JPH09288351A - Original plate of waterless planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure aging stability and superior productivity as well as superior image reproducibility and ink repellency by incorporating hydrophobic epoxy compd. and a hydrophilic epoxy compd. into a primer layer. SOLUTION: A primer layer, a photosensitive layer and a silicone rubber layer are successively laminated on a substrate to obtain the objective original plate. The primer layer contains a hydrophobic epoxy compd. and a hydrophilic epoxy compd. preferably in a ratio of 1:(0.1-10), especially 1:(0.2-6), more especially 1:(0.3-5). When the epoxy compds. are blended in a ratio of 1:(0.1-10), only satisfactory properties of hydrophobic and hydrophilic epoxy resins are ensured.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a waterless planographic printing plate precursor, and more specifically, a primer layer for the purpose of improving adhesiveness and plate inspection property on a substrate, and a photosensitive material capable of receiving an ink. The present invention relates to a waterless planographic printing plate precursor in which a layer and a silicone rubber layer capable of repelling ink are provided in this order.

[0002]

2. Description of the Related Art Conventionally, waterless lithographic printing plate precursors having a silicone rubber layer as an ink repellent layer have been known, and as a typical example, a waterless lithographic printing plate provided with a photosensitive layer and a silicone rubber layer in this order. The original version is known. Waterless lithographic printing means that the image area and the non-image area are basically on the same plane, the image area is ink-receptive, the non-image area is ink repellent, and ink adhesion In the lithographic printing method, in which ink is applied only to the image area by utilizing the difference, and then the ink is transferred to the printing medium such as paper to perform printing, the non-image area is silicone rubber or a fluorine-containing compound. It means a printing method which can be printed without using fountain solution and is made of a substance having ink repellency.

As a positive type waterless planographic printing plate precursor used for positive working, for example, a type using a photopolymerizable photosensitive layer as a photosensitive layer is disclosed in Japanese Examined Patent Publication No. 54-269.
No. 23, Japanese Patent Publication No. 56-23150, etc. are proposed. Further, JP-A-5-281714 proposes a highly sensitive waterless planographic printing plate precursor by using a specific amino group-containing monomer. As a type using a photodimerization type photosensitive layer, Japanese Patent Publication No. 55-2278 plate is disclosed. As a negative type waterless planographic printing plate precursor used for negative working, for example, JP-B-46-16044 in which an aluminum substrate as a support is used as an image area, only the silicone layer in the exposed area is selectively removed. ,
Japanese Patent Publication No. 61-54222, in which the photosensitive layer serves as the image area, is known. These waterless planographic printing plate precursors are usually exposed to actinic rays through a positive film or a negative film. After that, by performing development processing, only the silicone rubber layer corresponding to the image area is peeled off, and the photosensitive layer is exposed to form an ink-imprinted image area. As the method of crosslinking and curing the silicone rubber layer, the following two methods of crosslinking are usually used.

(1) Condensation reaction cross-linking type: A method in which a polyorganosiloxane having hydroxyl groups at both ends is condensed and cross-linked with a silane or siloxane having a hydrolyzable functional group directly bonded to a silicon atom to form a silicone rubber.

(2) Addition reaction crosslinking type: a method in which a polysiloxane having a -Si-H group and a polysiloxane having a -CH = CH- group are subjected to an addition reaction to form a crosslinkable silicone rubber.

In particular, the condensation reaction-crosslinking silicone rubber (1) is preferable for a waterless lithographic printing plate precursor as a silicone rubber which is excellent in ink repulsion and easily exhibits adhesiveness with a photosensitive layer and has practically excellent performance. Has been used. The condensation-crosslinkable silicone gum composition generally comprises a polyorganosiloxane, a condensation-crosslinking agent, a condensation catalyst, a solvent, and a filler.

[0007] These typical waterless planographic printing plate precursors are provided with a primer layer, and the function that the primer layer should have is to protect the substrate material as well as
Adhesion to the substrate and photosensitive layer, solvent resistance, the primer layer composition itself does not adversely affect the plate performance, and the removal of physical irregularities on the substrate surface. , Blocking the chemical adverse effect of the substrate on the photosensitive layer. Various proposals have hitherto been made for the primer layer in the waterless planographic printing plate precursor. For example, Japanese Patent Laid-Open No. 63-
133153, JP-A-63-305360, JP-A-1-172834, and JP-A-2-242.
255, JP-A-2-34857, JP-A-2
Proposals such as JP-A-34857 and JP-A-3-180848 are made. However, these primers have a problem that it takes a long time to harden the film and the pot life after coating the primer layer is extremely short.

Further, JP-A-1-172834 discloses a method of coating a primer layer with a hardener after coating the primer layer. In-line mixing methods have been proposed, but each of them has problems of low productivity and high investment cost.

Among the proposals of these various primers,
In particular, as a practical proposal, Japanese Patent Publication No. 4-2941 and Japanese Patent Laid-Open No. 5-127368 disclose methods of using polyurethane for the primer. When these are used, the scratch resistance is improved, but the adhesion to the substrate is insufficient, and there has been a problem that peeling occurs due to this. To solve this problem, Japanese Patent Laid-Open No. 3-20
No. 0965, JP-A-3-27043, JP-A-3-296752, JP-A-3-182754, JP-A-3-286899, etc., a silane coupling agent and a compound having an active silyl group are disclosed. Although a method of adding is proposed, satisfactory adhesiveness has not been obtained.

As an attempt to improve the adhesion to a substrate, Japanese Patent Application Laid-Open Nos. 55-161244 and 62-5
No. 0760, Japanese Patent Publication No. 61-54219, Japanese Patent Laid-Open No. 62-194255 and the like disclose a method of containing an epoxy resin in a primer layer. Especially 3-3-3
No. 6208 proposes a method of improving the solvent resistance of the primer layer by thermally crosslinking a block type isocyanate and an epoxy resin, and in Japanese Patent Publication No. 6-82214, a hydroxyl group is added to improve the adhesiveness. A primer using an aliphatic epoxy resin containing at least one in the molecule has been proposed and put to practical use. However, these primer layers assume peeling due to a strong scratching force from the plate surface, that is, only a strong scratching force on the plate surface in work such as registering marks at the time of plate making or printing work, and therefore, at the time of development. No measures have been taken to prevent peeling due to water or an organic solvent penetrating the interface between the primer layer and the substrate. Therefore, the primer layer made of such a conventional technique still has insufficient adhesiveness,
There was a problem that the primer layer was peeled off from the substrate during development and that the image reproducibility was deteriorated over time.
Therefore, as a result of studies to solve the above problems, a method of using a hydrophobic epoxy resin for the primer layer was found.
Although this method almost solved the above-mentioned problems, it was found that the adhesiveness slightly deteriorates with the passage of time.

[0011]

The present invention was devised in view of the above-mentioned drawbacks of the prior art. The object is to solve the above problems and to impair the advantages of conventional waterless lithographic printing plate precursors. It is an object of the present invention to provide a waterless lithographic printing plate precursor which has excellent image reproducibility and ink repulsion property, is stable over time, and is excellent in productivity.

The inventors of the present invention have conducted intensive studies on solutions to the above-mentioned problems in the prior art, and as a result, by blending and using a hydrophobic epoxy compound and a hydrophilic epoxy compound in the primer layer, the primer layer The present invention has been accomplished by finding that an epoch-making primer layer having the above-mentioned drawbacks can be obtained without impairing the function to be provided.

[0013]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
In a waterless planographic printing plate precursor obtained by laminating a primer layer, a photosensitive layer and a silicone rubber layer in this order on a substrate,
This is achieved by a waterless lithographic printing plate precursor characterized in that the primer layer contains a hydrophobic epoxy compound and a hydrophilic epoxy compound.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The substrate of the waterless lithographic printing plate precursor according to the present invention needs to be able to withstand the flexibility attached to an ordinary lithographic printing machine and the load applied during printing. Typical examples include metal plates made of aluminum, copper, iron, etc., and metal plates deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., polyethylene terephthalate,
Examples thereof include films or sheets of polystyrene, polypropylene, etc., supports having rubber elasticity such as chloroprene rubber, NBR and the like, paper, resin coated paper, paper covered with metal foil and the like. The substrate may be a composite of the above materials. On these substrates, other substances can be further laminated for preventing halation, dyeing an image, or improving printing characteristics. In the present invention, an aluminum plate is preferably used as the substrate.
The aluminum plate is a plate-like body made of pure aluminum or aluminum alloy containing aluminum as a main component and containing a trace amount of foreign atoms. The foreign atoms include silicon, iron, magnesium, chromium, zinc, bismuth, nickel, titanium and the like, and the content is at most 10% by weight or less. Aluminum suitable for the present invention is pure aluminum, but completely pure aluminum is difficult to manufacture because of refining technology.
It is preferable that the content of foreign atoms is as low as possible. In the present invention, any aluminum alloy having the above-mentioned content can be used. The composition of the aluminum alloy is not specified, and conventionally known and publicly available materials can be appropriately used.

If desired, such an aluminum substrate is subjected to a treatment for removing rolling oil on the surface, for example, a degreasing treatment with a surfactant or an alkaline aqueous solution. Further, if desired, an anodic oxidation treatment and / or a hydrophilic treatment may be performed. As the hydrophilization treatment, an alkali metal silicate aqueous solution treatment and application of a colloidal silica sol are desirable. Further, in order to further improve the adhesion between the support and the primer layer, treatment with a known silane coupling agent, organic titanate or the like is possible within a range that does not adversely affect the plate performance.

The primer layer will be described.

The present invention is characterized in that a hydrophobic epoxy compound and a hydrophilic epoxy compound are used. In terms of ratio, the hydrophilic epoxy compound is preferably in the range of 0.1 to 10 with respect to the hydrophobic epoxy compound 1. When blended in this range, only good properties of the hydrophobic and hydrophilic epoxy resins are obtained. More preferably, the hydrophilic epoxy compound is 0.2 to 6 with respect to the hydrophobic epoxy compound 1, and more preferably 0.3 to 1 with respect to 1.
5 For example, if the amount of the hydrophobic epoxy resin increases, the adhesiveness will decrease with time. Further, when the hydrophilic epoxy resin is increased, the initial adhesiveness is poor and the image reproducibility is affected by the passage of time. That is, in any case, as a result, the performance of the waterless planographic printing plate precursor is affected.

The epoxy compound used in the present invention preferably has an epoxy equivalent of 300 or less for both the hydrophobic epoxy compound and the hydrophilic epoxy compound. It is more preferably 250 or less, still more preferably 150 or less. The epoxy equivalent here is the number of grams of an epoxy compound containing 1 g equivalent of an epoxy group. Epoxy equivalent is 300
If it becomes larger, the reactivity becomes poor and the thermosetting reaction at the time of coating the primer layer takes a long time. That is,
Large lack of productivity, poor practicality. In addition, since the reaction of the primer layer is not completed, the reaction of the unreacted epoxy compound proceeds by after-curing, and a stable primer layer cannot be obtained. Therefore, over time, the adhesiveness to the substrate is inferior, or the image reproducibility is deteriorated due to the impregnation of the monomer or isocyanate in the photosensitive layer, and the like. This will adversely affect storage stability.

Typical examples of the epoxy compound in the present invention are the following compounds, but the present invention is not limited thereto.

(1) Reaction product of bisphenol A and epichlorohydrin.

(2) A reaction product of a novolak resin and epichlorohydrin.

(3) Reaction product of bisphenol F and epichlorohydrin.

(4) Reaction product of tetrabromobisphenol A and epichlorohydrin.

(5) Cyclic aliphatic epoxy resin (compound having cyclohexanoxide group, tricyclodecenoxide group, cyclopentenoxide group).

(6) Glycidyl ester-based epoxy resin (reaction product of polycarboxylic acid and epichlorohydrin) (7) Glycidylamine-based epoxy resin (reaction product of amine and epichlorohydrin)

(8) Heterocyclic epoxy resin (hydantoin type epoxy resin obtained by glycidylating hydantoin ring and triglycidyl isocyanurate having triazine ring)
G) (9) Condensates of polyhydric alcohols and epichlorohydrin.

Among the epoxy compounds used in the present invention, as the hydrophobic epoxy compound, (1),
A compound having an aromatic group obtained by the method (4) or the like is preferably used, and a bisphenol type epoxy compound is particularly preferable. As the hydrophilic epoxy compound, compounds obtained by the methods (6), (7) and (9) are preferably used, and glycerol type epoxy compounds are particularly preferable.

