JPH07175209A - Method for making waterless lithographic printing plate - Google Patents

Abstract

PURPOSE:To make a dry-release waterless lithographic printing plate with the picture reproducibility and stability improved by forming a negative resist picture on the adhesive layer of a sheet provided with the adhesive layer on a substrate. CONSTITUTION:A negative resist picture layer 4 is formed on the adhesive layer 3 of a sheet 1 with the adhesive layer 3 provided on one surface of a substrate 2, then the sheet 1 and a printing original plate 5 with an ink-repellent layer 7 furnished on a substrate 6 are press-bonded so that the ink-repellent layer 7 is confronted with the adhesive layer 3. The sheet 1 is then released from the plate 5. The part of the ink-repellent layer 7 bonded to the adhesive layer 3 is released from the substrate 6, only the part of the layer 7 opposed to the resist layer 4 is left on the plate 5, and a lithographic printing plate is formed. As a result, the waterless lithographic printing plate is obtained with the picture reproducibility and stability improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for making a lithographic printing plate which does not require fountain solution.
The present invention relates to a method for producing a lithographic printing plate that does not require fountain solution by dry peeling development.

[0002]

2. Description of the Related Art Dry peeling is a technique for avoiding the drawback of complicating the plate making process of a method for producing a photosensitive lithographic printing plate (hereinafter referred to as "waterless lithographic plate") which does not require fountain solution by a wet development process. Techniques for producing waterless lithographic printing by development are known.

As such a technique, after exposing a photosensitive printing plate comprising a composite sheet in which two layers of a silicone rubber layer and a photocurable photosensitive layer are sandwiched between two sheets, at least one of which is transparent, A lithographic plate having an ink-repellent silicone rubber surface lined with a sheet and a cured photosensitive layer on the exposed portion by peeling two sheets, and an unexposed portion having an uncured photosensitive film surface backed on the sheet. A method for producing a printing plate (Japanese Patent Laid-Open No. 48-94503), in which a coating layer of photocurable silicone is provided on a substrate, an ultraviolet-transparent sheet is pressure-bonded to the coated surface, and an image is transferred through the ultraviolet-transparent sheet. A method in which the photocurable silicone layer is imagewise cured by exposure, the sheet is peeled from the substrate together with the cured silicone layer, and then the uncured silicone layer on the substrate is cured (JP-A-54-121804). Publication), on one surface of the substrate, after crimping the surface of the photocurable silicone layer of Nursing uncured formed by coating the ultraviolet transmittance made a and insulating support member,
An electric charge is applied to the support, and then a conductive substance is contacted to form an electrostatic image, and then a charged toner is applied to form an ultraviolet non-transmissive image on the support, which is exposed from the image side. Then, a method is known in which the support is peeled from the substrate together with the uncured silicone layer to form a non-image substance composed of the cured silicone layer on the substrate (Japanese Patent Laid-Open No. 54-125032).

[0004]

However, in each of the above techniques, since the adhesiveness is changed by exposure, the difference in adhesiveness between the exposed portion and the non-exposed portion is not sufficient, and therefore the image Poor reproducibility, deterioration of reproducibility of highlights and shadows, uneven development in the peeling direction, and rinsing problems, and large variations in quality due to the environment due to temperature, humidity, and aging after manufacturing. There is a problem that the sex is not sufficient. The object of the present invention is to perform dry peeling development,
A method for producing a waterless planographic printing plate having improved image reproducibility and stability.

[0005]

The constitution of the present invention for achieving the above object is the following (1) to (4).

(1) A printing original plate having an ink repellent layer as the uppermost layer after forming a negative resist image on the adhesive layer of a sheet having an adhesive layer provided on a support. , The water-repellent planographic printing plate is characterized in that the ink repellent layer in the image area is removed by pressure-bonding the ink repellent layer side and the adhesive layer side so as to face each other and peeling off the sheet. Plate making method.

(2) After forming a negative resist image on the ink repellent layer of the printing original plate having the ink repellent layer as the uppermost layer, the printing original plate was provided with an adhesive layer on a support. A plate-making of a waterless planographic printing plate, characterized in that the sheet, the ink repellent layer side and the adhesive layer side are pressure-bonded to face each other and the printing plate precursor is peeled off to remove the ink repellent layer in the image area. Method.

(3) After forming a positive resist image on the adhesive layer of a printing plate precursor having an adhesive layer provided on the support, a sheet having an ink repellent layer on the support is printed on the sheet. It is possible to transfer the ink repellent layer in the non-image area to the printing original plate by pressing the ink repellent layer side and the adhesive layer side so that they face each other, and peeling off the sheet. A method of making a waterless planographic printing plate which is a feature.

(4) After a positive resist image is formed on the ink repellent layer of a sheet having an ink repellent layer provided on the support, the sheet is provided with an adhesive layer on the support. The printing plate precursor is pressure-bonded so that the adhesive layer side and the ink repellent layer side face each other, and the sheet is peeled off to transfer the ink repellent layer in the non-image area to the printing plate precursor. A method for making a waterless planographic printing plate characterized by:

First, an outline of the plate-making method of the present invention will be described with reference to the drawings. FIG. 1 illustrates a schematic cross-sectional view for explaining a step of producing a lithographic printing plate by the plate making method of the invention according to claim 1. In FIG. 1, (a)
Shows a state where the negative resist image layer 4 is formed on the adhesive layer 3 of the sheet 1 in which the adhesive layer 3 is provided on one surface of the support 2, and FIG. 1 shows a printing original plate 5 having an ink repellent layer 7 provided thereon, (c) shows a state in which the sheet 1 having the negative resist image layer 4 formed thereon and the printing original plate 5 are pressure bonded, and (d) shows the sheet 1 After the state shown in (d) in which the printing plate 5 and the printing original plate 5 are pressure-bonded, the sheet 1 is printed with the printing original plate 5
It shows the state of peeling from. As shown in (d),
In the area where the resist image layer 4 is not present on the adhesive layer 3, the ink repellent layer 7 and the adhesive layer 4 adhere to each other, and when the sheet 1 is peeled off from the printing original plate 5, the ink repellent of the area adhered to the adhesive layer 3 The photosensitive layer 7 is peeled off from the support 6, and only the part of the printing plate 5 where the ink repellent layer 7 faces the resist layer 4 remains to form a lithographic printing plate.

