,
Itaconic acid, acrylamide, N-alkylacrylic acid
(Alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms),
Styrene sulfonic acid, 2-acrylamido-2-methyl
Propanesulfonic acid, vinyl pyrrolidone, polyethylene
Oxy group-containing monomers are preferred. Acid is its salt
It's okay. Of these monomers, ease of synthesis
Therefore, acrylamide is particularly preferable. The weight average of the above-mentioned side chain hydrophilic monomer polymer is
The average molecular weight is preferably 1,000 to 50,000,
The weight average molecular weight of the aqueous graft polymer is 5,000.
~ 500,000 is preferred. Good on-board within this range
Developability and printing durability can be obtained. The hydrophilic graft polymer is a hydrophilic polymer.
Has a radically polymerizable functional group at one end of the nomeric polymer
Macromonomers such as acrylamide macromonomers
To polymerize or with this macromonomer
Obtained by copolymerizing with a copolymerizable monomer
The In the image forming layer of the present invention, a hydrophilic resin is used.
The hydrophilic graft polymer and the non-grafted parent
A water-based resin can be mixed and used as needed. The addition amount of the hydrophilic resin into the image forming layer is as follows:
2 to 40% of the solid content of the image forming layer is preferable. Within this range
Good on-press developability and high printing durability can be obtained. In the image forming layer of the lithographic printing original plate of the present invention,
In order to obtain various properties, other than the above,
Various compounds may be added. These are described below
To do. The image forming layer of the present invention has a heat-reactive functional group.
Adding a compound that initiates or accelerates the reaction of
it can. Such compounds include, for example,
List compounds that generate cal or cations
Lophine dimer, trihalomethyl compound,
Dioxides such as oxides, azo compounds, and diazodiphenylamine
Contains azonium salt, diphenyliodonium salt, etc.
Onium salt, acylphosphine, imide sulfonate
And so on. These compounds together with hydrophobic substances
You may make it contain in a capsule. These compounds are 1% in the image forming layer.
It can be added in a range of ˜20%. Preferably 3
% To 10%. Within this range, on-machine developability and durability
Good reaction initiation or acceleration effect without impairing printability
can get. Inorganic fine particles are added to the image forming layer of the present invention.
As inorganic fine particles, silica, alumina,
Magnesium oxide, titanium oxide, magnesium carbonate, aluminum
Calcium lumate or a mixture of these is preferred
These are examples of skins that are not photothermally convertible.
For strengthening of film and interfacial adhesion by surface roughening
Can be. The average particle size of the inorganic fine particles is 5 nm to 10 μm.
Are preferred, more preferably 10 nm to 1 μm
is there. Within this range, the polymer particles and photothermal conversion
Stable dispersion of metal fine particles in organic / inorganic composites
In addition, the film strength of the image forming layer is sufficiently maintained to prevent printing stains.
It is possible to form a non-image portion having excellent hydrophilicity that is difficult to bend. Take
Inorganic fine particles are commercially available products such as colloidal silica dispersions.
And can be easily obtained. The content of the inorganic fine particles in the image forming layer is determined by the image.
1.0 to 70% of the total solid content of the image forming layer is preferable, more
Preferably it is 5.0 to 50%. The surfactant used in the image forming layer is a parent.
The same amount of surfactant that can be added to the water layer
Can be used. Further, the image forming layer of the present invention has an image forming function.
Later, to make it easier to distinguish between image and non-image areas,
Use dyes with high absorption in the visible light region as colorants for images
Can be used. Specifically, Oil Yellow # 1
01, oil yellow # 103, oil pink # 31
2. Oil Green BG, Oil Blue BOS, Oil
Blue # 603, Oil Black BY, Oil Black
BS, Oil Black T-505 (orientated chemistry)
Industrial Co., Ltd.), Victoria Pure Blue, Crystal
Violet (CI42555), methyl violet
(CI42535), ethyl violet, rhodamine
B (CI145170B), Malachite Green (CI
42000), methylene blue (CI52015), etc.
And dyes described in JP-A-62-293247
Can be mentioned. In addition, phthalocyanine pigments,
Use pigments such as azo pigments and titanium oxides.
Can do. The amount added is based on the total solid content of the image forming layer.