The hydrophobic and hydrophilic epoxy compounds used in the present invention can be used alone to form a primer layer, and may be used in three-dimensional form by mixing with other components. Further, depending on the case, it may be used after being modified with other components. Examples of such other components include the following, but the present invention is not limited thereto.

(1) One or more of urethane resins, vinyl resins, acrylic resins, acrylic resins, alkyd resins, phenol resins, amino resins such as urea resins, melamine resins and benzoguanamine resins.

(2) Polyfunctional isocyanates such as paraphenylene diisocyanate, 2,4- or 2,6-
Toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl isocyanate or polymers thereof, adducts thereof, or block type isocyanate.

Typical examples are shown below, especially when used by mixing with other components. The present invention is not limited to these.

(1) Combination of Epoxy Resin and Base Resin (Carrier Resin) (2) Combination of Epoxy Resin, Base Resin (Carrier Resin) and Block Isocyanate The base resin (carrier resin) will be described in detail. In the primer layer of the present invention, various resins can be used as the base resin (carrier resin) for the purpose of the binder and for other purposes, and these resins can be used alone or in combination of two or more kinds. . Examples of representative resins are shown below, but are not limited thereto.

Urethane resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, epoxy polyester resin, polyamide resin, vinyl chloride-vinyl acetate copolymer, acrylate copolymer, acrylic resin, vinyl chloride resin, phenoxy resin, Polyvinyl butyral resin, polyvinyl acetate-polycarbonate resin,
Diene rubbers such as ethylene-vinyl acetate copolymer and polyacrylonitrile-butadiene copolymer, carboxy-modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, carboxy-modified acrylonitrile / butadiene rubber, polyisoprene rubber, acrylate rubber, cellulose and the like Derivatives, chitin, chitosan, milk casein, gelatin, soy protein, albumin, polyethylene, chlorinated polyethylene, chlorinated polypropylene, etc.

Typical examples of the use of (1) are shown below.
It is not limited to these.

(A) Epoxy resin and amino resin (b) Combination of epoxy resin, amino resin and phenol resin (c) Combination of epoxy resin and phenol resin (d) Combination of epoxy resin and urethane resin (e) Epoxy Combination of Resin and Curing Agent such as Amine, Polyamide, Acid Anhydride, etc. Further, typical use examples of (2) are shown below, but the invention is not limited thereto.

(F) Combination of Epoxy Resin, Urethane Resin and Block Isocyanate (g) Combination of Epoxy Resin, Urethane Resin, Amino Resin and Block Isocyanate In the present invention, good results are obtained in any of the above use examples. Although (a) is preferable, more preferable combinations include (b) and (g), and those containing an amino resin in the base resin are preferable. Particularly in the present invention, it is very preferable that the base resin contains a urethane resin and a block type isocyanate as in the use example (g).

The amino resin is extremely good as a curing agent for the epoxy resin, and when used in combination, the crosslinking reaction of the epoxy resin is promoted. In addition, by containing urethane resin and block type isocyanate, 3
The dimensional cross-linking reaction further improves the adhesiveness.

Examples of the amino resin include urea resin, melamine resin, benzoguanamine resin and urea melamine resin. N-butylation and is for easy handling
It may be o-butylated.

The optimum mixing ratio of (b) is 1 to 50 parts of amino resin and 1 to 30 parts of epoxy resin to 80 to 200 parts of phenol resin.

The optimum mixing ratio of (g) is 70 to 200 parts of the urethane resin, 1 to 50 parts of the block isocyanate, 1 to 60 parts of the amino resin, and 1 to 40 parts of the epoxy resin. .

Particularly in the present invention, it is preferable that the base resin (carrier resin) contains a urethane resin as in the use example (g). The urethane resin used in the present invention is
Any material may be used, and a polyurethane resin composed of a polyol component, an isocyanate component, a chain extender and the like is particularly preferably used. As typical polyol components, for example, as low molecular weight diols, ethylene glycol, propylene glycol, 1,4 butane diol, 1,6 hexane diol, diethylene glycol,
Examples include neopentyl glycol, bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, trishydroxymethylaminomethane and sorbitol.
Further, as the polymer diol, polypropylene glycol, polyethylene glycol, polytetraethylene glycol, ethylene oxide-propylene oxide copolymer, tetrahydrofuran-ethylene oxide copolymer, tetrahydrofuran-propylene oxide copolymer and succinic acid, glutaric acid, Polyester diol obtained from polycondensation reaction of saturated aliphatic carboxylic acid such as adipic acid or aromatic dicarboxylic acid such as phthalic acid and low molecular weight diol, or polyethylene adipate, polyhexamethylene adipate, polyneopentyl adipate,
Examples thereof include polyether diols such as polyhexamethylene neopentyl adipate and polyethylene hexamethylene adipate, and also polyether ester diol, polybutadiene diol, polycarbonate diol, polycaprolactone diol, and the like. Further, various phosphorus-containing polyols, halogen-containing polyols and the like can be used as the polyol.

Typical isocyanate components include p-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI) and chitosan. Siliene diisocyanate (XDI), hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, metaxylene diisocyanate (MXDI), hexamethylene diisocyanate (HDI or HMDI), lysine diisocyanate (LDI) (also known as 2,6-diisocyanate methylcaproate), hydrogen MDI (H12MDI) (alias 4,
4'-methylenebis (cyclohexyl isocyanate)), hydrogenated XDI (H6XDI) (also known as 1,3- (isocyanatomethyl) cyclohexane), isophorone diisocyanate (IPDI), diphenyl ether isocyanate, trimethylhexamethylene diisocyanate (TMDI), tetramethyl xylene diisocyanate , Polymethylene polyphenyl isocyanate, dimer acid cyisocyanate (DDI), triphenylmethane triisocyanate, tris (isocyanatophenyl) thiofesphate, tetramethyl xylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3 , 6-hexamethylene triisocyanate, biscloheptane triisocyanate and polyisocyanate Monomeric or modified products such as class and the like. Further, compounds obtained by reacting these isocyanate compounds with the above-mentioned polyol in such a ratio that the isocyanate groups remain can also be used as the isocyanate compound.

Typical chain extenders include p-xylenediamine, 1,4-diaminocyclohexane, p-phenylenediamine, bis (4-aminocyclohexyl) methane, 1,2-diaminopropane, 2,3-diaminobutane, Examples thereof include piperazine, 4,4'-diamino-diphenylmethane, trimethylene glycol-di-p-aminobenzoate, 4,4'-3,3'-diaminodichloro-diphenylmethane.

Typical examples of the block type isocyanate used in the present invention are shown below, but the present invention is not limited thereto. These can be used alone or in combination of two or more.

P-Phenylene diisocyanate, 2,4
-Or 2,6-toluene diisocyanate (TDI),
4,4-diphenylmethane diisocyanate (MD
I), tolidine diisocyanate (TODI), xylene diisocyanate (XDI), hydrogenated xylylene diisocyanate, cyclohexane diisocyanate,
Meta-xylene diisocyanate (MXDI), hexamethylene diisocyanate (HDI or HMDI),
Lysine diisocyanate (LDI) (also known as 2,6-diisocyanate methyl caproate), hydrogenated MDI (H
12MDI) (also known as 4,4'-methylenebis (cyclohexyl isocyanate)), hydrogenated XDI (H6XDI)
(Also known as 1,3- (isocyanatomethyl) cyclohexane), isophorone diisocyanate (IPDI), diphenyl ether isocyanate, trimethylhexamethylene diisocyanate (TMDI), tetramethyl xylene diisocyanate, polymethylene polyphenyl isocyanate, dimer acid cyisocyanate (DDI),
Triphenylmethane triisocyanate, tris (isocyanate phenyl) thiofesphate, tetramethyl xylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, biscloheptane triisocyanate, etc. Blocked polyisocyanates The reaction between each base resin and epoxy compound (epoxy resin) is described by Hashimoto, “Plastic Materials Lecture Epoxy Resin”.
(Published in Nikkan Kogyo Shimbun, 1969), Seino, “Synthetic Resin Industrial Technology Epoxy Resin” (Seibundo Shinkosha, 1962)
Annual publication) etc. can be followed.

Further, in the primer layer of the present invention, a white pigment or a yellow pigment such as titanium oxide or calcium carbonate can be added to prevent halation from the substrate and improve plate inspection. Along with dyes, pH indicators, exposure bakeout agents, photochromic compounds, photopolymerization initiators, thermal polymerization initiators, adhesion aids (eg, polymerizable monomers, diazo resins, silane coupling agents, titanate coupling agents, aluminum). Coupling agent, zirconia coupling agent,
Boron coupling agents, etc.), phosphorus-containing monomers, various catalysts,
Additives such as silica particles can also be added.

In particular, by combining the epoxy compound of the present invention with the organotin compound and the monomer represented by the following general formula (I), a waterless planographic printing plate precursor which is more stable over time and has excellent productivity is obtained. It becomes possible.

[0049]

Embedded image (However, R1 and R2 represent a hydrogen atom or a methyl group, a and b are integers of 1 or more, a + b = 3, and n is 0 to 20.
Represents an integer. ) Specific examples of typical organotin compounds are shown below, but the present invention is not limited thereto.

## [*****] represents the common name [composition formula].

Allyltri-n-butyltin [C15H32S
n], allyltrimethyltin [C6 H14 Sn], allyltriphenyl tin [C21 H20 Sn], bis (2-ethylhexanoate) tin [C16 H30 O4 Sn], bis (2,4-
Pentanedionate) Dichlorotin [C10H14O4 Cl2
Sn], bis (triphenyltin) oxide [C36H30
OSn2], bis (triphenyltin) sulfide [C
36H30SSn2], poly (n-butyltin hydroxide)
Oxide [(C4 H10 O2 Sn) n], n-Butyltrichlorotin [C4 H9 Cl3 Sn], n-Butyl tris (2-ethylhexanoate) tin [C28 H54 O6 S
n], cyclopentadienyltri-n-butyltin [C17
H32Sn], 1,3-diacetoxy-1,1,3,3-
Tetrabutyltin oxide [C20 H42 O5 Sn2], tin (II) acetate [C4 H6 O4 Sn], di-n-butyltin dilauryl mercaptide [C32 H68 S2 Sn], di-n
-Butyltin dioctoate [C28H48O4Sn], di-
n-butylbis (2,4-pentanedionate) tin [C
18H32O4 Sn], di-n-butyltin diacetate [C
12H24O4 Sn], di-n-butyldichlorotin [C8 H
18Cl2 Sn], di-t-butyldichlorotin [C8 H18
Cl2 Sn], di-n-butyldifluorotin [C8H18
F2 Sn], di-n-butyldilauryl tin [C32 H64 O
4 Sn], di-n-butyldimethoxytin [C10H24O2
Sn], poly (di-n-butyl (aleate) tin)
[(C12H20O4Sn) n], di-n-butyl-S, S
'-Bis (isooctylmercaptoacetate) tin [C
28H56O4 S2 Sn], poly (di-n-butyltin oxide) [(C8 H18OSn) n], poly (di-n-butyltin sulfide) [(C8 H18SSn) n], dimethylaminotri-n-butyltin []. C14H33NSn], dimethyl-S, S'-bis (isooctylmercaptoacetate) tin [C22H44O4S2Sn], dimethyldichlorotin [C2H6Cl2Sn], dimethyldineodecanoate tin [C22H44O4Sn], dimethylhydroxy (oleate). ) Tin [C20H40O3 Sn], dioctylchlorotin [C16H34Cl2 Sn], dioctyltin dilaurate [C40H80O4 Sn], poly (dioctyltin oxide) [(C16H34OSn) n], diphenyldichlorotin [C12H10Cl2Sn], ethynyltri-n-butyl-ethynyltri-n-n. [C14H28Sn], hexa-n-butylditin [C24H 54
Sn2], hexamethylditin [C6 H18 Sn2], methacryloxytri-n-butyl tin [C17 H32 O2 S
n], methyltrichlorotin [CH3Cl3Sn], octyltrichlorotin [C8H17Cl3Sn], phenyltri-n-butyltin [C18H32Sn], phenyltrichlorotin [C6H5Cl3Sn], sodium tin ethoxide [C18H45O9NaSn2], tetraallyl. Tin [C12
H20Sn], tetra-t-butoxytin [C16H36O4S
n], tetra-n-butyltin [C16H36Sn], tetraethyltin [C8H20Sn], tetraisopropyltin [C]
12H28Sn], tetramethyltin [C4H12Sn], tetra-n-octyltin [C32H68Sn], tetraphenyltin [C24H20Sn], tin (II) ethoxide [C4H10].
O2 Sn], tin (II) methoxide [C2 H6 O2 S
n], tin (II) oxalate [C2 O4 Sn], tin (II)
2,4-Pentanedionate [C10H14O4Sn], Tri-n-butylacetoxytin [C14H30O2Sn], Tri-n-butylbenzoyloxytin [C19H32O2S]
n], tri-n-butylbromotin [C12H27BrS
n], tri-n-butylchlorotin [C12H27ClS
n], tri-n-butylethoxytin [C14H32OS
n], tri-n-butylfluorotin [C12H27FS
n], tri-n-butyliodotin [C12H27ISn],
Tri-n-butylmethoxotin [C13H30OSn], tri-n-butyltin halide [C12H28Sn], tri-n-
Butyl (trifluoromethanesulfonate) tin [C13
H27F3 O3SSn], triethylbromotin [C6 H15
BrSn], (triisopropoxy titanoxy) tri-
n-Butyltin [C21H48O4TiSn], Trimethylchlorotin [C3H9ClSn], Trimethylsilyltri-
n-Butyltin [C15H36SiSn], Triphenylacetoxytin [C20H18O2Sn], Triphenylchlorotin [C18H15ClSn], Triphenylfluorotin [C18]
H15FSn], triphenylhydroxytin [C18H16OS
n], triphenyltin halide [C18H16Sn], vinyltri-n-butyltin [C14H30Sn], acrylic oxide tri-n-butyltin [C15H30O2Sn], acrylic oxide triphenyltin [C21H18O2Sn], diallyldibromotin [C6H10Br2Sn]. ], Diallyldi-
n-Butyltin [C14H28Sn], Di-n-butylbis (2-ethylhexylmaleate) tin [C32H56O8S
n], di-n-butyl bis (methyl maleate) tin [C
18H28O8Sn], tin di-n-butyl acrylate [C14
H24O4 Sn], di-n-butyl tin methacrylate [C16
H28O4 Sn], poly (dioctyl (maleate) tin)
[(C20H36O4Sn) n], divinyldi-n-butyltin [C12H24Sn], 1-ethoxyvinyltri-n-butyltin [C16H34OSn], tetravinyltin [C8H]
12Sn] etc.