In the state shown in FIG. 1C, the adhesive force between the formed resist image layer and the ink repellent layer is Vn, the adhesive force between the adhesive layer and the ink repellent layer is Vi, and the sheet support. If the adhesive force between the ink and the ink repellent layer is Vs, then Vi>Vs>
Peeling as shown in (d) is possible under the condition of Vn.

FIG. 2 is a schematic cross-sectional view illustrating a step of producing a lithographic printing plate by the plate-making method of the invention according to claim 2, (a) showing on the surface of the support 2. Shows a sheet 1 having an adhesive layer 3 provided on the surface thereof, and (b) shows a negative resist image layer 4 on the adhesive layer 3 of the printing original plate 5 having an ink repellent layer 7 provided on the surface of a support 6. FIG. 3C shows a state in which the sheet is formed by pressing the printing original 5 having the negative resist image layer 4 formed on the ink repellent layer 7 and the sheet 1 with the resist image layer 4 and the ink repellent layer 7 facing each other. And (d) shows a state in which the sheet 1 is subsequently peeled from the printing original plate 5. As shown in (d), the ink repellent layer 7 and the adhesive layer 3 are adhered to each other at a portion where the resist image layer 4 is not provided on the ink repellent layer 7, and at the same time, the resist image layer 4 and the adhesive layer 3 are adhered to each other. And the sheet 1 is peeled off from the printing original plate 5, the ink repellent layer 7 at the portion adhered to the adhesive layer 3 is peeled off from the support 6, and the printing original plate 5 has the ink repellent layer 7 on the resist layer 4 A lithographic printing plate is created by leaving only the portion facing the.

FIG. 3 exemplifies a schematic cross-sectional view for explaining a step of producing a lithographic printing plate by the plate making method of the invention according to claim 3. (A) shows a sheet 1a in which an ink repellent layer 7 is provided on a support 2,
(B) shows a state in which a positive resist image layer 4 is formed on the adhesive layer 3 of the printing original plate 5a in which the adhesive layer 3 is provided on the support 6, and (c) shows a positive resist. Shown is a state in which the printing original plate 5a on which the image layer 4 is formed and the sheet 1a are pressure-bonded with the adhesive layer 3 and the ink repellent layer 7 facing each other,
(D) shows a state in which the sheet 1a is separated from the printing original plate 5a. As shown in (d), the ink repellent layer 7 and the adhesive layer 3 are bonded to each other in the portion where the resist image layer 4 is not provided on the adhesive layer 3, and the resist image layer 4 and the adhesive layer 3 are bonded to each other. Then, when the sheet 1a is peeled off from the printing original plate 5a,
The ink repellent layer 7 in the portion without the adhesive layer 3 is the adhesive layer 3
Adhere to each other, and when the sheet 1a is peeled off from the printing original plate 5a, the ink repellent layer 7 in the portion where the adhesive layer 3 is absent
Then, the ink repellent layer 7 in the portion where the resist layer 4 is not present remains on the printing original plate 5a, and the planographic printing plate is prepared.

In the layer structure shown in FIG. 3 (c), the adhesive force between the resist image layer and the ink repellent layer is Vn, the adhesive force between the adhesive layer and the ink repellent layer is Vi, and the support of the printing plate precursor. If the adhesive force between the ink and the ink repellent layer is Vs ', Vi>Vs'>
Peeling as shown in (d) is possible under the condition of Vn.

The invention according to claim 4 is the same as that described with reference to FIG. 3 above, except that the positive resist image layer 4 of FIG. 3B is provided toward the ink repellent layer 7 of FIG. 3C. is there.

As the ink repellent layer in the inventions according to claims 1 to 4, a layer formed of silicone rubber or fluororesin can be applied.

The silicone rubber has a molecular weight of several thousands to have a repeating unit represented by the following general formula [1].
It is preferable that the main component is a linear organic polysiloxane having a hydroxyl group in the main chain of several hundreds of thousands or at the end of the main chain.

[0018]

[Chemical 1]

Here, n is an integer of 2 or more and R is 1 carbon atom.
The alkyl group, halogenated alkyl group, alkoxyl group, vinyl group, aryl group or hydroxyl group of -10 is preferable, and 60% or more of R is a methyl group. The hydroxyl group may be in the main chain or at the end of the main chain, but is preferably at the end.

As the silane coupling agent (or silicone crosslinking agent), R _n SiX _4-n (where n is an integer of 1 to 3 and R is an alkyl group, an aryl group or an alkenyl group or a combination thereof) Represented by the formula (1), and these groups may have a functional group such as halogen, amine, hydroxyl, alkoxy, aryloxy and thiol.

X is --OH, --OR ² , --OAc, --ON--C (R ² ).
(R ^3), - represents Cl, -Br, substituents such as -I. Here, R ² and R ³ represent the same as the above R, and R ² and R ³ may be the same or different. Ac represents a silane compound).

Thus, the silicone rubbers useful in the present invention are those obtained by the condensation reaction of such silicone base polymers with the silicone crosslinking agents listed above.

Specific examples of the silane coupling agent include:
_{HN [(CH 2) 3 Si} (OMe) 3] 2, vinyltriethoxysilane, Cl
(CH ₂ ) ₃ Si (OMe) ₃ , CH ₃ Si (OAc) ₃ , HS (CH ₂ ) ₃ Si (OMe) ₃ , vinyltris (methylethylketoxime) silane and the like can be mentioned.