The ratio is 0.01 to 10%. The image forming layer of the present invention comprises the necessary components described above.
Dissolved in water or a mixed solvent with an organic solvent added if necessary.
Dissolve or disperse to prepare a coating solution.
It is formed into a film by applying and drying using either
The The coating amount (solid content) of the image forming layer varies depending on the application.
In general, however, 0.1-30 g / m²Is preferred
0.3 to 10 g / m²Is more preferable, 0.3-5
g / m²Is particularly preferred. [Water-soluble protective layer] Image-forming layer surface of the present invention
Since the surface is hydrophilic, the original plate was transported in product form
Be stored, stored, or handled before use
When it becomes hydrophobic due to the influence of the environmental atmosphere,
Affected by the degree, mechanical scratches or dirt, etc.
Susceptible to. Therefore, the planographic printing original plate of the present invention
In order to prevent this, water-soluble polymer is the main component.
A water-soluble protective layer can be provided. This water soluble
The protective layer is easily removed during development on a printing press,
There is no need for removal. Water-soluble polymer contained in water-soluble protective layer
Functions as a binder in the water-soluble layer. High water solubility
Examples of molecules include hydroxyl groups, carboxy groups, and basic nitrogen.
Examples thereof include polymers having sufficient groups such as element-containing groups. Specifically, Japanese Patent Laid-Open No. 2001-162961.
Polyvinyl alcohol, gum arabic, poly
Acrylamide or acrylamide copolymer, poly
Water-soluble polymers such as crylic acid, JP2002-01931
Carboxymethyl cellulose described in No. 8, methyl cellulose
And water-soluble cellulose such as cellulose. [0211] The water-soluble protective layer has various other components.
A surfactant may be contained. Surfactants that can be used
For example, an anionic surfactant or a nonionic surfactant may be used.
I can get lost. Specific examples of these include image formation as described above.
Examples thereof include the same surfactants used for the layer. World
The amount of surfactant to be added is preferable per total solid content of the water-soluble layer.
Or 0.01 to 1%, more preferably 0.05.
~ 0.5%. The water-soluble protective layer is disclosed in JP-A-2001-341.
Contains fluorine atom and / or silicon atom described in No. 448
Compound, for example, water-soluble or water-dispersible fluorosurfactant
Contains water-soluble or water-soluble or water-dispersible silicone oil
Can be. By containing these compounds
Prevents sticking between printing masters when stacked
it can. In addition to the above components, if necessary, as a wetting agent
Glycerin, ethylene glycol, triethyleneglycol
A lower polyhydric alcohol such as a polyol can also be used.
The amount of these wetting agents used is 0.1 to 5.0 in the surface protective layer.
% Is suitable, and the preferred range is 0.5-3.
The amount is 0%. In addition to the above, the planographic printing material of the present invention
Add antiseptics to the coating solution for the surface protection layer of the plate.
You can. For example, benzoic acid and its derivatives, phenol
0.005% of water, formalin, sodium dehydroacetate
It can be added in the range of 5 to 2.0%. In addition, the coating solution
A foaming agent can also be added. Preferred antifoaming agents are organic
Silicone compound is included, and the amount added is 0.0001
A range of ˜0.1% is preferred. Further, the water-soluble protective layer has a photothermal conversion product.
Quality can be added. As a photothermal conversion substance, it is written for hydrophilic layer.
The listed substances can be added in the same range of addition amounts. The coating amount (solid content) of the water-soluble protective layer is:
0.1 to 5 g / m²Is preferably 0.2 to 3 g / m²Gayo
More preferable. [Water Resistant Support] Next, the present invention is provided for the present invention.
The water resistant support will be described. As a water resistant support
Aluminum plate, zinc plate, copper-aluminum plate, copper
-Stainless steel plates, bimetal plates such as chrome-copper plates, black
Mu-copper-aluminum plate, chrome-lead-iron plate, chrome-
Trimetal plate such as copper-stainless steel plate.
Those having a thickness of 0.1 to 3 mm, particularly 0.1 to 1 mm are mentioned.
In addition, a water-resistant treatment with a thickness of 80 μm to 200 μm is performed.