Particularly preferred among these are di-n-
Butyltin diacetate [C12 H24 O4 Sn], di-n-
Butyldilauryltin [C32H64O4Sn] and di-n-butyltin dioctoate [C28H48O4Sn]. These organotin compounds accelerate the reaction between the base resin (carrier resin) and the block type isocyanate, and the reaction at a low temperature. Enables the completion of. Further reaction can be promoted by combining with the epoxy compound of the present invention. The amount added is preferably 0.0 based on the total primer composition.
The amount is 05 to 5% by weight, and more preferably 0.01 to 1% by weight. If the addition amount is less than 0.005% by weight, the above effect is poor, and if the addition amount is more than 5% by weight, the photosensitive layer is adversely affected and troubles such as development failure occur.

As the monomer represented by the general formula (I) used in the present invention, a compound in which a part of phosphoric acid is (meth) acrylic acid esterified is used. Examples of the (meth) acrylic acid ester used herein include 2-hydroxyethyl (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and 2-hydroxypropyl (meth). Acrylate, dipropylene glycol (meth) acrylate,
It is a (meth) acrylic acid ester containing a hydroxyl group at the terminal such as tripropylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate.
Among these, 2-hydroxypropyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable. When these (meth) acrylic acid esters are reacted with phosphoric acid to form phosphoric acid esters, one or two hydroxyl groups of phosphoric acid are used.
It is desirable that the individual be esterified. If all the hydroxyl groups are esterified, the adhesiveness to the support is adversely affected, causing peeling. These phosphoric acid ester-based monomers have photosensitivity, but when used in combination with an organic tin compound in the primer layer for thermosetting reaction, they bring about improvement in adhesiveness. Further, by combining with the epoxy compound of the present invention, the reaction of the epoxy compound is promoted, the reaction is completed in a short time, and the adhesiveness can be further improved. The amount of the phosphoric acid ester-based monomer added varies somewhat depending on the combination of the base resin (carrier resin) forming the primer layer, but is preferably 0.05 to 10% by weight with respect to the total primer composition.
More preferably, it is 0.1 to 7 parts by weight. If the addition amount is less than 0.05% by weight, the above effect is poor, and if it is more than 10% by weight, the photosensitive layer is adversely affected and troubles such as development failure occur.

For the stability of the coating solution, it is possible to add a polymerization inhibitor such as hydroquinone or phenothiazine as a thermal polymerization inhibitor. In order to further improve coating properties, it is optional to add alkyl ethers such as ethyl cellulose and methyl cellulose, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and the like. A plasticizer may be added to impart abrasion resistance. Representative plasticizers are shown below, but are not limited thereto.

Butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid, polyvinyl butyl ether, epoxy triglyceride, polyvinyl formal, and the like.

The composition for forming the primer layer used in the present invention is dissolved in a suitable organic solvent such as DMF, methyl ethyl ketone, methyl isobutyl ketone, dioxane, methyl lactate and ethyl lactate to give a composition solution. Is prepared. When a pigment or the like is contained, it is preferable to disperse it by using a known dispersing method such as SGI or a homogenizer as needed.

The film thickness of the primer layer used in the present invention is preferably in the range of 0.1 to 20 g / m 2 in terms of dry weight.
More preferably, the range is from 10 to 10 g / m2. If it is too thin, it will not function as a primer, and if it is too thick, it will not be economical.

Next, the photosensitive layer used in the present invention will be described. The photosensitive layer used in the present invention may be any as long as it changes the solubility in a developer before and after exposure. Specific examples include an ethylenically unsaturated compound, a diazo compound, a quinonediazide compound, an azide compound, an o-nitrobenzylcarbinol ester compound, and the like. A positive waterless planographic printing plate precursor is obtained by utilizing the photocuring reaction of these compounds, and a negative waterless planographic printing plate precursor is obtained by utilizing the photolysis reaction. The image formation in the present invention may be either a positive type or a negative type.

First, the positive type will be described in detail. As the photosensitive layer for positive working, a photocurable layer is mainly used, and a photopolymerizable layer and a photocrosslinkable layer are exemplified.

First, the photopolymerizable layer will be described. Examples of the photopolymerizable layer include a photopolymerizable adhesive layer having the following composition.

(1) Photopolymerizable unsaturated monomer or oligomer 1.0 to 100 parts by weight (2) Photopolymerization initiator 0.1 to 20 parts by weight (3) Photopolymerizable layer added as necessary Shape-maintaining filler (polymer or inorganic powder) 0.01 to 100 parts by weight Specific examples of the monomer or oligomer mentioned in (1) are shown below.

Examples of the monomers preferably used in the present invention include the monomers represented by the following general formula (II).

R 1 R 2 N- (X 1) p-(X 2) q -NR 3 R 4 (II) (wherein X 1 is a substituted or unsubstituted cyclic or acyclic alkylene having 1 to 20 carbon atoms, substituted or The substituent of unsubstituted phenylene or substituted or unsubstituted aralkylene is a divalent linking group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group and an aryl group.
X2 is -OE 1-, -S-E2-, -NH-E3-, -CO-OE4-.
, -SO2-NH-E 5-, E1, E2, E3, E4, E5
Represents a divalent linking group selected from the same as the above alkylene, phenylene and aralkylene. p represents an integer of 1 or more, q represents 0 or an integer of 1 or more. R1 and R2
, R3 and R4 are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, and a compound represented by the following formula (II
I), (IV), (V) means a functional group selected from
They may be the same or different. The substituent has 1 to 1 carbon atoms.
6 represents an alkyl group, a halogen atom, a hydroxyl group and an aryl group. However, at least one ethylenically unsaturated group is contained in one molecule of the compound (II). R5, R6, R
7 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, a CH2 = CH- group, or a CH2 = CCH3-group. Y represents -CO-O-, -CO-NH-, or a substituted or unsubstituted phenylene group. X3, X4 and X5 are the above X1 and X
Synonymous with 2. m and n represent 0 or 1. )

Embedded image In particular, a glycidyl (meth) acrylate having a photopolymerizable group and a monoglycidyl ether compound having no photopolymerizable group are subjected to an addition reaction with the following diamine compound are preferably used.

(A) Diamine compound (monooxyethylene diamine, dioxyethylene diamine, trioxyethylene diamine, tetraoxyethylene diamine, pentaoxyethylene diamine, hexaoxyethylene diamine, heptaoxyethylene diamine, octaoxyethylene diamine, nonaoxyethylene diamine, decaoxyethylene diamine, trioxyethylene diamine Triacontaoxyethylenediamine, monooxypropylenediamine, dioxypropylenediamine, trioxypropylenediamine,
Tetraoxypropylenediamine, pentaoxypropylenediamine, hexaoxypropylenediamine, heptaoxypropylenediamine, octaoxypropylenediamine, nonaoxypropylenediamine, decaoxypropylenediamine, tritriacontaoxypropylenediamine, N-hydroxyethylhexapropylenediamine, N-hydroxyisopropylhexapropylenediamine, N, N'-dihydroxyethylhexapropylenediamine, N, N'-dihydroxyisopropylhexapropylenediamine, trimethylenebis (4-aminobenzoate), (tetramethyleneglycolbis (4-aminobenzoate ), Dibutylene glycol bis (4-aminobenzoate), o-xylylenediamine, m-xylylenediene Amine, p-xylylenediamine, N-hydroxyethyl-m-xylylenediamine,
N-hydroxyisopropyl-m-xylylenediamine, N, N'-dihydroxyethyl-m-xylylenediamine, N, N-dihydroxyisopropyl-m-xylylenediamine, etc.) 1 mol (b) glycidyl (meth) acryle- To
4-n mol (c) monoglycidyl ether compound (methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl Ether, n-hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, n-decyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, glycidyl, etc. nmol (n is 0) ≦ n ≦ 4) addition reaction products are useful.

In addition to the ethylenically unsaturated compound having an amino group described above, known monomers and oligomers, small amounts of polydimethylsiloxane, silicone resins, known various modified polydimethylsiloxanes, and polyether modified polyethers. It is also possible to add a silicone compound such as polydimethylsiloxane or silicone (meth) acrylate. Specific examples of known monomers and oligomers are shown below.

Alcohols (ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, isoamyl alcohol, lauryl alcohol, stearyl alcohol, butoxyethyl alcohol, ethoxyethylene glycol, methoxyethylene glycol, methoxypropylene) (Meth) acrylic acid ester of glycolphenoxyethanol, phenoxydiethylene glycol, tetrahydrofurfuryl alcohol, etc.

Carboxylic acids (acetic acid, propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) and glycidyl (meth) acrylate or tetraglycidyl-m-xylylenediene Addition reaction product with amine or tetraglycidyl-m-tetrahydroxylylenediamine. Amide derivatives (acrylamide, methacrylamide, n-methylolacrylamide, methylenebisacrylamide, etc.). An addition reaction product of an epoxy compound and (meth) acrylic acid can be used. More specifically, Japanese Patent Publication No. 48-417
08, JP-B-50-6034, JP-A-51
Urethane acrylate described in JP-A-37193, JP-A-48-64183, JP-B-49-4
No. 3191, Japanese Patent Publication No. 52-30490, polyester acrylate, polyfunctional epoxy (meth) acrylate obtained by reacting an epoxy resin with (meth) acrylic acid, and N described in US Pat. No. 4,540,649. -A methylol acrylamide derivative. Furthermore, Japan Adhesion Association magazine VOL.20, No.
Photocurable monomers and oligomers described in 7, pages 300 to 308 can also be used. When a free acid is used as a raw material for the synthesis of ethylenically saturated monomer, the reaction mixture may have unreacted free acid. It can function as part or all.

It is also possible to use a polymerizable compound having a structure represented by the following general formula (VI) having no amino group structure in the photosensitive layer of the present invention.