The above silicone rubber is also available as a commercial product, such as YE-3085 manufactured by Toshiba Silicone Co., Ltd.
Another useful silicone rubber is a reaction between the above-mentioned base polymer and a silicone oil having a repeating unit represented by the following general formula [2], or about 3% of R is a vinyl group. Silicone base
It can also be obtained by addition reaction with a polymer or reaction between the silicone oils.

[0025]

[Chemical 2]

(In the formula, R has the same meaning as R which is a substituent of the polymer represented by the general formula [1], m is an integer of 2 or more, and n is 0 or an integer of 1 or more.) In order to obtain a silicone rubber by various crosslinking reactions, the crosslinking reaction is carried out using a catalyst. As the catalyst, an organic carboxylate of a metal such as tin, zinc, cobalt, lead, calcium, manganese, for example, dibutyltin laurate, tin (II) octoate, cobalt naphthenate, or chloroauric acid is used. .

Further, in order to improve the strength of the silicone rubber and to obtain the silicone rubber which can withstand the frictional force generated during the printing operation, a filler can be mixed. The silicone rubber in which the filler is mixed in advance is commercially available as a silicone rubber stock or a silicone rubber dispersion, and when it is preferable to obtain a silicone rubber film by coating as in the present invention, RTV or LTV silicone rubber Disversion is preferred. Examples of these include Tray Silicone Sy1 OFF 23, SRX-257, SH237
There is a silicone rubber distribution for paper coating.

In the present invention, it is preferable to use condensation-crosslinking type silicone rubber.

The silicone rubber layer preferably contains a silane coupling agent having an amino group in order to further improve the contact property.

Preferred silane coupling agents are:
For example:

(A) H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (b) H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (CH ₃ ) ( c) H ₂ N (CH ₂ ) ₃ Si (OEt) ₃ The silicone rubber layer used in the present invention may further contain a small amount of a photosensitizer.

The silicone rubber layer used in the present invention is
After the silicone rubber is dissolved in a suitable solvent, it is coated on a support and dried.

Fluorine resins include those disclosed in JP-A-52-74404,
52-74405, 58-83011, 58-88750, 58-905
No. 24, etc., and is conventionally known, or has already been proposed by the applicant as described in Japanese Patent Application Nos. 63-182466, 63-83011, 63-288129, etc. Any fluororesin can be used.

The thickness of the ink repellent layer is preferably in the range of 0.5 to 10 μm, more preferably 1 to 3 μm. A protective layer may be laminated on the ink repellent layer.

A primer layer is preferably provided between the ink repellent layer and the support of the sheet of the invention according to claim 3 or 4 in order to adjust the adhesive force between the ink repellent layer and the support. . In addition, in order to improve the adhesiveness with the adhesive layer,
A primer layer or a photocurable layer may be further provided on the surface of the ink repellent layer.

As the above-mentioned primer layer, one having good adhesion to a support and containing a pigment is suitable. Examples of the resin used for the primer layer include epoxy resin, cellulose resin, vinyl resin, alkyd resin, coumarone, indene resin, phenol resin, polyester resin, urethane resin, acrylic resin and butadiene.
-Acrylonitrile rubber, neoprene rubber, polysulfide rubber, epoxy resin to phenol, resorcinol,
One or two of polyamide, furan resin, polysulfide, melamine, urea, synthetic rubber, polyester, etc.
Examples thereof include resins modified with one or more, resins obtained by esterifying an epoxy resin with fatty acids, and resins modified with one or more of phenolic resins such as vinyl acetals, polyamide, nitrile rubber, and neoprene.

It is also possible to use these resins by mixing or polymerizing with each other or with resins other than those mentioned above within the range where compatibility is allowed.

The resin used in the present invention can be used as a mixture with various curing agents. The curing agent may be a crosslinkable or polymerizable compound that is cured by various energy rays such as light or heat, or may be one that is naturally cured at room temperature only by mixing or drying.

Various additives such as reaction accelerators, catalysts, plasticizers and heat deterioration inhibitors can be used for the purpose of improving productivity and production stability, and improving various physical properties.

As the anchor agent constituting the above-mentioned primer layer, for example, the above-mentioned silane coupling agent, silicone primer or the like can be used, and organic titanate or the like is also effective.

The adhesive layer provided on the sheet or the printing original plate used in the invention according to any one of claims 1 to 4 is formed by forming a resist image and then facing the ink repellent layer side and the adhesive layer side. The adhesive force between the resist image layer and the ink repellent layer in the image area (the area without the resist image layer) is Vn, and the resist image layer in the non-image area (the area with the resist image layer) is If the adhesive force between the ink repellent layer is Vi, the adhesive force between the sheet support and the ink repellent layer is Vs, and the adhesive force between the printing plate precursor and the ink repellent layer is Vs ′, Vi>Vs> Vn or Vi>Vs'> Vn
Any adhesive can be used as long as the adhesive strength is obtained.

As such an adhesive layer, vinyl acetate resin, acrylic resin, epoxy resin, polyamide, urethane resin, polyester, butyral resin, phenol resin, resorcinol resin, urea resin, silicone resin, chloroprene rubber, nitrile rubber, Butyl rubber, urethane rubber, for example, "Development of new technology of adhesive (adhesive), its application, various applied products, Management Development Center Publishing Department"
It is possible to use layers formed by using the materials described in 1.

In the invention according to claim 1 or 2, it is preferable that the adhesive layer of the sheet is provided with a photo-curing property or a thermosetting property, and in the invention according to claim 3 or 4, the original plate for printing is used. It is preferable to impart photocurability to the adhesive layer. In order to impart photocurability to the adhesive layer, various photocurable photosensitive compounds or compositions can be used. For example, the following compounds (1) to (4) are used. You can

(1) Diazo resin As the diazo resin, various kinds of diazo resins can be used, but preferably, a diazo resin represented by a condensate of p-diazodiphenylamine and formaldehyde, which is water-soluble. It may be soluble or organic solvent-soluble, but is preferably Japanese Patent Publication Nos. 47-1167 and 57-
Water-insoluble and ordinary organic solvent-soluble substances such as those described in Japanese Patent No. 43890 are used. Particularly preferred is a diazo resin represented by the following general formula [3].