Paper, plastic film (eg, cellulose acetate)
, Cellulose triacetate, cellulose propionate, butyric acid
Cellulose, cellulose acetate butyrate, polyethylene terf
Talate, polyethylene, polystyrene, polypropylene
Polycarbonate, polyvinyl acetal, etc.)
Or paper or plastic film laminated with metal foil
Or the like. These supports are in contact with the upper layer to be applied.
Known surface treatment can be performed to increase the adhesion.
The As surface processing of plastic film support,
For example, corona discharge treatment, plasma treatment, blast treatment
Surface treatment such as adhesives (acrylic, urethane,
(Rulose, epoxy, etc.) coating treatment,
316183, 8-272088 and 9-17
No. 9311 and JP-A-2001-199175
Undercoat layer coating (eg, polyvinyl alcohol or
Droxyalkyl acrylate or methacrylate
Homopolymer or copolymer, hydrolyzed orthosilicate
Tetraethyl or methyl acid, and preferably two more
Contains fine particles of silicon oxide and / or titanium dioxide
Application of a hydrophilic undercoat layer). metal
In the case of a support, a publicly known surface treatment technique may be performed.
it can. For example, in an aluminum support, roughening treatment,
Anodizing treatment, Anodizing pore enlargement and sealing treatment, Surface
Known surface treatment techniques such as hydrophilization treatment may be mentioned. In the case of a metal support, the heat spread to the support.
Insulation layer is provided as an undercoat to suppress scattering and increase sensitivity.
Can Such a heat insulating layer is the main component
Contains organic or inorganic resins. Organic or inorganic resin
Is known hydrophobic polymer, hydrophilic polymer, hydrophilic polymer
Cross-linked, aluminum with hydroxyl or alkoxy groups
Sol-gel modification such as Ni, Si, Titanium, Zirconium
Select widely from inorganic polymers, etc.
You can. [Exposure and Printing] Planographic printing original plate of the present invention
Is imaged by heat. Specifically, thermal recording head
Direct image-like recording, etc., scanning dew with infrared laser
High intensity flash exposure such as light, xenon discharge lamp and infrared
Line lamp exposure or the like is used, but the wavelength is 700 to 120.
Semiconductor laser, YAG laser emitting 0nm infrared light
For example, exposure with a solid high-power infrared laser is suitable. The original plate for lithographic printing of the present invention has a laser output.
Can be irradiated with a laser of 0.1-300W
The If a pulse laser is used, the peak output
A laser with a power of 1000 W, preferably 2000 W
It is preferable to shoot. The exposure amount in this case is the image for printing.
The surface exposure intensity before modulation with 0.1 to 10 J / cm²of
The range is preferably 0.3 to 1 J / cm.²Range of
More preferably, it is a range. When the support is transparent
Can be exposed through the support from the back side of the support.
Yes. Image-exposed lithographic printing original plate of the present invention
Is attached to the printing press cylinder without further processing
After that, dampening water and ink are supplied, and paper is usually supplied.
Developed on the machine by printing start operation, and then prints
be able to. Further, the lithographic printing original plate of the present invention is a printing machine.
After mounting on the plate cylinder, the laser mounted on the printing press
-A system that exposes and then develops on-machine and prints
Also used for. Further, the lithographic printing original plate of the present invention is exposed to light.
After that, liquid development processing using water or an appropriate aqueous solution as a developer is performed.
Then, it can be used for printing. [0224] The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. <Example of preparation of support>
Polyethylene terephthalate prepared and corona treated
(PET) film (thickness 180μm, Toray Industries, Inc.)