[0069]

Embedded image (In the formula, R3 is a hydrogen atom, a halogen atom, or a carbon number of 1-10.
0 substituted or unsubstituted alkyl group, alkoxy group,
Amide group, acyloxy group, alkanoyl group, formyl group, carboxyl group, substituted or unsubstituted alkenyl group having 2 to 100 carbon atoms, alkenyloxy group, 4 carbon atoms
It is at least one selected from the group consisting of １００100 substituted or unsubstituted aryl groups and aryloxy groups. R4
Is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, an alkoxy group, an amide group,
Acyloxy group, alkanoyl group, formyl group, carboxyl group, C2-C100 substituted or unsubstituted alkenyl group, alkenyloxy group, C4-C100 substituted or unsubstituted aryl group, aryloxy group At least one selected. L1 and L2
Is a linking group. a and b indicate the presence or absence of a linking group, and are 0 or 1, which may be the same or different. In particular, it is preferable to include a polymerizable compound having at least one structure represented by the following general formula (VII) and having no amino group structure.

[0070]

Embedded image (In the formula, R3, R4, L2 and b are the same as those in the general formula (VI). L3 is a linking group, and is an ester bond, an amide bond, a urethane bond, a urea bond, a carbonate bond,
It is at least one selected from the group consisting of an ether bond, a neoether bond, a substituted or unsubstituted boron atom, a substituted or unsubstituted carbon atom, a substituted or unsubstituted phosphorus atom, and a substituted or unsubstituted silicon atom. L4 is a linking group. c represents the presence or absence of a linking group, and is 0 or 1. The linking group in the general formulas (VI) and (VII) may be any linking group as long as there is no amino group in the molecular skeleton. Since a, b, and c are 0 or 1,
In some cases, some of these linking groups may not be present. Specific examples of L1, L2 and L3 include substituted or unsubstituted boron, oxygen atom, halogen atom, alkaline earth metal, substituted or unsubstituted aluminum atom, substituted or unsubstituted silicon atom, substituted or unsubstituted At least one selected from the group consisting of a phosphorus atom, a sulfur atom and a transition metal, or an alkyl group, an alkenyl group, an aryl group and the like can be mentioned, and they may be the same or different. Further, these groups may have various bonds such as ester bond, urethane bond, urea bond, amide bond and carbonate bond. For example, an alkyl group containing an ester bond, an alkyl group containing an ester bond and an aromatic ring, an alkyl group containing an ether bond and an aromatic ring, an alkyl group containing an amide bond and an aromatic ring, and containing an urethane bond and an aromatic ring. But not limited thereto. More specifically, for example, an alkyl group containing an ether bond includes an ethylene oxide chain and a propylene oxide chain, and an alkyl group containing an ether bond and an aromatic ring includes a phenylene oxide chain. It is.

Specific examples of the silicone (meth) acrylate include 1,3-bis (3-methacryloxypropyl) -1,1,3,3, -tetramethyldisiloxane,
3-methacryloxypropylmethyldimethoxysilane,
1- (3-methacryloxypropyl) 1,1,3,3
3-pentamethyldisiloxane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltris (trimethylsiloxy) silane, α, ω-methacryloxypropylpolydimethylsiloxane, poly (methacryloxypropylmethyl-co-dimethyl) Siloxane and the like. Further, glycidyl (meth) acrylate having a photopolymerizable group in the following diamine silicone compound or (meth) acrylic acid chloride and a monoglycidyl ether compound having no photopolymerizable group,
The thing which added-reacted acid chloride etc. is also mentioned.

(A) Diamine silicone compound α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polymethylvinylsiloxane, α, ω-bis (3-aminopropyl) ) Polydiphenylsiloxane and the like.

1 mol (b) Glycidyl (meth) acrylate, (meth) acrylic acid chloride and the like.

4-n mol (c) monoglycidyl ether compound (methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether , Isobutyl glycidyl ether, n-hexyl glycidyl ether, 2 ethylhexyl glycidyl ether, n-decyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, glycidyl, etc.), acetic acid chloride , 2-ethylbutyric acid chloride, caproic acid chloride, caprylic acid chloride, 2-ethylhexanoic acid chloride, capric acid chloride, oleic acid chloride, lauric acid chloride, propionic acid chloride,
Benzoic acid chloride, succinic acid chloride, maleic acid chloride, phthalic acid chloride, tartaric acid chloride,
An addition reactant of n mol (n is an integer of 0 ≦ n ≦ 4) such as citric acid chloride is useful.

As the ethylenically unsaturated compound having an organic silyl group used in the present invention, a photopolymerizable ethylenically unsaturated compound is used in the case of a photopolymerizable layer, and a photocrosslinkable compound is used in the case of a photocrosslinkable layer. It is preferable to use a polar ethylenically unsaturated compound. The organic silyl group referred to in the present invention can be roughly classified into two groups: a hydrolyzable active silyl group and a non-hydrolyzable silyl group.

Examples of the hydrolyzable active silyl group include an alkoxysilyl group which regenerates a highly reactive group such as a silanol group by hydrolysis, an acetoxysilyl group, a silyl group such as an oximesilyl group, and a trimethylsiloxy group or a triethylsiloxy group. , Triphenylsiloxy groups and the like, in which alcoholic hydroxyl groups are regenerated by hydrolysis.

Specific examples of the alkoxysilyl group include trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group, vinyldimethoxysilyl group, vinylethoxysilyl group, allyldimethoxysilyl group and allyldiethoxysilyl group. Group, 3-methacryloxypropyldimethoxysilyl group, 3-methacryloxypropyldiethoxysilyl group, dimethylmethoxysilyl group, dimethylethoxysilyl group, divinylmethoxysilyl group, divinylethoxysilyl group, dianylmethoxysilyl group, dianylethoxy Examples thereof include a silyl group, a 3-methacryloxypropylmethoxysilyl group, and a 3-methacryloxypropylmethylethoxysilyl group.

Specific examples of the acetoxysilyl group include a triacetoxysilyl group, a methyldiacetoxysilyl group, an ethyldiacetoxysilyl group, a dimethyldiacetoxysilyl group and a diethylacetoxysilyl group.

Further, specific examples of the oxime silyl group include:
Examples thereof include trioxime silyl group, methyldiketoxime silyl group, ethyl ketoxime silyl group and the like.

As these ethylenically unsaturated compounds having a hydrolyzable active silyl group, the above-mentioned active silyl group and photopolymerizable or photocrosslinkable ethylenically unsaturated group are present in the same molecule. Although its molecular structure is not limited, the following compounds are common because of their ease of synthesis and availability.

That is, as the photopolymerizable one, polyhydric alcohol having 30 or less carbon atoms, (meth) acrylamide derived from polyhydric acid or acid anhydride or polyhydric amine, epoxy ester or allyl ester, (Meta)
In the middle or at the end of the step of synthesizing an ethylenically unsaturated compound such as an acrylamide or an addition reaction product of an epoxy ester, a compound having an organic silyl group as defined above is reacted into the same molecule. A method of incorporating an organic silyl group is generally used.

Examples of the above-mentioned organic silyl group compound used in the reaction include a chlorosilyl compound, an epoxyalkylsilyl group, an aminoalkylsilyl compound, a mercaptoalkylsilyl compound and an isocyanate alkylsilyl compound. These chlorosilyl group, epoxy group, The reaction is carried out using an amino group, a mercapto group, an isocyanate group or the like.

Specific examples are shown below, but the invention is not limited thereto.

(A) 3-methacryloxypropyltrimethoxysilane (b) 2-hydroxypropyl (meth) acrylate 1 mol triethoxychlorosilane 1 mol (c) pentaerythritol triacrylate 1 mol trimethoxychlorosilane 1 mol (d) ethylene Glycol diglycidyl ether / methacrylic acid addition reaction product 1 mol 3-isocyanatopropyltriethoxysilane nmol (n is an integer of 1 ≦ n ≦ 2) (e) diethylenetriamine 1 mol glycidyl (meth) acrylate 4-nmol 3- Glycidoxypropyltrimethoxysilane nmol (n is an integer of 1 ≦ n ≦ 3) (f) Triethylenetetraamine 1 mol Glycidyl (meth) acrylate 4-nmol 3-glycidoxypropyltri Methoxysilane nmol (n is an integer of 1 ≦ n ≦ 4) (g) Diaminodiphenylmethane 1 mol Glycidyl (meth) acrylate 4-nmol 3-glycidoxypropyltrimethoxysilane nmol (n is 1 ≦ n ≦ 4) (H) m-xylylenediamine 1 mol glycidyl (meth) acrylate 4-n mol 3-glycidoxypropyltrimethoxysilane nmol (n is an integer of 1 ≦ n ≦ 4) (i) 3-aminopropyl Trimethoxysilane 1 mol Glycidyl Methacrylate 2 mol The photocrosslinkable one is also similar to the photopolymerizable one in the method of introducing the organic silyl group. Specific examples include cinnamic acid esters of hydroxyl group-containing polymers such as polyvinyl alcohol, starch, and cellulose, in which some of the hydroxyl groups are organically silylated with trimethoxychlorosilane.

The non-hydrolyzable silyl group means a non-reactive silyl group, and examples thereof include an alkylsilyl group and an allylsilyl group. As these ethylenically unsaturated group compounds having a non-hydrolyzable silyl group, if the above-mentioned non-reactive silyl group and the photopolymerizable or photocrosslinkable ethylenically unsaturated group are present in the same molecule, The molecular structure is not limited at all, but the following compounds are generally used because of their ease of synthesis and availability. Specific examples are shown below, but are not limited thereto.

(A) m-Xylenediamine 1 mol Glycidyl (meth) acrylate 4-n mol Allyl glycidyl ether n mol (n is an integer of 1 ≦ n ≦ 4) The above addition reaction product and trimethoxysilane n mol (b ) 2-Hydroxypropyl (meth) acrylate 3 mol Methyltriacetoxysilane 1 mol Especially in the present invention, it is preferable to use an ethylenically unsaturated compound using a hydrolyzable active silyl group as the organic silyl group.

Specific examples of the photopolymerization initiator referred to in (2) are shown below. Various benzophenone compounds, substituted thioxanthone compounds, substituted acridone compounds, US Pat.
Bicinal polyketaldonyl compounds proposed in US Pat. No. 3,676,660, α-types proposed in U.S. Pat. Nos. 2,367,661 and 2,367,670.
Carbonyl compounds, acyloin ethers proposed in US Pat. No. 2,448,828, US Pat.
Aromatic acyloin compounds in which the α-position is substituted with a hydrocarbon proposed in JP-A-12, polynuclear quinone compounds proposed in US Pat. No. 3,046,127 and US Pat. No. 2,951,758, and proposed in US Pat. No. 3,549,367. Triaryl imidazole dimer / p-
A combination of aminophenyl ketones, US Patent 38705
No. 24, benzothiazole compounds, US Pat. No. 4,239,850, benzothiazole / trihalomethyl-s-triazine compounds, US Pat. No. 3,751,259, acridine and phenazine compounds, US Patent 42197
Oxadiazole compounds proposed in US Pat. No. 0,394,475, US Pat. No. 4,189,323.
JP, JP-A-53-133428, JP-A-60-133
-105667, JP-A-62-58241, and trihalomethyl-s-triazine-based compounds having a chromophore group proposed in JP-A-63-153542, JP-A-59-197401, JP-A-60-
And benzophenone group-containing peroxyester compounds proposed in Japanese Patent No. 76503. In particular, the photopolymerization initiator preferably used in the present invention includes a combination of a benzophenone compound represented by Michler's ketone and a substituted thioxanthone compound represented by 2,4-diethylthioxanthone.
Further, it is preferable to combine a substituted acridone compound represented by N-alkylacridone from the viewpoint of improving sensitivity and image reproducibility, particularly highlight reproducibility.

It is also possible to add various additives such as dyes and pigments, pH indicators, leuco dyes, surfactants, polymerization inhibitors and photoacid generators to the photosensitive layer used in the present invention.

It is also possible to add an organic acid as an agent for preventing discoloration of the dye due to a change with time and as an adhesive retainer for the photosensitive layer and the silicone rubber layer. For example, typical acids include saturated or unsaturated fatty acids having free carboxyl groups or aromatic mono- or polycarboxylic acids. Particularly, a saturated or unsaturated fatty acid having a free carboxyl group or an aromatic monovalent or polyvalent carboxylic acid having a solubility in water at 20 ° C. of 1 g or less is effective. As a specific example of such an organic carboxylic acid, Is an aliphatic dicarboxylic acid such as caproic acid, caprylic acid, capric acid, lauric acid, mistyric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid, cyclohexanecarboxylic acid, and fumaric acid. Acid, orthophthalaldehyde acid, phthalamic acid, tannic acid, o-troylic acid, m-troylic acid, p-troylic acid, benzoic acid, p-hydroxybenzoic acid, o-bromobenzoic acid, m
-Bromobenzoic acid, p-bromobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-methoxybenzoic acid, m-methoxybenzoic acid, p
-Aromatic monocarboxylic acids such as methoxybenzoic acid salicylic acid and aromatic dicarboxylic acids such as o-phthalic acid, m-phthalic acid and p-phthalic acid.