[0045]

[Chemical 3]

[In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group. X is PF ₆ or B
Indicates F _4, Y is -NH -, - shows S- or -O-. Examples of the diazo monomer in the diazo resin used in the present invention include 4-diazodiphenylamine and 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-benzoylmonobenzene, 1-diazo-4-N-benzylaminobenzene, 1-diazo-4-morpholinobenzene, 1-
Diazo-2,5-dimethoxy-4-p-trimercaptobenzene,
1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene,
p-diazodimethylaniline, 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-tolyl Mercapbenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-3-ethoxy-4-N-methyl
-N-benzylaminobenzene, 1-diazo-3-chloro-4-N, N
-Diethylaminobenzene, 1-diazo-3-methyl-4-pyrrolidinobenzene, 1-diazo-2-chloro-4-N, N-dimethylamino-5-methoxybenzene, 1-diazo-3-methoxy-4- Examples include pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- (n-propoxy) -4-diazodiphenylamine, 3- (isopropoxy) -4-diazodiphenylamine. .

Examples of the aldehyde used as the condensing agent with the diazo monomer include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde and the like.

As for the anion, a water-soluble diazo resin can be obtained by using chlorine ion, tetrachlorozinc acid, etc., and tetrafluoroboron, hexafluorophosphoric acid, triisopropylnaphthalene sulfonic acid, 4 Diazo resin soluble in organic solvent by using 4,4'-biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, etc. Can be obtained. Particularly preferably, a diazo resin composed of hexafluorophosphoric acid is used.

The diazo resin is preferably used as a mixture with a film-forming resin, particularly a polymer compound having a hydroxyl group. Particularly preferably, the polymer compound is a monomer having an aliphatic hydroxyl group in the side chain, for example, a copolymer of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate and another copolymerizable monomer.
In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin and the like may be added if necessary.

As the binder used in combination with the diazonium salt, various polymer compounds can be used, but it is preferable to use a monomer having an aromatic hydroxyl group as described in JP-A-54-98613. Polymers such as N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o-, m- or p-hydroxyphenylmethacrylate, etc. Copolymer with monomers of US Pat. No. 4,123,276
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit, as described in U.S. Pat.No. 5,849,984, natural resins such as shellac and rosin, polyvinyl alcohol, U.S. Pat. Polyamide resin, linear polyurethane resin described in U.S. Pat. No. 3,660,097, phthalated resin of polyvinyl alcohol, epoxy resin condensed from bisphenol A and epichlorohydrin, cellulose acetate, cellulose acetate cellulose acetate phthalate resin. To be

Examples of alkali-soluble resins include novolac resins, vinyl polymers having phenolic hydroxyl groups, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. . Examples of the novolac resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-formaldehyde resin as described in JP-A-55-57841.
Cresol / formaldehyde copolycondensation resin, JP-A-55
Examples of the copolymer resin of p-substituted phenol and phenol or cresol and formaldehyde as described in JP-A-127553.

In addition to the above-mentioned materials, these photosensitive compositions may further contain dyes such as dyes and pigments, sensitizers, plasticizers, surfactants, organic acids, acid anhydrides, and exposures, if necessary. A compound capable of generating an acid can be added.

These binders are contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight.
The diazo fat is contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

Other dyes, pigments and other pigments, oil sensitizers, plasticizers, surfactants and the like can be added to these photosensitive compositions.

(2) --CH.dbd.CH-- on the main chain or side chain of the polymer.
Photosensitive Composition Containing Polymer Compound Having CO-Group Examples of such a polymer compound include polyesters and polyamides containing -CH = CH-CO- as a photosensitive group in the main chain or side chain of a polymer. , Whose main component is a photosensitive polymer such as polycarbonates (eg, US Pat. No. 3,030,20
No. 8, compounds 3,707,373 and 3,453,237); cinnamylidene malonic acid and the like (2
-Properidene) those containing photosensitive polyesters derived from malonic acid compounds and difunctional glycols as main components (for example, US Pat. Nos. 2,956,878 and 3,173,787).
A photopolymer as described in each of the specifications);
Cinnamic acid esters of hydroxyl group-containing polymers such as polyvinyl alcohol, starch, cellulose and the like (such as those described in U.S. Pat.Nos. 2,690,966, 2,752,372 and 2,732,301). Such a polymer) and the like.

These photosensitive compositions contain other sensitizers,
Stabilizers, plasticizers, pigments, dyes and the like can be included.

(3) Photopolymerizable Composition Comprising Addition-Polymerizable Unsaturated Compound This composition preferably comprises (a) a monomer having at least two terminal vinyl groups, (b) a photopolymerization initiator and (C) A polymer compound as a binder.

As the vinyl monomer of this component (a),
For example, acrylic acid or methacrylic acid ester of polyol, that is, diethylene glycol, described in JP-B Nos. 35-5093, 35-14719, and 44-28727.
(Meth) acrylate, triethylene glycol di (meth)
Acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc., bis (meth) acrylamides such as methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, or urethane group-containing Saturated monomers, such as di- (2'-methacryloxyethyl) -2,4-tolylenediurethane, di- (2-acryloxyethyl) trimethylenediurethane and other diol mono (meth) acrylates and diisocyanates Reaction products with and the like can be mentioned.

As the photopolymerization initiator of the above component (b),
The compound represented by the general formula [3] can be used, but other types can also be used. For example, carbonyl compounds, organic sulfur compounds as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar,
Examples include persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes. More specifically, it is disclosed in US Pat. No. 1,459,563.

The following can be used as the photopolymerization initiator.

Benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-α-phenylacetophenone, benzophenone,
2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4,
Benzophenone derivatives such as 4'-bis (diethylamino) benzophenone, thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone, anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone, N-methylacridone, N-butyl Acridone derivatives such as acridone, α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds and halogen compounds.