Applied) and dried, and the dry coating amount is 1.0 g / m.²Under
A PET support having a coating layer was prepared. [0226] (Coating solution for undercoat)   Methanol silica   (Nissan Chemical Industry Co., Ltd. 30% methanol dispersion) 0.75 g   Titanium dioxide dispersion (preparation method below, solid content 27%) 1.20 g   Sol-gel preparation liquid (preparation method below) 0.66g   PVA117 (Kuraray Co., Ltd. polyvinyl alcohol,     0.38 g of 4% aqueous solution with a saponification degree of 98.5%)   S-113 (Asahi Glass Co., Ltd. fluorine-based surfactant)     0.25g of 3% aqueous solution   2.93 g of methanol   8.65g of water (Production method of titanium dioxide dispersion)
Tan powder (rutile type manufactured by Aldrich) 6.00 g, PVA
117% 4% aqueous solution 15.00g, water 3.00g 10
Filled with 0mm glass bottle and filled with 3mmφ glass beads
After filling, disperse by stirring for 20 minutes in a paint shaker
Was made. (Method for preparing sol-gel preparation solution) Tetramethoxy
Sisilane (LS540 manufactured by Shin-Etsu Silicone Co., Ltd.) 8.4
7g, methanol 1.82g, water 14.5g, phosphoric acid
(0.1 mol / l) 0.28 g of mixed solution at room temperature for 2 hours
Aged to prepare a sol-gel preparation. <Example of preparation of hydrophobized precursor (1)> Oil phase formation
As a part, 30g of polymethyl methacrylate and anion
Surfactant Pionein A-41C (Takemoto Yushi Co., Ltd.) 0.5
g is a mixture of 75 g of ethyl acetate and 30 g of methyl ethyl ketone.
Dissolved in the combined solvent. As a water phase component, polyvinyl alcohol
(Kuraray Co., Ltd. PVA205, saponification degree 88%)
100 g of a 4% aqueous solution of was prepared. Oil phase components and water phase formation
Minute emulsify the mixture with a homogenizer at 10,000 rpm
It was. Then 80 g of water was added, 30 minutes at room temperature, 4 more
Stir at 0 ° C. for 3 hours. Fine particles obtained in this way
The solid content concentration of the polymer dispersion is 16%, and the fine particles
The average particle size of was 0.23 μm. <Example of preparation of hydrophobized precursor (2): self-water
Dispersible polyurethane fine particles> Stirrer, reflux device, drying
A 1 L four-necked flask equipped with a nitrogen inlet tube and a thermometer
-Knock DN-980 (Dainippon Ink Chemical Co., Ltd.)
Of polyisocyanate), 2,2-bis (hydride)
Roxymethyl) propionic acid 33.5 g, dibutyltin di
Add 0.05 g of laurate and 300 g of ethyl acetate,
By stirring at 80 ° C. for 3 hours, the dry solid content ratio is 5
Poly with 0.0% isocyanate group content of 6.80%
A solution of urethane prepolymer was obtained. This polyure
To 100 g of tan prepolymer solution,
Add 30 g, neutralize with 3.50 g triethylamine,
Water was added dropwise with stirring. The prepolymer solution gradually
After thickening and adding about 300 g of water, diethylenetria
An aqueous solution in which 2.51 g of min was dissolved in 50 g of water was stirred.
Slowly added. The resulting dispersion is
Heat to 0 ° C to remove organic solvent and excess water under reduced pressure
By dry solid content ratio 33.5%, average particle size
An aqueous dispersion of 0.08 μm polyurethane fine particles was obtained.
It was. The acid value was 31.0. <Example of preparation of hydrophobized precursor (3): self-water
Dispersible core-shell type fine particles> Condenser, mechanical stirring
Stirrer, thermometer, nitrogen inlet / outlet and two monomers
-In a 500 ml flask equipped with a supply pipe,
Acid 25 g, styrene 10 g, ethyl acrylate 2 g,
Raw materials of 3 g of benzoyl peroxide and 70 g of n-butanol
Add 40 ml of a homogeneous mixture and keep at 110 ° C.
The mixture was heated for 2 hours with stirring. After cooling to room temperature, steam
Add 200 ml of distilled water and 10 ml of 25% ammonia water.
The mixture was stirred until it became clear. After that,
0.9 g of scorbic acid and 1.48 g of potassium persulfate
Was added. Styrene (71.21 g), glycidyl meta
Chrylate (3.744 g) and bromotrichlorometa
(3 g) was added and the temperature was raised to 35 ° C. under a nitrogen atmosphere.
I got it. The temperature was maintained at 35 ° C. for 7 hours. Solid content is
25%. Core is styrene / glycidyl methacrylate
A rate copolymer that associates with the core as a shell material
Carboxylated acrylate copolymer. <Synthesis of hydrophilic organic polymer (B-1)>
Acrylamide 25g, 3-mercapto in a three-necked flask
3.5 g propyltrimethoxysilane and dimethylphospho
Add 51.3 g of lumamide and heat to 65 ° C under nitrogen flow.