Among these acids, organic dicarboxylic acids are effective, and aromatic dicarboxylic acids are particularly effective.
The organic carboxylic acid in the present invention is used alone or in such a manner that the acid concentration in the photosensitive layer composition becomes 0.01 to 1.0 milligram equivalent / g, particularly preferably 0.02 to 0.5 milligram equivalent / g. It can be mixed and added. When the acid concentration is 0.01 mg / g or less, the effect on storage stability is weak, and when the acid concentration is 1.0 mg / g or more, photopolymerization is inhibited.

From the viewpoint of controlling the reaction between the photosensitive layer and the silicone rubber layer, a small amount of a known organic metal catalyst represented by dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate or the like is added to the photosensitive layer. It is also possible. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butylcresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2, 2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine, tempol and the like are useful. It is also preferable to add a fluorine-based surfactant for the purpose of improving the coating properties of the photosensitive layer composition.

The shape-retaining filler (polymer) referred to in (3)
Alternatively, any of inorganic powders) can be used as long as it is soluble in an organic solvent and has a film-forming ability, but preferably includes polymers and copolymers having a glass transition temperature (Tg) of 0 ° C. or lower. it can. Representative examples are shown below, but are not limited thereto. (Meth) acrylic acid compound copolymer, crotonic acid compound copolymer, maleic acid compound copolymer, partially esterified maleic acid compound copolymer such as rosin modification, acidic cellulose derivative, polyvinylpyrrolidone, polyethylene oxide ,
Alcohol-soluble nylon, polyester resin, unsaturated polyester resin, polyurethane resin, polystyrene resin, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl formal, polyvinyl chloride, polyvinyl alcohol, partially acetalized polyvinyl alcohol, water-soluble nylon, water-soluble urethane , Gelatin, water-soluble cellulose derivatives and the like can be used alone or as a mixture of two or more. Further, a polymer compound having a photopolymerizable or photocrosslinkable olefinic unsaturated double bond group in its side chain can be used alone or in combination with two or more kinds in addition to the above polymers. In particular,
Allyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomer copolymers proposed in JP-A-59-53836, and alkali metal salts or amine salts thereof, Japanese Patent Publication 59-459
Hydroxyethyl (meth) proposed in Japanese Patent No. 79
Acrylate / (meth) acrylic acid / alkyl (meth)
Acrylate copolymer and its alkali metal salt or amine salt reacted with (meth) acrylic acid chloride, maleic anhydride copolymer proposed in JP-A-59-71048 and pentaerythritol triacrylate. Added by half-esterification, its alkali metal salt or amine salt, styrene / maleic anhydride copolymer to monohydroxyalkyl (meth) acrylate and / or polyethylene glycol mono (meth) acrylate and / or polypropylene glycol mono ( (Meth) acrylate added by half-esterification, and its alkali metal salt or amine salt,
(Meth) acrylic acid copolymer or crotonic acid copolymer partially reacted with glycidyl (meth) acrylate, its alkali metal salt or amine salt, hydroxyalkyl (meth) acrylate copolymer , Polyvinyl formal and / or polyvinyl butyral with maleic anhydride or itaconic anhydride, its alkali metal salt or amine salt, hydroxyalkyl (meth) acrylate / (meth) acrylic acid copolymer, 2,4- Tolylene diisocyanate / hydroxyalkyl (meth) acrylate = 1: 1 addition reaction product further reacted, and its alkali metal salt or amine salt, (meth) acryl proposed in JP-A-59-53836. Part of acid copolymer reacted with allyl glycidyl ether Allowed ones and their alkali metal salts or amine salts, (meth) allyl acrylate / styrene sulfonate sodium copolymers, (meth) vinyl acrylate / styrene sulfonate sodium copolymers,
(Meth) allyl acrylate / acrylamide / 1,1
-Sodium dimethylethylene sulfonate copolymer,
(Meth) vinyl acrylate / acrylamide / 1,1-
Sodium dimethylethylene sulfonate copolymer,
Examples thereof include 2-allyloxyethyl (meth) acrylate / methacrylic acid copolymer, 2-allyloxyethyl (meth) acrylate / 2-methacryloxyethyl hydrogen succinate copolymer, and the like. In the present invention, a polyurethane resin is preferably used. In particular, when the same resin as the polyurethane resin used for the primer layer is used for the photosensitive layer, the adhesiveness at the interface between the primer layer and the photosensitive layer is improved, and peeling between the photosensitive layer and the primer layer is prevented. Therefore, the peeling between the primer layer and the substrate due to the peeling hardly occurs, and by using the epoxy resin of the present invention together, it is possible to solve the problem of poor adhesion between the layers.

Next, the photocrosslinkable photosensitive layer will be described.
Examples of the substance used for the photocrosslinkable photosensitive layer include the following compounds.

Polyesters and polycarbonates having the following structure in the main chain or side chain of a photosensitive layer or polymer containing a photodimerization type photosensitive resin, such as polyvinyl cinnamate,
Polyamides, poly (meth) acrylates, polyvinyl alcohol derivatives, epoxy resin derivatives, diazo compounds, azide compounds and the like.

For example, P-phenylenediacrylic acid and 1,4-
Such as 1: 1 polycondensation unsaturated polyester of dihydroxyethyloxycyclohexane, photosensitive polyester derived from cinnamylidenemalonic acid and bifunctional glycols, polyvinyl alcohol, starch, cellulose and the like. Cinnamate esters of hydroxyl-containing polymers.

The photocrosslinkable photosensitive layer is also the same as the above-mentioned photocurable photosensitive layer, in addition to the photocrosslinkable compound, a compound having one or more organic silyl groups in the molecule, a photosensitizer, and if necessary. It is mainly composed of a thermal polymerization inhibitor and a shape-retaining filler added.

The ethylenically unsaturated compound having at least one organic silyl group in the molecule used for the photocrosslinkable layer is preferably a photocrosslinkable ethylenically unsaturated compound.

The method of introducing these organic silyl groups is also based on the photopolymerizable method. As a specific example, polyvinyl alcohol
Examples of cinnamic acid esters of hydroxyl group-containing polymers such as starch, starch, cellulose and the like, in which some of the hydroxyl groups are organically silylated with trimethoxychlorosilane and the like.

In addition to the above components, if necessary, a dye,
Addition of additives such as a pigment, a photochromic agent, a catalyst, and a light absorber is optional as in the case of the photocurable photosensitive layer.

Next, the diazo compound will be described in detail. Examples of the diazo compound used in the present invention include a water-insoluble organic solvent-soluble diazo resin represented by a condensate of p-diazodiphenylamine and formaldehyde. Specifically, Japanese Patent Publications 47-1167 and 57-
There is something like that described in 43890. Generally, a diazo resin represented by the following general formula (VIII) is preferably used.

[0101]

[Chemical 6] (In the formula, R6, R7, and R8 represent a hydrogen atom, an alkyl group, and an alkoxy group, and R9 represents a hydrogen atom, an alkyl group, or a phenyl group. X represents PF6, B.
It means F4. Y means -NH-, -S-, -O-. ) Examples of the diazo monomer in the diazo resin used in the present invention include 4-diazo-diphenylamine, 1-
Diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N- Methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1-diazo-4-N
-Benzylaminobenzene, 1-diazo-4-N, N-
Dimethylaminobenzene, 1-diazo-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-p
-Tolylmercaptobenzene, 1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene, p-diazo-dimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo- 2,5-diethoxy-4-morpholinobenzene, 1-diazo-
2,5-dimethoxy-4-morpholinobenzene, 1-
Diazo-2,5-diethoxy-4-p-tolylmercaptobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-benzyl Aminobenzene, 1-
Diazo-3-chloro-4-diethylaminobenzene, 1
-Diazo-3-methyl-4-pyrrolidinobenzene, 1-
Diazo-2-chloro-4-N, N-dimethylamino-5
-Methoxybenzene, 1-diazo-3-methoxy-4-
Pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- (n-propoxy) -4-diazodiphenylamine, 3- (isopropoxy) -4-diazodiphenylamine and the like can be mentioned. .

Examples of the aldehyde used as a condensing agent with these diazo monomers include formaldehyde, acetaldehyde, propionaldehyde,
Butyraldehyde, isobutyraldehyde, benzaldehyde and the like can be mentioned.

Further, as the anion, a water-soluble diazo resin can be obtained by using chlorine ion or trichlorozinc acid, and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalene sulfonic acid, 4,
4'-biphenyl sulfonic acid, 2,5-dimethylbenzene sulfonic acid, 2-nitrobenzene sulfonic acid,
By using 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid or the like, an organic solvent-soluble diazo resin can be obtained.

Further, these diazo resins are preferably used as a mixture with a polymer compound having a hydroxyl group as described below. That is, as the polymer compound having a hydroxyl group, a monomer having an alcoholic hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,
3-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, 1,3-propanediol mono (meth) acrylate, 1, Copolymer between at least one kind of monomer selected from 4-butanediol mono (meth) acrylate, di (2-hydroxyethyl) maleate, etc. and another monomer having no hydroxyl group, and phenol. Monomers having a hydroxyl group, for example N- (4-hydroxyphenyl) (meth) acrylamide, N- (4-hydroxyphenyl)
Maleimide, o-, m-, p-hydroxystyrene, o
-, M-, p-hydroxyphenyl (meth) acrylate, etc., copolymers, ring-opening reaction products of p-hydroxybenzoic acid and glycidyl (meth) acrylate, salicylic acid and 2-hydroxyethyl (meth). ) A copolymer with a hydroxyl group-containing monomer or the like such as a reaction product with an acrylate. Further, polyvinyl alcohol, cellulose, polyethylene glycol, polypropylene glycol, glycerin, pentaerythritol and the like, epoxy addition reaction products thereof, and other hydroxyl group-containing natural polymer compounds can also be used.

These diazo compounds may or may not have the above-mentioned organic silyl group, but at least one organic silyl group and at least one diazo group are contained in the same molecule. Preferably present. These diazo compounds may be used alone or in admixture of two or more. When the organic silyl group and the diazo group are present in the same molecule, the organic silyl group content is 0.01 to 50.
It is preferably in the range of mol%.

When the compound having an organic silyl group and the diazo compound are mixed and used, the mixing ratio of the compound having an organic silyl group to the diazo compound and other components is determined by the kind of the polymer compound or diazo compound to be used. Generally, the compound having an organic silyl group is preferably in the range of 90 to 0.1% by weight, and more preferably in the range of 50 to 1% by weight. .

Next, the negative type will be described in detail. As the photosensitive layer for negative working, a quinonediazide compound is preferably used as a photo-soluble photosensitive layer or a photo-peelable photosensitive layer. The photo-soluble photosensitive layer is a type of photosensitive layer in which the exposed portion of the photosensitive layer is dissolved by exposure and development, and the primer layer is exposed. This means that the silicone rubber layer thereon is removed without substantially removing the photosensitive layer. It is obtained by cross-linking a known quinonediazide compound with a polyfunctional compound or by modifying the active group in the quinonediazide compound with a monofunctional compound so as to make it insoluble or insoluble in a developing solution. . In the present invention, a photo-peelable photosensitive layer is preferably used from the viewpoint of problems such as application of a photosensitive solution and ink mileage.

Examples of the quinonediazide compound used herein include quinonediazide compounds used in positive PS plates, Wipon plates, photoresists and the like. Specifically, for example, 1,2-benzoquinone diazide 4-sulfonic acid chloride, 1,2-naphthoquinone diazide 4-sulfonic acid chloride, 1,2-naphthoquinone diazide 5-sulfonic acid chloride, 1,2-naphthoquinone diazide 6 A condensate of sulfonic acid chloride and a compound containing a hydroxyl group and / or an amino group is preferably used.