As the binder of the component (c), various known polymers can be used. Details of specific binders are described in US Pat. No. 4,072,527.

In addition to this, the binder used when used in combination with the above-mentioned diazonium salt is used.

The photopolymerizable composition may contain a thermal polymerization inhibitor, a plasticizer, a dye or a pigment.

(4) Photosensitive Composition Containing Azido Group As the photosensitive azide compound, an aromatic azido compound having an azido group bonded to an aromatic ring directly or through a carbonyl group or a sulfonyl group is preferably used. .

For example, polyazidostyrene, polyvinyl as described in US Pat. No. 3,096,311.
-p-azidobenzoate, polyvinyl-p-azidobenzal, a reaction product of an azidoarylsulfonyl chloride and an unsaturated hydrocarbon-based polymer described in JP-B-45-9613, and JP-B-43-21017. 44-229, 44-22954,
Examples thereof include polymers having a sulfonyl azide or a carbonyl azide as described in JP-A-45-24915.

An oil sensitizer, a surfactant, a sensitizer, a stabilizer, a thermal polymerization inhibitor, a plasticizer, which is added to the photosensitive composition,
Additives such as dyes and pigments differ in the amount added depending on the type, but generally 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the photosensitive composition contained in the photosensitive coating liquid.
Is appropriate.

The dyes preferably used in the present invention include basic dyes and oil-soluble dyes. Specifically, Victoria Pure Blue BOH, Victoria Blue BH, Methyl Violet, Eisen Malachite Green (above, Hodogaya Chemical Co., Ltd.), Patent
Basic dyes such as Pure Blue VX, Rhodamine B. Methylene Blue (above, Sumitomo Chemical Co., Ltd.), Sudan Blue II, Victoria Blue F4R
(Above made by B.A.S.F.), Oil Blue # 603,
Oil-soluble dyes such as Oil Blue BOS, Oil Blue IIN (above, manufactured by Orient Chemical Industry) and the like can be mentioned.

In the present invention, the adhesive layer may be provided with photo-peeling property. Examples of the compound that imparts photo-releasing property include an o-quinonediadi compound, an acid-decomposable ether compound, and an ester compound.

(1) Specific examples of o-quinonediazide compounds include, for example, JP-A-47-5303, JP-A-48-63802, and JP-A-48-63802.
63803, 49-38701, 56-1044, 56-1045,
Japanese Patent Publication No. 41-11222, No. 43-28403, No. 45-9610, No. 49-
17481, U.S. Pat.Nos. 2,797,213, 3,046,120,
No. 3,188,210, No. 3,454,400, No. 3,544,323
Issue No. 3,573,917, No. 3,674,495, No. 3,785,82
5, British Patent Nos. 1,227,602, 1,251,345, and
1,267,005, 1,329,888, 1,330,932, German Patent 854,890, etc., as examples of acid-decomposable compounds, JP-A-60-37549, 60-10247, 60-3625.
And the like, and these compounds can be preferably used alone or in combination as a photosensitive component.

These photosensitive components include o-quinonediazidecarboxylic acid ester of aromatic hydroxy compound, o-quinonediazidesulfonic acid of aromatic amino compound, o-quinonediazidecarboxylic acid amide, and the like.
The o-quinonediazide compound is used alone, or the o-quinonediazide compound is mixed with another resin and the mixture is provided as a photosensitive layer.

(2) Examples of the compound having a bond capable of being decomposed by an acid include, for example, ≡C—O—C≡ bond and ≡Si—O—C≡.
Compounds having a bond or ≡C-O-CO- bond or ≡Si-
The compound etc. which have an O-CO- bond are mentioned.

Specific compounds having a ≡C-O-C≡ bond include, for example, compounds having an acetal or ketal group,
Compounds having an orthocarboxylic acid ester group and / or a carboxylic acid amide acetanol group described in JP-A-51-120714, and polymers having an acetal or ketanol group in the main chain described in JP-A-53-133429. , JP-A-55
-12995 publication containing an ethanol ether group-containing compound, JP-A No. 55-126236 JP-containing compound having an N-acyliminocarbonate base, or JP-A No. 56-17345 main chain Examples thereof include polymers having an orthocarboxylic acid ester group.

Specific compounds having a ≡Si-O-C≡ bond include, for example, the compounds described in JP-A-60-37549, 60-52845 or 60-121446. it can.

Further, specific compounds having an ester group include, for example, the compounds described in JP-A-60-3625 or 60-10247.

Among these compounds having a bond capable of being decomposed by an acid, a compound having a ≡Si—O—C≡ bond is preferable. Among them, ≡Si-O described in JP-A-60-121446
A compound having at least one —C≡ bond and at least one hydrophilic group is particularly preferable. The compounds that can be decomposed by these acids may be used alone or in combination of two or more. The content of the compound capable of being decomposed by these acids is preferably 5 to 70% by weight, and particularly preferably 10 to 50% by weight, based on the total solid content of the photosensitive adhesive layer composition.

Further, the compound which can be decomposed by an acid needs to include a compound which produces an acid upon irradiation with actinic rays. Such compounds, many of the known compounds and mixtures, such as diazonium salts, phosphonium salts, sulfonium salts and iodonium _{^{BF 4 -, PF 6 -,}} Sb
_{^{F 6 -, SiF 6 2-,}} ClO 4 - salt of such an organic halogen compound, as the active ray sensitive component which forms or separates an acid during irradiation of o-quinonediazide sulfonyl chloride and organometallic / organohalogen compounds also active ray Can be used.

In principle, all organohalogen compounds known as free-radical-forming initiators can be used as photosensitive compounds capable of forming halohydrogenic acid. Examples of such compounds include U.S. Patents 3,515,552 and 3,536,4.
89, 3,779,778 and West German Patent Publication No. 2,2
No. 43,621.

Further, for example, West German Patent Publication No. 2,61
0,842, JP 54-74728, 55-77742, 57-1632
The compounds capable of generating an acid by photolysis described in JP-A No. 3 and 60-3626 can also be used.