And heated to 2,2'-azobis (2,4-dimethylvale
Nitrile) was added to start the reaction. 6
After stirring for an hour, it was cooled to room temperature and ethyl acetate 1.5
When charged into a liter, a solid precipitated. after that,
Filtered, washed thoroughly with ethyl acetate and dried
(Yield 21 g). Heavy weight by GPC (polystyrene standard)
The weight average molecular weight was found to be 5000. <Synthesis of Microcapsule (1)> Oil Phase Composition
Epoxy resin epicoat 1003 (oil shell)
Epoxy) 30g, trimethylolpropane and xylyl
Adduct D110N with range isocyanate (Takeda Pharmaceutical)
(Product made in industry) 30g, photothermal conversion substance (below IR-1) 8g,
Anionic surfactant (Pionine A41 made by Takemoto Yushi)
C) was dissolved in 90 g of ethyl acetate. As an aqueous phase component
Polyvinyl alcohol (Kuraray PVA217E) 4%
180 g of an aqueous solution was prepared. Oil phase component and water phase component
The emulsification was performed at 10,000 rpm using a modifier. This
Concentration of solid content of microcapsule liquid obtained as above
Was 18%, and the average particle size was 0.4 μm. [0234] [Chemical 8] <Synthesis of Microcapsule (2)> Oil Phase Composition
Polybutylene adipate glycol (number average minute)
The molecular weight 1000) 800 g and 4,4'-diphenylmethane
Kneading 200g of diisocyanate at 70 ° C with a kneader
30 g of adipate-based urethane resin obtained as above, D11
0N 30g, photothermal conversion substance (IR-1) 8g, Pio
Nin A41C 0.5g, ethyl acetate 70g, acetoni
Dissolved in 20 g of tril. Hereinafter, the microcapsule
In the same manner as in the synthesis example of (1), the microcapsule (2)
Synthesized. The solids concentration is 18% and the average particle size is 0.
It was 6 μm. <Synthesis of Microcapsule (3)> Oil Phase Composition
Thermoplastic alkylphenol-modified resin HP-7
0 (Mitsubishi Gas Chemical Co., Ltd.) 6.0g, D110N (Takeshi
30g, manufactured by Tayaku Kogyo Co., Ltd., photothermal conversion substance (IR-1) 8
g, 0.5 g of Pionein A41C into 90 g of ethyl acetate
Dissolved. Hereafter, the synthesis example of the said microcapsule (1)
In the same manner as above, a microcapsule (3) was synthesized. solid
The concentration was 18% and the average particle size was 0.8 μm.
It was. <Synthesis of Microcapsule (4)> Oil Phase Composition
Thermosetting novolac resin NP-100 (Mitsubishi Gas
6.0 g, D110N 30 g, photothermal
Conversion substance (IR-1) 8 g, Pionein A41C 0.
5 g was dissolved in 90 g of ethyl acetate. Hereinafter, the microphone
Microcapsule in the same way as the synthesis example of Locapsule (1)
(4) was synthesized. Solid content is 18%, average
The particle size was 0.7 μm. <Synthesis of Microcapsule (5)> Oil Phase Composition
Trimethylolpropane and xylylene diisocyanate as minutes
50% ethyl acetate solution of adduct with Anato (Takeda Pharmaceutical)
Industrial Co., Ltd. D119N) 15g, Epicoat 1004
(Oilized Shell Epoxy Co., Ltd., Tg 60 ° C.) 30 g,
Photothermal conversion substance (IR-1) 8g, anionic surfactant
(Takemoto Yushi Co., Ltd. Pionein A41C) 0.5g vinegar
Dissolved in 90 g of ethyl acid. Polyvini as the water phase component
4% of rualcohol (PVA217E manufactured by Kuraray Co., Ltd.)
180 g of an aqueous solution was prepared. Oil phase component and water phase component
The emulsification was performed at 10,000 rpm using a modifier. So
After that, 120 g of water was added, and at room temperature for 30 minutes, further 40 ° C.
For 3 hours. The microcapsule thus obtained
The solid concentration of the liquid is 23.4%, and the average particle size is 0.