Examples of the hydroxyl group-containing compound include dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dihydroxyanthraquinone, bisphenol A, phenol formaldehyde novolac resin (phenol, p-tert-butylphenol, p-octylphenone). -, P-nonylphenol, cardanol, cresol, xylenol, catechol and pyrogallol, and phenols and formaldehydes are condensed in the presence of an acidic catalyst. Soluble fusible resin), Resole resin (for example,
Resin obtained by condensing the above-mentioned phenols and formaldehyde in the presence of an alkali catalyst), resorcinbenzaldehyde condensation resin, pyrogallolacetone resin, p
-Hydroxystyrene copolymer resin, poly-4-vinylphenol, poly-4-oxymethacrylanilide, polyvinyl alcohol, cellulose and its derivatives, chitin, chitosan, polyurethane having a hydroxyl group and the like.

Examples of the amino group-containing compound include aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4'-diaminodiphenylamine,
4,4'-diaminobenzophenone, poly-4-aminostyrene and the like.

Further, Japanese Patent Application Nos. 6-183757 and 6
The compounds described in Japanese Patent Application No. 183758, Japanese Patent Application No. 6-143276, Japanese Patent Application No. 6-143277 can also be used as the quinonediazide compound.

Regarding the quinonediazide compounds including those described here, Nagamatsu and Inui jointly published “Photosensitive Polymer” (Kodansha, published in 1977) and Tsunoda “New photosensitive resin”.
(Published by Printing Society of Japan, published in 1981), jointly written by Yamada and Morita, "Photosensitive Resin" edited by The Polymer Society of Japan (Kyoritsu Shuppan, 1988).
And published by Tsuda, edited by the Surface Science Society of Japan, "Molecular Design of Ultra LSI Resist" (Kyoritsu Shuppan, 1990).

Among these quinonediazide compounds,
A combination of 1,2-naphthoquinone-2-diazido-5-sulfonic acid chloride and a phenol formaldehyde novolac resin is preferable, and more preferable is a phenol formaldehyde novolak resin in which 5% to 65% of the hydroxyl groups of the phenol formaldehyde resin are esterified. 1,2-naphthoquinone-2-diazide 5-sulfonic acid ester.

Examples of the polyfunctional compound used for introducing the crosslinked structure include the polyfunctional isocyanates described in the section of the primer layer and the polyfunctional epoxy compounds shown below.

Examples of polyfunctional epoxy compounds include polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, and the like. To be Preferred among these are polyfunctional isocyanate compounds.

The amount of these polyfunctional compounds used is preferably 1 to 150 parts by weight, more preferably 5 to 100 parts by weight, and even more preferably 10 to 80 parts by weight, based on 100 parts by weight of the photosensitive compound. ..

It is necessary to carry out the thermal curing at a temperature which does not lose the photosensitivity of the photosensitive material, usually at 150 ° C. or lower. For this reason, it is preferable to use a catalyst in combination.

As a method of modifying a quinonediazide compound with a monofunctional compound to make it slightly soluble or insoluble in a developing solution, similarly, the active group of the photosensitive compound may be esterified, amidated or urethane. It can be mentioned that The compound that reacts with the active group of the photosensitive compound may be a low molecular weight compound or a relatively high molecular weight compound, or a monomer may be graft-polymerized to the photosensitive compound.

As the binder polymer of the photosolubilizing type photosensitive layer, various polymers and copolymers described for the primer layer and the photocurable type photosensitive layer can be used.

The polymers which can be used as the binder polymer may be used alone or in combination of several kinds.

Among the binder polymers, polyurethane resin, polyester resin, vinyl polymer resin and unvulcanized rubber are preferable. The binder polymer is preferably used in an amount of 0.5 to 80% by weight, more preferably 10 to 65% by weight, most preferably 15 to 5% by weight based on the components of the photosensitive layer.
5 wt%. When the binder polymer content is less than 0.5 wt%, it is difficult to develop satisfactory physical properties of the photosensitive layer. On the other hand, when the binder polymer content is more than 80 wt%, the amount of the quinonediazide compound is decreased, resulting in image reproduction. Causes problems with respect to developability, developability, SK adhesion, and the like.

Further, a binder polymer of 0.5 to 80 wt% with respect to the components of the photosensitive layer, and a 1,2-naphthoquinone-2-diazide 5-sulfonic acid ester of a phenol formaldehyde novolac resin having an esterification rate of 5 to 65% as a quinonediazide compound. The combination of is a particularly preferable composition. When the quinonediazide sulfonic acid esterification rate of the hydroxyl groups of the phenol formaldehyde resin is less than 5%, the number of photosensitive groups is small, which causes a problem that image reproducibility and developability are deteriorated. On the other hand, the esterification rate is 65
When it is higher than%, it means that the residual hydroxyl group, that is, the number of cross-linking points is reduced, and thus causes a problem in solvent resistance and SK adhesive strength of the photosensitive layer.

In addition to the above components, it is optional to add additives such as acids, dyes, pigments, photocolor formers, catalysts and light absorbers as required.

The thickness of the various photosensitive layers described above is 0.1 to 100 μm, preferably 0.5 to 10 μm. If the thickness is too thin, defects such as pinholes are likely to occur during coating, while if it is too thick, it is disadvantageous from an economic viewpoint.

Examples of the silicone rubber layer used in the present invention include, but are not limited to, those having the following (1) condensation crosslinking type and (2) addition crosslinking type.

(2) The condensation-crosslinking type silicone rubber layer is a silicone rubber layer obtained by condensing a linear polyorganosiloxane, and the polyorganosiloxane referred to in the present invention is represented by the following general formula (IX). Means linear polyorganosiloxane. The silicone gum composition according to the present invention refers to an uncured (non-rubberized) solution composition obtained by dissolving the polyorganosiloxane in an appropriate solvent to form a solution and then mixing the solution with a crosslinking agent, a catalyst, and the like. On the other hand, the term "silicone rubber" means a cured product obtained by subjecting the silicone gum composition to a cross-linking reaction under appropriate curing conditions and rubberized.

[0127]

Embedded image (Here, n is an integer of 1 or more, R10 and R11 are carbon atoms 1
-10 alkyl group, alkoxy group, aminoalkyl group, haloalkyl group, hydroxyalkyl group, carbon number 2
A carboxyalkyl group having 10 to 10, a cyanoalkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
An aryloxy group, an aralkyl group, or a group selected from a hydrogen atom and a hydroxyl group, which may be the same or different. Further, it has at least one or more hydroxyl group in the molecular chain at the chain end or in the form of a side chain. As the condensation reaction crosslinkable silicone gum composition, a so-called room temperature (wherein a crosslinker and, if necessary, a catalyst are added to an organic solvent solution of the linear polyorganosiloxane represented by the above general formula (IX)). Low temperature) Moisture-curing type. As the condensation reaction cross-linking agent used for constituting the silicone gum composition, acetoxysilane, ketoxime silane, alkoxy silane, amino silane, amido silane and the like as shown by the following general formula (X) are preferably used. Generally, a cross-link which is reacted with a linear polyorganosiloxane having at least one hydroxyl group in the molecular chain and cross-linked by a condensation reaction in the form of deacetic acid, deoxime, dealcohol, deamine, deamide, etc., respectively. The agents are used in single or mixed form or in the form of condensates. Particularly in the present invention, acetoxysilane,
Ketoxime silane, alkoxysilane and the like are preferably used.

Rm · Si · Xn (X) (where m and n are integers satisfying m ≧ 0 and n ≧ 1 and m + n = 4. R is a substituted or unsubstituted C 1 to C 20 Alkyl group, aminoalkyl group, aminoalkyleneaminoalkyl group, aminoalkyleneaminomethylphenethyl group, substituted or unsubstituted carbon number 6 to 20
X represents -OR1, -OCOR2,-.
ON-CR = CR3-R4, -OC-CR5H. R
1 to R5 mean a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms) Specific examples of the condensation reaction crosslinking agent or its condensate are as follows.

Tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, Ethyltriacetoxysilane, dimethyldiacetoxysilane, γ-aminopropyltriethoxysilane, N- (βaminoethyl) -γ-aminopropyltrimethoxysilane, N- (βaminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-chloropropyltriethoxysilane, N- (βaminoethyl) aminomethylphenethyltrimethoxysilane, - (beta-aminoethyl) aminomethyl phenethyl triethoxysilane, tris (methyl ethyl ketoxime) methylsilane, tris (methyl ethyl ketoxime) ethylsilane, tris (methyl ethyl ketoxime) vinylsilane, tetrakis (methyl ethyl ketoxime) silane and the like.

As the condensation catalyst, a compound selected from the group consisting of organic tin compounds, organic titanium compounds, organic aluminum compounds, organic lead compounds, organic boron compounds and organic zirconium compounds can be used. In particular, a compound selected from the group consisting of an organotin compound, an organic titanium compound and an organic aluminum compound is preferable in terms of efficiently exhibiting a condensation catalyst effect, and more preferably a compound selected from the group consisting of an organic tin compound. Specific examples of the organotin compound include the following.

#### [*****] represents the common name [compositional formula].

Allyltri-n-butyltin [C15H32S
n], allyltrimethyltin [C6 H14 Sn], allyltriphenyl tin [C21 H20 Sn], bis (2-ethylhexanoate) tin [C16 H30 O4 Sn], bis (2,4-
Pentanedionate) Dichlorotin [C10H14O4 Cl2
Sn], bis (triphenyltin) oxide [C36H30
OSn2], bis (triphenyltin) sulfide [C
36H30SSn2], poly (n-butyltin hydroxide)
Oxide [(C4 H10 O2 Sn) n], n-Butyltrichlorotin [C4 H9 Cl3 Sn], n-Butyl tris (2-ethylhexanoate) tin [C28 H54 O6 S
n], cyclopentadienyltri-n-butyltin [C17
H32Sn], 1,3-diacetoxy-1,1,3,3-
Tetrabutyltin oxide [C20 H42 O5 Sn2], tin (II) acetate [C4 H6 O4 Sn], di-n-butyltin dilauryl mercaptide [C32 H68 S2 Sn], di-n
-Butyltin dioctoate [C28H48O4Sn], di-
n-butylbis (2,4-pentanedionate) tin [C
18H32O4 Sn], di-n-butyltin diacetate [C
12H24O4 Sn], di-n-butyldichlorotin [C8 H
18Cl2 Sn], di-t-butyldichlorotin [C8 H18
Cl2 Sn], di-n-butyldifluorotin [C8H18
F2 Sn], di-n-butyldilauryl tin [C32 H64 O
4 Sn], di-n-butyldimethoxytin [C10H24O2
Sn], poly (di-n-butyl (aleate) tin)
[(C12H20O4Sn) n], di-n-butyl-S, S
'-Bis (isooctylmercaptoacetate) tin [C
28H56O4 S2 Sn], poly (di-n-butyltin oxide) [(C8 H18OSn) n], poly (di-n-butyltin sulfide) [(C8 H18SSn) n], dimethylaminotri-n-butyltin []. C14H33NSn], dimethyl-S, S'-bis (isooctylmercaptoacetate) tin [C22H44O4S2Sn], dimethyldichlorotin [C2H6Cl2Sn], dimethyldineodecanoate tin [C22H44O4Sn], dimethylhydroxy (oleate). ) Tin [C20H40O3 Sn], dioctylchlorotin [C16H34Cl2 Sn], dioctyltin dilaurate [C40H80O4 Sn], poly (dioctyltin oxide) [(C16H34OSn) n], diphenyldichlorotin [C12H10Cl2Sn], ethynyltri-n-butyl-ethynyltri-n-n. [C14H28Sn], hexa-n-butylditin [C24H 54
Sn2], hexamethylditin [C6 H18 Sn2], methacryloxytri-n-butyl tin [C17 H32 O2 S
n], methyltrichlorotin [CH3Cl3Sn], octyltrichlorotin [C8H17Cl3Sn], phenyltri-n-butyltin [C18H32Sn], phenyltrichlorotin [C6H5Cl3Sn], sodium tin ethoxide [C18H45O9NaSn2], tetraallyl. Tin [C12
H20Sn], tetra-t-butoxytin [C16H36O4S
n], tetra-n-butyltin [C16H36Sn], tetraethyltin [C8H20Sn], tetraisopropyltin [C]
12H28Sn], tetramethyltin [C4H12Sn], tetra-n-octyltin [C32H68Sn], tetraphenyltin [C24H20Sn], tin (II) ethoxide [C4H10].
O2 Sn], tin (II) methoxide [C2 H6 O2 S
n], tin (II) oxalate [C2 O4 Sn], tin (II)
2,4-Pentanedionate [C10H14O4Sn], Tri-n-butylacetoxytin [C14H30O2Sn], Tri-n-butylbenzoyloxytin [C19H32O2S]
n], tri-n-butylbromotin [C12H27BrS
n], tri-n-butylchlorotin [C12H27ClS
n], tri-n-butylethoxytin [C14H32OS
n], tri-n-butylfluorotin [C12H27FS
n], tri-n-butyliodotin [C12H27ISn],
Tri-n-butylmethoxotin [C13H30OSn], tri-n-butyltin halide [C12H28Sn], tri-n-
Butyl (trifluoromethanesulfonate) tin [C13
H27F3 O3SSn], triethylbromotin [C6 H15
BrSn], (triisopropoxy titanoxy) tri-
n-Butyltin [C21H48O4TiSn], Trimethylchlorotin [C3H9ClSn], Trimethylsilyltri-
n-Butyltin [C15H36SiSn], Triphenylacetoxytin [C20H18O2Sn], Triphenylchlorotin [C18H15ClSn], Triphenylfluorotin [C18]
H15FSn], triphenylhydroxytin [C18H16OS
n], triphenyltin halide [C18H16Sn], vinyltri-n-butyltin [C14H30Sn], acrylic oxide tri-n-butyltin [C15H30O2Sn], acrylic oxide triphenyltin [C21H18O2Sn], diallyldibromotin [C6H10Br2Sn]. ], Diallyldi-
n-Butyltin [C14H28Sn], Di-n-butylbis (2-ethylhexylmaleate) tin [C32H56O8S
n], di-n-butyl bis (methyl maleate) tin [C
18H28O8Sn], tin di-n-butyl acrylate [C14
H24O4 Sn], di-n-butyl tin methacrylate [C16
H28O4 Sn], poly (dioctyl (maleate) tin)
[(C20H36O4Sn) n], divinyldi-n-butyltin [C12H24Sn], 1-ethoxyvinyltri-n-butyltin [C16H34OSn], tetravinyltin [C8H12].
Sn] and the like.