Further, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209 can also be used.

In addition to the above-mentioned compound having a trihalomethyl group in combination with a suitable dye in the present invention, o-naphthoquinonediazide-4-sulfonic acid halogenide or JP-A-55-6244 and JP-A-59-218442. When an o-naphthoquinonediazide-based compound described in JP-A No. 1993-154 is used in combination, a clear visible contrast with good temporal stability can be obtained between the unexposed and exposed areas during exposure.

The content of these compounds capable of generating an acid upon irradiation with actinic rays can be varied over a wide range depending on its chemical properties and the composition or physical properties of the photosensitive resin layer. About 0.1 based on the total weight of solids
To about 10% by weight is suitable, preferably 0.2 to 5
It is in the range of% by weight.

In addition to the materials described above, dyes, pigments, plasticizers, etc. may be added to the photosensitive adhesive layer composition of the present invention, if desired, and the composition may be used for various purposes. Accordingly, if necessary, a so-called sensitizer (a compound which increases the acid generation efficiency of the compound capable of generating the acid) can be added.

Examples of such additive compounds include naphthalene, anthracene, phenanthrene, chrysene,
Pyrene, perylene, p-dinitrobenzene, p-nitrodiphenyl, p-nitroaniline, 2,4-dinitroaniline, picramide, 2-chloro-4-nitroaniline, 2,6-dichloro-
4-nitroaniline, p-nitrophenol, 9-anthraldehyde, benzophenone, dibenzalacetone, p,
p′-dimethylaminobenzophenone, Michler's ketone, 1,4-naphthoxynone, anthraquinone, 1,2-benzanthraquinone, anthrone, 1,9-benzanthrone,
3-methyl-1,3-diaza-1,9-benzanthrone and the like can be mentioned. Other examples include acridine dyes, merocyanine dyes, styryl dyes and the like, and in this case, an amine compound can be added if necessary.

In addition, (4) a type which reduces adhesiveness by photo-curing and brings about photo-peeling property, and (5) a type which uses a diazo compound or an azide compound and in which nitrogen gas generated by photolysis reduces adhesiveness, etc. Can be used.

The support of the sheet of the invention according to any one of claims 1 to 4 is such that it does not affect the photographic properties, is dimensionally stable and transparent to the light used for recording. Any material can be used. Typical supports include nitrocellulose film, triacetyl cellulose film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, poly α-olefin such as polyethylene, polypropylene film and other resin films. The surface of these supports is preferably subjected to an appropriate undercoating treatment in order to improve the coatability of the photosensitive layer and the adhesiveness of the photosensitive layer. Further, an antihalation layer containing a dye or a pigment may be provided on the front surface or the back surface of these supports for the purpose of preventing halation. The surface of the support opposite to the side where the photosensitive resin layer is provided is preferably matted for the purpose of improving the slipperiness of the recording material and the adhesion to the original during exposure.
The thickness of this support is preferably 50 μm or less,
More preferably, it is 4 to 20 μm.

The support of the printing plate precursor of the invention according to any one of claims 1 to 4 is preferably one which can be set in a normal lithographic printing machine and can withstand the load applied during printing, such as aluminum, Metal plates such as zinc, copper and steel, metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum and iron, paper, plastic films and glass plates, resin coated paper, metal foils such as aluminum. And the like. Among these, an aluminum plate is preferable.

The treatment of the support itself for improving the adhesion to the layer provided on the support is not particularly limited, and various surface-roughening treatments are included.

In the case of a support made of an aluminum plate, it is preferable that surface treatment such as graining treatment, anodic oxidation treatment and, if necessary, pore sealing treatment is performed.

As a method for the graining treatment, a technique of degreasing the surface of an aluminum plate or the like and then applying a brush polishing method, a ball polishing method, a chemical polishing method, an electric field etching method or the like is adopted.

The above-mentioned anodizing treatment is carried out by using, for example, an inorganic salt such as phosphoric acid, chromic acid, boric acid, sulfuric acid, etc., or an organic acid such as oxalic acid, sulfamic acid, etc., alone or in an aqueous solution or a mixture of two or more kinds of these acids. It is performed by passing an electric current in an aqueous solution using an aluminum plate or the like as an anode.

Further, the sealing treatment is carried out with an aqueous solution of sodium silicate,
It is carried out by dipping in hot water and a hot aqueous solution of some inorganic or organic salt, or by a steam bath.

The method of applying the coating solution used in the present invention includes dip coating, roll coating, reverse roll coating, air doctor coating, blade coating, rod coating, knife coating, squeeze coating, gravure coating, cast coating and curtain coating. A method such as extrusion coating is used.

A primer layer may be provided between the adhesive layer of the sheet of the invention according to claim 1 or 2 and the support,
Further, it is preferable to provide a primer layer between the ink repellent layer of the printing original plate and the support. Further, claim 3
Alternatively, a primer layer may be provided between the adhesive layer of the printing plate precursor of the invention according to 4 and the support. As these primer layers, the primer layers in the sheet of the invention according to claim 3 or 4 can be applied.

A protective film may be laminated on the uppermost layer on the side of the adhesive layer or the ink repellent layer of the sheet provided with the adhesive layer or the ink repellent layer. As the protective film, a transparent and flexible film is preferable, and for example, a polyester film (for example, polyethylene terephthalate film) can be used.

In the inventions according to claims 1 to 4, the resist image formed on the adhesive layer or the ink repellent layer is:
It is sufficient to change the adhesive force between the adhesive layer and the ink repellent layer to be equal to or less than the adhesive force in the non-image area (the area without the resist image layer). It can be formed by a known technique such as an electrophotographic method, a thermal transfer method including a diffusion type or a fusion type, and an inkjet method. When a resist image is formed on the release sheet side, it is preferable to provide a primer layer on the upper side thereof. This primer layer can be similar to the primer layer. Further, the resist layer is preferably colored in order to obtain image visibility.