It was 45 μm. Example 1 <Formation of hydrophilic layer> Prepare a hydrophilic layer coating solution of the following composition,
A bar on a PET support having an undercoat layer obtained in the above preparation example
Dry weight at coater is 3.0g / m²Painted to be
Make cloth and then dry in oven at 60 ° C for 10 minutes
And then, at 55 ° C. under 60% RH temperature and humidity conditions
Heating was performed after 3 days. [0240] (Hydrophilic layer coating solution composition)   Anionic surfactant (Nikko Chemicals, Nikkor OTP-100s)     0.24g of 4% aqueous solution of   Hydrophilic binder polymer preparation liquid (A) (the following production method) 4.7 g   Hydrophobized precursor (1) aqueous solution of the preparation example 3.47 g   4.8 g of a 1.5% aqueous solution of a photothermal conversion substance (the following dye IR-2)   3.2g of water (Hydrophilic binder polymer preparation liquid (A)
Production method) 5.12 g of purified water, 8.1 of ethyl alcohol
In 4g, tetramethoxysilane (Shin-Etsu Silicone)
LS540 manufactured by Co., Ltd. 1.23 g, colloidal silica fine
Particles (Nissan Chemical Industry Co., Ltd., Snowtex C20%
Of aqueous solution) 2.04 g, hydrophilic organic polymer (B-1)
10.2 g of 4% aqueous solution, aluminum acetylacetone
0.15 g of salt, and mix by stirring at 60 ° C. for 2 hours
did. Then, slowly cool to room temperature to hydrophilic binder poly
A polymer preparation solution (A) was obtained. [0242] [Chemical 9] <Formation of surface graft layer> Surface of the hydrophilic layer
Flat plate magnetron sputtering equipment (Shibaura Elette
CFS-10-EP70) manufactured by Kubo
Elementary glow treatment was performed. (Oxygen glow treatment conditions) Initial vacuum: 1.2x10^-3Pa, Argon pressure: 0.9 Pa, RF glow: 1.4kW Processing time: 60 sec Next, the glow-treated film was subjected to nitrogen bubbling.
Soaked in water (20%) for 4 hours at 60 ° C
Pickled. By washing the immersed membrane with running water for 10 minutes
The hydrophilicity of acrylic acid graft polymerized on the surface
A support S having a layer was obtained. <Formation of Image Forming Layer> Next, an image having the following composition is prepared.
An image forming layer coating solution was prepared. This coating solution is used as the support S.
Bar applied on top and dried in oven at 90 ° C for 120 seconds
Application amount 0.5 g / m²A lithographic stamp having an image forming layer
A printing plate was obtained. [0247] (Image forming layer coating solution composition)     70g of water     30 g of 1-methoxy-2-propanol     Microcapsule (1) (in terms of solid content) 5g     Polyhydroxyethyl acrylate 0.5g     p-diazodiphenylamine sulfate 0.3 g     Photothermal conversion substance (said IR-1) 0.3 g <Evaluation of original plate for lithographic printing>
The obtained original plate for lithographic printing is converted into a water-cooled 40W infrared semiconductor.
To the Trendsetter 3244VFS made by Creo with laser
Output 9W, outer drum rotation speed 210rpm, plate surface error
Energy 100mJ / cm²With a resolution of 2400 dpi
Heidelberg without processing after exposure under conditions
Attached to the cylinder of SOR-M printing machine
After supplying the ink, supply the ink, and further supply the paper for printing
Went. Can be developed on-machine without problems and can be printed
Met. Use a 20X magnifier for the 10th printed material
Evaluation, there was no background stain, the density of the solid image area
The uniformity of was very good. If you continue to print
However, there is no loss of fine lines or letters and uneven solid image density.
In addition, non-image areas are not smudged and a good printed product is 200.
More than 00 sheets were obtained. Example 2 Formation of the surface graft layer from the support S used in Example 1
The omitted support was used. Otherwise, the same as in Example 1.
An original plate for lithographic printing was prepared. Implemented this planographic printing plate
Exposure and printing were performed in the same manner as in Example 1. As a result, the example
Similar to 1, it shows good on-machine developability, and fine lines and characters
There are no missing or solid image density irregularities, and non-image areas are dirty.