The composition of the silicone rubber layer is not particularly limited, but 3 to 20 parts by weight of the condensation reaction crosslinking agent and 0.001 to 0.05 parts by weight of the condensation catalyst are added to 100 parts by weight of the polyorganosiloxane. Different compositions are preferred.

(2) The addition-crosslinking type silicone rubber layer comprises a polyvalent hydrogenorganopolysiloxane and 2 molecules per molecule.
It is obtained by a reaction with a polysiloxane compound having one or more —CH═CH— bonds, and preferably the following component (1) has an alkenyl group (preferably vinyl group) directly bonded to a silicon atom in one molecule. 100 parts by weight of organopolysiloxane having at least 2 (2) 0.1 to 1000 parts by weight of organopolysiloxane having at least 2 SiH bonds in one molecule (3) Addition catalyst 0.00001 to 10 parts by weight Crosslinked and cured. Ingredient (1)
The alkenyl group may be at either the terminal or the middle of the molecular chain. Examples of the organic group other than the alkenyl group include a substituted or unsubstituted alkyl group and an aryl group. Ingredient (1)
May contain a trace amount of a hydroxyl group. The component (2) reacts with the component (1) to form a silicone rubber layer, and plays a role of imparting adhesiveness to the photosensitive layer. The hydroxyl group of the component (2) may be at the terminal of the molecular chain or at the middle thereof. The organic group other than hydrogen is selected from the same groups as the component (1). From the viewpoint of improving the ink resilience, it is preferable that the organic groups of the components (1) and (2) are methyl groups in a total number of 60% or more. The molecular structure of the component (1) and the component (2) may be any of linear, cyclic and branched, and it is preferable that at least one of the molecular weights exceeds 1,000 in view of rubber physical properties. ) Has a molecular weight of 1,0
Preferably, it exceeds 00.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxane and a (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and the component (2) includes hydroxyl groups at both ends. Examples of the polydimethylsiloxane, α, ω-dimethylpolymethylhydrogensiloxane, copolymers of methyl groups at both ends (methylpolymethylhydrogensiloxane) (dimethylsiloxane), cyclic polymethylhydrogensiloxane, and the like.

The addition catalyst of the component (3) is arbitrarily selected from known ones, but a platinum-based compound is particularly desirable,
Platinum alone, platinum chloride, olefin-coordinated platinum and the like are exemplified. In order to control the curing rate of these compositions, a vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane, a carbon-carbon triple bond alcohol, acetone, methyl ethyl ketone, methanol,
It is also possible to add a crosslinking inhibitor such as ethanol or propylene glycol monomethyl ether.

In addition to these compositions, a known adhesion-imparting agent such as alkenyltrialkoxysilane may be added, a hydroxyl group-containing organopolysiloxane which is a composition of a condensation type silicone rubber layer, and a trimethylsilyl group at the end. Silicone oil made of dimethylpolysiloxane, dimethylpolysiloxane having a trimethylsilyl group at the end, and hydrolyzable functional group-containing silane (or siloxane) may be added. Further, a known filler such as silica may be added to improve the rubber strength.

The tensile properties of such a silicone rubber layer are such that the initial modulus of elasticity is 0.008 kgf / mm 2 or more and 0.1.
Less than 09 kgf / mm 2, preferably 0.012 kgf /
mm2 or more and less than 0.07 kgf / mm2, and 50% stress value is 0.005 kgf / mm2 or more and 0.04 kgf / mm2
Less than 0.007 kgf / mm2 and more than 0.02
It is important to make it less than 5 kgf / mm2.

The above initial elastic modulus is 0.008 kgf / mm
If it is less than 2 and the 50% stress value is less than 0.005 kgf / mm @ 2, printing durability becomes poor. On the other hand, the initial elastic modulus is 0.09
More than kgf / mm2, 50% stress value is 0.04kgf / mm
In the case of 2 or more, for example, the initial tensile elastic modulus of the silicone rubber layer described in Example 1 of JP-B-56-23150 is 0.15 kgf / mm @ 2 and the 50% stress value is 0.06 kgf.
/ Mm2, the silicone rubber layer is hard and the ink repulsion and scratch resistance are reduced. Further silicon
It is important that the elongation of tensile properties of the rubber layer is 100% or more, preferably 150% or more and less than 1200%. When the elongation is 100% or less, the printing durability deteriorates.

Known fillers, inorganic particles, silicic acid sol, etc. are added to the silicone gum composition for the purpose of appropriately reinforcing the ink repellent layer, and no known crosslinkable functional group is added. It is also possible to add a small amount of the modified silicone oil of. As a solvent for diluting and dissolving these silicone gum compositions, paraffinic hydrocarbons, isoparaffinic hydrocarbons, cycloparaffinic hydrocarbons and aromatic hydrocarbons are used in a single or mixed form. Representative examples of these hydrocarbon solvents include petroleum fractionated products and reformed products thereof. The thickness of the silicone rubber layer used as the ink repellent layer of the present invention is 0.5 to 10 in terms of dry weight from the viewpoint of maintaining printing durability and ink repellent property and maintaining good image reproducibility.
The range of g / m2 is preferable, and the range of 1 to 3 g / m2 is more preferable. If it is too thin, problems may occur in terms of printing durability and ink repellency, while if it is too thick, it is not only economically disadvantageous, but also it becomes difficult to remove the silicone rubber layer during development, and image reproduction Causes a decrease in sex.

On the surface of the ink-repellent layer of the waterless planographic printing plate having the above-described constitution, a suitable protective layer is formed on the ink-repellent layer by coating for the purpose of protecting the ink-repellent layer. It is also possible to laminate a protective film. The protective layer may also contain a photobleachable substance for the purpose of protecting the photosensitive layer from exposure to light (meaning that light other than the exposure light source is originally irradiated to the non-irradiated portion). it can. Specific examples of the protective film include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, cellophane, and the like. In addition, these protective films are preferably subjected to a matte treatment or a plastic layer containing silica particles or the like on the surface of the protective film to improve the vacuum adhesion in a printing frame during image exposure. Done.

Next, the method for producing a waterless planographic printing plate in the present invention will be described. An ordinary coater such as a reverse roll coater, an air knife coater, and a Mayer bar coater, or a spin coater such as a whaler is used to coat the substrate with the primer layer composition, if necessary.
After curing at ˜300 ° C. for several minutes, the photosensitive layer composition coating liquid is applied, dried at 50 to 150 ° C. for several minutes and thermally cured if necessary, and the silicone gum composition is applied thereon.
It is formed by heat treating rubber at 0 to 150 ° C. for several minutes to cure the rubber. After that, a protective film is laminated if necessary.

Next, the exposure and development step of the waterless planographic printing plate referred to in the present invention will be described. In the waterless lithographic printing plate as referred to in the present invention, the plate material is image-exposed by a usual exposure light source through a vacuum-contacted positive film or negative film. Examples of the light source used in the exposure step include a high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, and the like. After such a normal exposure, the plate surface is rubbed with a developing pad or a brush containing a developing solution described below, and in the case of positive working, the silicone rubber layer in the unexposed portion is removed and the photosensitive layer is removed. When exposed, the ink receiving portion (image portion) is exposed to form a positive printing plate. In the case of negative working, the silicone rubber layer in the exposed portion is removed to expose the photosensitive layer, and the ink receiving portion (image area) is exposed to form a negative printing plate.

As the developing solution used in the present invention, a known developing solution can be used, and a developing solution capable of appropriately dissolving or swelling the photosensitive layer is preferable. For example, aliphatic hydrocarbons (hexane, heptane, “isopar E, H, G” (ESSO
Product name of isoparaffin hydrocarbons, gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (tricrene, etc.), etc. A solvent containing at least one type of solvent is preferably used.

Alcohols (methanol, ethanol,
Propanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, hexylene glycol, 2-ethyl-1,3
Ethers (ethylene glycol monoethyl ether,
Diethylene glycol, monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-
2-ethylhexyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dioxane,
Tetrahydrofuran, etc. Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, etc.) Esters (ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether ethate, etc.) Carboxylic acid (2-ethylbutyric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, oleic acid,
Water is added to the above organic solvent-based developer composition,
A known surfactant can be freely added.
Further, an alkaline agent such as sodium carbonate, monoethanolamine, diethanolamine, triethanolamine, sodium silicate, potassium silicate, potassium hydroxide, sodium borate and the like can be added.

To these developing solutions, known basic dyes such as crystal violet, Victoria pure blue, and Astrazone red, acid dyes, and oil-soluble dyes may be added to dye the image area simultaneously with development. You can

When developing the waterless planographic printing plate used in this study, an automatic developing machine commercially available from Toray Co., Ltd. is used, and the plate surface is pretreated with the above developing solution. After that, the plate surface is rubbed with a rotating brush while showering with tap water or the like, so that suitable development can be performed.
Further, development can be carried out by spraying hot water or steam onto the plate surface instead of the above-mentioned developer.

[0148]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The epoxy compounds used in the examples are shown in Table 1.

[0149]

[Table 1] Example 1 Using a bar coater, a primer solution prepared by adding 5 parts by weight of the epoxy compound shown in Table 2 to the following composition on a degreased aluminum plate (manufactured by Sumitomo Metal Industries, Ltd.) having a thickness of 0.3 mm was used. Applied, and dried by heating at 230 ° C for 1 minute, film thickness 3
A primer layer of g / m ² was applied.

Base resin (carrier resin) (a) Polyurethane resin (Samprene LQ-SZ18, manufactured by Sanyo Chemical Industries, Ltd.) 115 parts by weight (b) Blocked isocyanate (Takenate B830, manufactured by Takeda Pharmaceutical Co., Ltd.) 20 parts by weight Parts (c) Butylated urea resin 15 parts by weight Others (d) Titanium oxide 10 parts by weight (e) Dimethylformamide 750 parts by weight Subsequently, a photosensitive layer composition having the following composition was coated on the primer layer with a bar coater. It was applied and dried at 115 ° C. for 1 minute to form a photosensitive layer having a film thickness of 1.5 g / m ² .

(A) 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolac resin (Sumilite Resin PR50622, manufactured by Sumitomo Dures Co., Ltd.) (elemental analysis method) Degree of esterification by 36%) 70 parts by weight (b) 4,4'-diphenylmethane diisocyanate 21 parts by weight (c) Polyurethane resin (Miractran P22S manufactured by Nippon Miractolane Co., Ltd.) 30 parts by weight (d) Dibutyl Tin diacetate 0.2 parts by weight (e) P-toluene sulfonic acid 0.8 parts by weight (f) Tetrahydrofuran 800 parts by weight Next, a silicone gum composition having the following composition was formed on this photosensitive layer using a bar coater. coated, 115 ° C., dew point 30 ° C., 3.5 minutes wet heat-cured in a thickness of 2 g / m ² silicone - down It was coated with a beam layer.