[0097]

EXAMPLES Next, the present invention will be described more specifically by way of examples. In the following examples, "part" means "part by weight".

Example 1 Preparation of printing original plate (A) The following primer layer coating composition was applied on a smooth aluminum plate degreased by a usual method so that the film thickness after curing was 5 μm, and dried. , High pressure mercury lamp (output 80W / c
m) and exposed and cured.

Coating composition for primer layer 100 parts copolymer of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 40/60 100 parts trimethylolpropane triethoxytriacrylate 80 parts 2,4-diethylthioxanthone 4 parts p- Dimethylaminobenzoic acid ethyl ester 4 parts Yellow pigment (KET-YELLOW402, Dainippon Ink and Chemicals, Inc.) 8 parts White pigment (zinc oxide, FINEX-25, Sakai Chemical Co., Ltd.) 25 parts Propylene glycol monomethyl ether 600 parts On the primer layer thus formed, a photosensitive adhesive layer coating composition having the following composition was applied and dried at 100 ° C. for 2 minutes to form a photosensitive adhesive layer having a thickness of 10 μm.

Coating composition for adhesive layer Adduct of glycidyl methacrylate / xylenediamine (molar ratio 4: 1) 3 parts Adipic acid and hexane-1,6-diol, 2,2-dimethylpropane-1,3-diol Polyurethane of polyester polyol with isophorone diisocyanate 1 part Michler's ketone 0.2 part Preparation of sheet (A) Dry the following silicone rubber composition as a coating composition for ink repellent layer on a polypropylene film support with a thickness of 10 μm Apply so that the weight is 2.0 g / m ² , and apply at 90 ° C for 1
After drying for 0 minutes, a sheet (A) having a silicone rubber layer as an ink repellent layer on the support was prepared.

Silicone rubber composition Dimethylpolysiloxane having hydroxyl groups at both ends (Molecular weight 52000) 100 parts Triacetomethylsilane 10 parts Isopar G (trade name, manufactured by Esso Kagaku) 900 parts Separately, conductive aluminum is prepared by the following method. A toner image was formed on the vapor deposited polyethylene terephthalate film.

A composition liquid obtained by dispersing the following composition for 2 hours with a sand grinder was applied at a dry weight of 50 g / m ² on a conductive aluminum vapor-deposited polyethylene terephthalate film and dried at 90 ° C. for 15 minutes to give an electrophotographic photoreceptor. Created.

Ε-type copper phthalocyanine 30 parts Phenol / m-cresol / p-cresol-formaldehyde polycondensation novolac resin (mixing ratio = 10:50:40 (weight ratio)) 70 parts Propylene glycol monomethyl ether 4 parts This electronic photograph A toner image was formed on the photoreceptor by the following method. After using a scorotron to charge the plate surface potential to +200 V, scan with a semiconductor laser with an output of 3 mW at a scanning speed of 250 m /
Exposure for sec was performed to form an electrostatic latent image. Immediately after that, the liquid was developed using the liquid developing apparatus disclosed in Japanese Examined Patent Publication No. 2-19952, dried, and then heat-fixed at 130 ° C. for 10 seconds.

The liquid developer was manufactured as follows.

Octadecyl methacrylate / methacrylic acid copolymer (copolymerization ratio 90:10) 1 part Isopar G (trade name, manufactured by Esso Kagaku) 5 parts MA-100 (carbon black, manufactured by Mitsubishi Kasei) 1 part with glass beads for 5 hours After dispersion, a solution of 4 parts of Isopar G was added and further dispersed for 10 hours. This solution was diluted with Isopar G so that the solid content concentration became 0.3% by weight and used. In this way, a toner image was formed on the electrophotographic photosensitive member.

The electrophotographic photosensitive member on which the toner image was formed was stuck to the adhesive layer side of the printing original plate (A) so that the surface on which the toner image was formed was aligned.
When this polyethylene terephthalate film was peeled off, the toner image was transferred onto the printing original plate (A).

Next, the sheet (A) was laminated so that the adhesive layer side of the printing plate and the silicone rubber layer side of the sheet (A) face each other, laminated at 90 ° C., and then from the sheet (A) side. 500mJ / cm ² using metal halide lamp
The whole surface was irradiated with the ultraviolet rays. When the sheet (A) was peeled from the printing original plate (A), only the non-image area silicone rubber layer was transferred from the printing original plate to the sheet, and only the image area silicone rubber layer remained on the printing original plate. On the printing plate, 3 to 96% of dots with 175 screen lines were reproduced.
No background stain was generated during printing, and a good printing plate could be obtained.

Comparative Example 1 The printing original plate (A) and the sheet (A) were laminated at 90 ° C. without transferring the toner image onto the printing original plate,
Next, the same experiment as in Example 1 was conducted except that a positive film was adhered from the side of the sheet (A) and exposed to ultraviolet rays of 500 mJ / cm ² using a metal halide lamp. as a result,
When the sheet was peeled from the printing plate, a part of the silicone rubber in the image area remained in the printing plate, and the dot reproducibility on the plate surface was reduced to 10 to 80%. In addition, even at 50% halftone dots, a phenomenon was observed in which one halftone dot was not completely removed and a part of the halftone dot remained on the printing original plate.

Example 2 In place of the toner image in Example 1, the following resist image was formed on the adhesive layer of the printing original plate (A).

A 25 μm-thick ionomer resin (“High Milan 1652”, manufactured by Mitsui DuPont Polychemical Co., Ltd., VI on a 30 μm-thick polyethylene terephthalate film support)
CAT softening point 80 ℃) on the surface of the ionomer resin layer formed by extrusion laminator method, the dispersion for colored photosensitive layer of the following composition, dry film thickness by reverse roll coater
It was coated so as to have a thickness of 1.5 μm and dried at a drying temperature of 70 ° C. for 4 minutes to prepare a colored photosensitive sheet.