There were no more than 20000 good prints. Examples 3 to 5 Example 1 Microcapsules of the image forming layer coating solution composition
In Example 3, the microcapsule (2) is replaced with the actual (1).
In Example 4, the microcapsule (3) is used.
Same as Example 1 except that it was replaced with the micro capsule (4)
Thus, an original plate for lithographic printing was produced. Next, Example 1
Similarly, these lithographic printing plates are exposed and printed.
went. As a result, all original plates have good on-machine developability.
, Lack of fine lines and fine characters, and uneven solid image density
No non-image area stains and good prints 2000
0 or more sheets were obtained. Example 6 Microcapsules of image forming layer coating solution composition of Example 2
Except for replacing (1) with microcapsules (6)
A lithographic printing original plate was produced in the same manner as in Example 2. Next
Then, in the same manner as in Example 1, these lithographic printing original plates
Exposed and printed. As a result, both original plates are good.
Shows good on-press developability, lack of fine lines and fine characters, and solid images
There is no unevenness in image density, no smudges on non-image areas, and good marks
More than 20000 copies were obtained. Examples 7 to 8 Hydrophilic layer coating solution for a support having a hydrophilic layer used in Example 1
The same as in Example 1 except that the composition was changed to the following composition.
Thus, an original plate for lithographic printing was produced. The following hydrophilic layer coating composition
As the hydrophobizing precursor of Example 9, in Example 9, the hydrophobizing precursor
(2) was used in Example 10 using the hydrophobized precursor (3)
It was. [0253] (Hydrophilic layer coating solution composition)   4.7 g of hydrophilic binder polymer preparation liquid (A)   Hydrophobized precursor (as a dilute aqueous solution with a solid content concentration of 16%) 3.5 g   4.8 g of 1.5% aqueous solution of photothermal conversion substance (Dye IR-2)   3.4g of water A lithographic printing plate produced as described above
Was exposed and printed in the same manner as in Example 1,
The printing original plate is also good as in Example 1, on-press developability,
Staining resistance and printing durability were shown. Comparative Example 1 The hydrophilic layer coating solution used in the production of the support of Example 1 was made hydrophobic.
Instead of the following coating liquids that do not contain the chemical precursor and photothermal conversion substance:
For lithographic printing for comparison as in Example 1 except for
An original plate was produced. [0256] (Comparative hydrophilic layer coating solution composition)   Anionic surfactant (manufactured by Nikko Chemicals,     Nikkor OTP-100s) 4% aqueous solution 0.24g   4.5 g of sol-gel preparation solution for hydrophilic layer (same as in Example 1) This lithographic printing plate was exposed in the same manner as in Example 1.
Lighted and printed. As a result, the non-image area of the printed material
The dirt was at a level where there was no practical problem, but it was printed
From this, it can be seen that thin lines and characters are missing.
It was. From the above results, the lithographic printing plate of the present invention
Is an excellent original plate for lithographic printing that has both stain resistance and printing durability.
It turns out that it is. [0259] According to the present invention, it is based on a digital signal.
After scanning exposure, the printer is installed without any processing.
A lithographic printing plate that can be worn and printed.
It has developability and the stain resistance in printing is further improved.
For lithographic printing with fine halftone dots and fine lines and high printing durability
Can provide original plate.

─────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme code (reference) G03F 7/11 503 G03F 7/11 503 F-term (reference) 2H025 AA12 AA13 AB03 AC08 AD01 BH03 BJ03 CC11 DA10 DA40 2H096 AA06 BA01 BA20 CA20 EA04 EA23 2H114 AA04 BA01 EA01 EA06

Claims (1)

What is claimed is: 1. A hydrophilic layer containing hydrophobized precursor fine particles and a hydrophilic binder polymer on a water-resistant support, a microcapsule enclosing the hydrophobic substance, and a photothermal conversion substance. A lithographic printing plate having an image forming layer containing in this order, wherein the hydrophilic binder polymer has a bond in which at least one atom selected from the group consisting of a metal atom and a metalloid atom is connected via an oxygen atom. Is a composite of a resin having a hydrophilic organic polymer, and a hydrophobic substance,
The contribution of cohesive energy within the minimum repeating unit is 10 kJ /
An original plate for lithographic printing, which is a hydrophobic resin having two or more mol groups of mol or more.