(A) Polydimethylsiloxane (molecular weight of about 25,000, terminal hydroxyl group) 100 parts by weight (b) Vinyltri (methylethylketoxime) silane 10 parts by weight (c) "Isopa-E" (manufactured by Exxon Chemical Co., Ltd.) 800 parts by weight To the laminated plate obtained as described above, a polypropylene film “Trefan” having a thickness of 10 μm (manufactured by Toray Industries, Inc.)
Was laminated using a calendar roller to obtain a waterless planographic printing plate precursor.

A metal halide lamp (Idlefin 2000 manufactured by Iwasaki Electric Co., Ltd.) was used as the printing original plate.
The entire surface was exposed with a UV meter (Light Measure Type UV-402A, manufactured by Oak Manufacturing Co., Ltd.) at an illuminance of 11 mW / cm ² for 6 seconds.

1 is added to the printing original plate obtained as described above.
A negative film having a halftone dot image of 50 lines / inch was vacuum-contacted and exposed for 60 seconds from a distance of 1 m using the above metal halide lamp.

Then, the "trephan" of the above-mentioned exposed plate was peeled off, and a non-exposed portion was scratched on the plate surface using a writing brush so as to reach the aluminum plate. Brush the treatment liquid consisting of "isopa-H" / diethylene glycol dimethyl ether / ethyl cellosolve / N-methyldiethanolamine = 87/7/3/3 (weight ratio) under the conditions of room temperature 32 ° C. and humidity 80%. It was applied to the plate surface. After processing for 1 minute, the processing liquid attached to the plate surface is removed with a rubber squeegee,
Next, a developing solution (water / butyl carbitol / 2-ethylbutyric acid / crystal violet = 70) is applied to the plate surface and the developing pad.
When the plate surface was lightly rubbed with a developing pad, the silicone rubber layer at the image-exposed portion was removed, exposing the surface of the photosensitive layer. On the other hand, in the non-image portion where only the entire surface was exposed, the silicone rubber layer remained firmly, and an image faithfully reproducing the negative film was obtained.

The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine), and fine paper was prepared using "Dry Okara" ink, indigo, red, and yellow ink manufactured by Dainippon Ink and Chemicals, Inc. (62.5 g / Chrysanthemum) was printed to perform a printing durability test. It was evaluated by visually observing the stains on the printed matter and the damage state of the silicone rubber layer on the plate surface after printing. When 130,000 sheets were printed on this sample, good printed matter was printed, and the printing plate after the printing was inspected, but the printing plate was found to be slightly damaged.

Regarding the evaluation of the adhesiveness, the scratches on the cross-cut previously attached to the unexposed area were evaluated by rubbing the plate surface with a developing pad, and visually observing how many times the peeling occurred. It was confirmed that the adhesiveness was similar at the initial stage and after the passage of time. After preparing the printing plate precursor, 60
When stored for 2 weeks in an atmosphere of ℃ and relative humidity of 80%, the same evaluation was carried out as a lithographic printing plate precursor after a lapse of time. It was possible to obtain a waterless planographic printing plate precursor that was stable over time.

Examples 2 to 10 In the same manner as in Example 1 except that the epoxy compounds shown in Table 2 were used, a waterless planographic printing plate precursor was prepared, exposed and developed, and then each An evaluation was made. The results are shown in Table 2.

Examples 11 to 14 Water-free lithographic printing plate precursors were prepared in the same manner as in Example 1 except that the blending ratios shown in Table 2 were changed. An evaluation was made. The results are shown in Table 2.

Example 15 Waterless lithographic printing was carried out in the same manner as in Example 1 except that the photosensitive layer composition was changed to the following composition to provide a photosensitive layer and the epoxy compound shown in Table 2 was used. Each plate was prepared, exposed and developed, and then evaluated. Table 2 shows the results
Shown in

A photosensitive solution having the following composition was coated on the primer layer, and then dried by heating at 100 ° C. for 1 minute to give a thickness of 4 g.
A photosensitive layer of / m ² was provided.

(1) Polyurethane consisting of adipic acid and polyethylene glycol Polyol and isophorone diisocyanate 60 parts by weight (2) N, N, N′-tri- (2-hydroxy-) 3-methacryloyloxypropyl) -N'-mono- (2-hydroxy-3-methoxypropyl) pentaoxypropylenediamine 10 parts by weight (3) tetraethylene glycol diacrylate 10 parts by weight (4) N, N'- Di- (2-hydroxy-3-methacryloyloxypropyl) -N, N'-di- (2-hydroxy-3-methoxypropyl) m-xylenediamine 10 parts by weight (5) 4,4'-bis (dimethyl) Amino) benzophenone 4 parts by weight (6) N-methylacridone 5 parts by weight (7) Victoria Pure Blue BOH Naphthalene sulfonate 0.5 part by weight (8) Ethyl cellosolve 580 parts by weight (9) Maleic acid 1 part by weight Example 16 In Example 1, 1 part by weight of mono (2-methacryloyloxyethyl) acid phosphate and A waterless lithographic printing plate precursor was prepared in the same manner as in Example 1 except that 0.5 part by weight of dibutyltin acetate was added, exposed and developed, and then evaluated. The results are shown in Table 2.

Example 17 In Example 1, 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolac resin (Sumilite resin PR5062) were used.
2. A waterless planographic printing plate precursor was prepared and exposed in the same manner as in Example 1 except that the degree of esterification of the partially esterified product of Sumitomo Durez Co., Ltd. was set to 8% (analyzed by elemental analysis). After development, each evaluation was performed. The results are shown in Table 2.

Example 18 In Example 1, 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolac resin (Sumilite resin PR5062) were used.
2. A waterless planographic printing plate precursor was prepared and exposed in the same manner as in Example 1 except that the esterification degree of the partially esterified product of Sumitomo Durez Co., Ltd. was set to 19% (analyzed by elemental analysis). After development, each evaluation was performed. Table 2 shows the results
Shown in

Example 19 In Example 1, 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolac resin (Sumilite resin PR5062) were used.
2. A waterless lithographic printing plate precursor was prepared and exposed in the same manner as in Example 1 except that the esterification degree of the partially esterified product of Sumitomo Durez Co., Ltd. was set to 60% (analysis by elemental analysis). After development, each evaluation was performed. Table 2 shows the results
Shown in

Comparative Examples 1 to 8 In the same manner as in Example 1 except that the epoxy compounds shown in Table 2 were used, waterless planographic printing plate precursors were prepared, exposed and developed. An evaluation was made. The results are shown in Table 2.

[0167]

[Table 2] As shown in Table 2, by blending and using the epoxy compound, adhesiveness, image reproducibility,
A waterless planographic printing plate precursor having excellent printing durability was obtained. or,
Since the reaction of the primer layer is completed by using the present invention, a waterless planographic printing plate precursor that is extremely stable over time could be obtained (Examples 2 to 11). In particular, it is found that the hydrophobic epoxy compound having an aromatic group and the hydrophilic epoxy compound being a glycerol type epoxy compound are preferable (Example 3).

Furthermore, the epoxy equivalent of both epoxy compounds is 3
Those of 00 or less are extremely good (Examples 1, 2,
4, 7).

Further, the above effect is not affected by the blending ratio within the scope of the present invention, and the same effect can be obtained by changing the hydrophilic epoxy from 0.6 to 3 with respect to the hydrophobic epoxy 1 ( Examples 11-14). These effects are
It can be confirmed that the same is obtained when the photosensitive layer is changed to the photopolymerizable type (Example 15). In addition, the combination of the present invention with mono (2-methacryloyloxyethyl) acid phosphate and dibutyltin acetate gave good results because the reaction was further promoted (Example 16). In Example 1, the degree of esterification of the partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolac resin (Sumilite Resin PR50622, manufactured by Sumitomo Dures Co., Ltd.) was determined. Even with a change of 8 to 60%, it was possible to obtain a plate material having good performance both initially and over time.

However, when the primer layer did not contain an epoxy compound, the performance of the waterless lithographic plate was inferior to that of the Examples both initially and after aging (Comparative Example 1). Even when the epoxy compound is not blended and used, good performance cannot be obtained as compared with the examples (Comparative Example 2).
To 8). For example, when the hydrophobic epoxy compound is used alone, the initial adhesiveness is good, but the adhesiveness decreases with time (Comparative Examples 2 to 5). Similarly, when a hydrophilic epoxy compound is used alone, the initial adhesiveness is poor and the adhesiveness does not decrease with time, but the image reproducibility decreases (Comparative Examples 6 to 8).

Examples 20 to 22 Waterless planographic printing plate precursors were prepared, exposed and developed in the same manner as in Example 1 except that the base resin (carrier resin) shown in Table 3 was used. After that, each evaluation was performed.
The results are shown in Table 3.

Examples 23 to 25 Waterless planographic printing plate precursors were prepared, exposed and developed in the same manner as in Example 4 except that the base resin (carrier resin) shown in Table 3 was used. After that, each evaluation was performed.
The results are shown in Table 3.

Comparative Examples 9 to 11 Waterless lithographic printing plate precursors were prepared, exposed and developed in the same manner as in Example 1 except that the base resin (carrier resin) shown in Table 3 was changed. After that, each evaluation was performed.
The results are shown in Table 3.

Comparative Examples 12 to 14 In Comparative Example 6, a waterless planographic printing plate precursor was prepared and exposed and developed in the same manner as in Example 1 except that the base resin (carrier resin) shown in Table 3 was changed. After that, each evaluation was performed.
The results are shown in Table 3.

[0175]

[Table 3] As shown in Table 3, even when the base resin (carrier resin) was changed, by using the present invention, good initial performance was exhibited, and a waterless planographic printing plate precursor that was stable over time could be obtained. (Examples 18-23). In particular, the hydrophobic epoxy compound contained in the primer layer has an aromatic group,
Moreover, it can be confirmed that the hydrophilic epoxy compound is a glycerol type epoxy compound, and that the epoxy equivalent of both epoxy compounds is 300 or less is extremely good (Examples 18 to 20).

Although the effect is slightly inferior to the case where the base resin contains polyurethane, a block type isocyanate and an amino resin, in the present invention, the base resin containing an amino resin (implementation) Examples 19, 2
0, 22, 23) is good.

However, even when the base resin (carrier resin) was changed, when the epoxy resin was not blended and used, inferior results were obtained both in the initial stage and after aging as compared with the examples. For example, when the hydrophobic epoxy compound is used alone, the initial adhesiveness is good, but the adhesiveness decreases with time (Comparative Examples 9 to 11). Similarly, when a hydrophilic epoxy compound is used alone, the initial adhesiveness is poor and the adhesiveness does not decrease with time, but the image reproducibility decreases (Comparative Examples 12 to 14).

[0178]

According to the present invention, it is possible to obtain an epoch-making primer layer which has good adhesiveness to a substrate and is stable over time without impairing the function of the primer layer. By using a primer, it is possible to provide a waterless planographic printing plate precursor that has excellent image reproducibility and an ink repellent layer and is also excellent in productivity.

Claims (6)

[Claims] 1. A waterless planographic printing plate precursor obtained by laminating a primer layer, a photosensitive layer and a silicone rubber layer on a substrate in this order, wherein the primer layer contains a hydrophobic epoxy compound and a hydrophilic epoxy compound. A waterless planographic printing plate precursor featuring. 2. The hydrophobic epoxy compound in the primer layer is an epoxy compound having an aromatic group, and the hydrophilic epoxy compound is a glycerol type epoxy compound.
The waterless planographic printing plate precursor described. 3. The waterless planographic printing plate precursor according to claim 1, wherein the epoxy equivalent of the hydrophobic epoxy compound and / or the hydrophilic epoxy compound in the primer layer is 300 or less. 4. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the primer layer contains an organic tin compound and a monomer represented by the following general formula (I). Embedded image (However, R1 and R2 represent a hydrogen atom or a methyl group, a and b are integers of 1 or more, a + b = 3, and n is 0 to 20.
Represents an integer. ) 5. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the primer layer contains an amino resin. 6. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the primer layer contains polyurethane and a block type isocyanate.