Dispersion liquid for colored photosensitive layer 2,3,4-trihydroxybenzophenone-naphthoquinone-1,2-diazide-4-sulfonic acid ester 0.616 parts Vinyl acetate-vinyl versatic acid copolymer (80:20 wt%, weight Average molecular weight 50000, 50% methanol solution) 8.768 parts Cyanine Blue 4920 (trade name, cyan dye, manufactured by Dainichiseika) 0.55 parts Toluene 35.2 parts 2-Propanol 2 parts A positive original is overlaid on the colored photosensitive sheet obtained above. Image exposure was carried out from a distance of 1 m with a 4 kW metal halide lamp for 40 seconds, and development was performed by immersing in the following developing solution for 30 seconds. Only the photosensitive layer in the image area remained.
The non-image area was eluted and removed. There was no background stain on the non-image portion, and a pigmented image having good pigment dispersibility in the image portion was formed.

Developer SDR-1 (Konica Corporation, developer for positive PS plate) 20 g Surfactant (Pelex NBL, manufactured by Kao Atlas) 50 g Distilled water 400 g Then, in the same manner as in Example 1, the above-mentioned colored sensitization was performed. The image side of the sheet and the adhesive layer side of the printing original plate (A) are brought into close contact with each other,
An image is transferred onto the adhesive layer of the printing original plate (A) by passing it between a pair of nip rolls heated to 80 ° C. under a pressure condition of 5 kg / cm ² at a speed of 50 cm / min. When the support of the colored photosensitive sheet was peeled off, only the image portion was satisfactorily transferred onto the printing original plate (A) to obtain a printing original plate (A) having a resist image. Then, in the same manner as in Example 1, the printing plate was laminated with the sheet (A), exposed, and peeled off to print only the silicone rubber layer in the non-image portion (the portion without the resist image layer). It was transferred to the original plate (A). The halftone dot reproduction area on the plate surface of the obtained printing plate was 3 to 96%, and there was no background stain, and a good printed matter could be obtained.

Example 3 A resist image was formed on the adhesive layer of the printing original plate (A) as follows. That is, a coating composition for a thermal transfer layer having the following composition was coated on a polyethylene terephthalate film having a thickness of 3.5 μm so as to have a dry film thickness of 2 μm by using a wire bar, thereby forming a thermal transfer layer. I made a film.

Coating composition for thermal transfer layer Carbon black (# 30, manufactured by Mitsubishi Kasei Co., Ltd.) 20 parts Carnauba wax 60 parts Xylene 100 parts The thermal transfer layer surface of this thermal transfer film is used as a printing original plate (A).
Thermal transfer recording was performed with an applied energy of 3 mj / dot using a thermal printer having a thermal head (on which a thin-film serial head having a heating element density of 7 dots / mm was mounted and printing pressure was 600 g / head). As a result, a good positive resist image was formed on the printing original plate (A). Hereinafter, when a printing plate was formed and evaluated in the same manner as in Example 1, the same results as in Example 1 were obtained.

Example 4 Except that the sheet in Example 2 was changed as follows,
The same experiment as in Example 2 was conducted.

Sheet (B) The following photosensitive composition was coated on a polypropylene film support to form a primer layer having a thickness of 0.1 μm in the same manner as in Example 1, and then a silicone rubber layer was coated. Dry at 90 ° C for 10 minutes. High pressure mercury lamp (80W /
cm) to expose a sheet. As a result, the reproduction range of the obtained printing plate was 2 to 97%, and other than that, the same results as in Example 1 were obtained.

[0117]

According to the present invention, since the adhesiveness is changed by exposure, which is a drawback of the conventional waterless planographic printing, the difference in adhesiveness between the exposed portion and the non-exposed portion is not sufficient. Therefore, the image reproducibility is poor, the reproducibility of highlights and shadows is reduced, development unevenness occurs in the peeling direction, and the rinsing problem, and there are variations in quality due to the environment due to temperature, humidity, and aging after manufacturing. Provided is a method for producing a waterless planographic printing plate which is large and has an improved problem of insufficient image reproducibility and has improved image reproducibility and stability.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view for explaining a plate making method of the invention according to claim 1.

FIG. 2 is a schematic cross-sectional view for explaining the plate making method of the invention according to claim 2.

FIG. 3 is a schematic cross-sectional view for explaining the plate making method of the invention according to claim 3.

[Explanation of symbols]

 1,1a sheet 2,6 support 3 adhesive layer 4 resist layer 5,5a printing original plate 7 ink repellent layer

Claims (4)

[Claims] 1. A negative resist image is formed on an adhesive layer of a sheet having an adhesive layer provided on a support,
The sheet is pressure-bonded to a printing original plate having an ink-repellent layer as the uppermost layer so that the ink-repellent layer side and the adhesive layer side face each other, and the sheet is peeled to remove the ink-repellent portion of the image area. A method for making a waterless planographic printing plate, which comprises removing the water-soluble layer. 2. A sheet in which a negative resist image is formed on the ink repellent layer of a printing original plate having an ink repellent layer as the uppermost layer, and then the printing original plate is provided with an adhesive layer on a support. And a method for making a waterless planographic printing plate, characterized in that the ink repellent layer side of the image area is removed by press-bonding the ink repellent layer side and the adhesive layer side so as to face each other and peeling off the printing original plate. . 3. A sheet having an ink repellent layer as an upper layer on a support after forming a positive resist image on the adhesive layer of a printing original plate having an adhesive layer provided on the support. It is characterized in that the ink repellent layer of the non-image area is transferred to the printing original plate by pressure-bonding to the original plate so that the ink repellent layer side and the adhesive layer side face each other and peeling off the sheet. Waterless planographic printing plate making method. 4. A positive resist image is formed on the ink-repellent layer of a sheet provided with an ink-repellent layer on the support, and then the sheet is provided with an adhesive layer on the support. It is possible to transfer the ink repellent layer in the non-image area to the printing original plate by pressure-bonding it to the printing original plate so that the adhesive layer side and the ink repellent layer side face each other and peeling off the sheet. A method of making a waterless planographic printing plate which is a feature.