JPH09311442A - Photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive planographic printing plate having good chemical resistance, high sensitivity and a wide application range for development by forming photosensitive layers in such a manner that a photosensitive layer far away from a supporting body has higher glass transition temp. than a layer nearer to the supporting body. SOLUTION: Two layers of photosensitive layers of photosensitive layers having a photosensitive compsn. containing an o-quinone diazide compd. and an alkali-soluble resin are formed on a substrate. The glass transition temp. (Tg) of the photosensitive layer farther from the substrate is controlled higher by >=5 deg.C than that of the photosensitive layer nearer to the substrate. The proportion of the o-quinone diazide compd. is higher in the photosensitive layer farther from the substrate than in the photosensitive layer near to the substrate. The photosensitive layer far away from the substrate has a higher content of an inclusion compd. than the photosensitive layer nearer to the substrate, or only the farther photosensitive layer contains an inclusion compd. Thereby, the obtd. photosensitive planographic printing plate has good chemical resistance, high sensitivity and a wide application range for development.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-working photosensitive lithographic printing plate, and more specifically to a positive-working photosensitive material having good chemical resistance or visible imageability upon exposure, high sensitivity, and a wide range of application and development. Regarding lithographic printing plates.

[0002]

2. Description of the Related Art A lithographic printing method is a printing method that utilizes the fact that water and oil are not essentially mixed with each other. An image area receiving the oily ink is formed by repulsion, and printing is performed by supplying water and oily ink from a printing machine and transferring only the oily ink received in the image area to paper. The printing press once transfers the oil-based ink received in the image area of the printing plate to a rubber blanket,
An offset printing method of transferring to paper is generally used.

Conventionally, as a support used in a photosensitive lithographic printing plate, a support excellent in hydrophilicity, water retention, and adhesion to a photosensitive layer has been required from the viewpoint of printability. Therefore, an aluminum plate which has been subjected to a surface roughening treatment called graining is usually used. The surface roughening treatment includes mechanical surface roughening methods such as ball polishing, brush polishing, blast polishing, buff polishing, and honing polishing, and electrolysis of the support surface by alternating current or direct current in an acidic electrolyte such as hydrochloric acid or nitric acid. Electrochemical surface roughening methods and the like for processing are known. Since the aluminum plate grained by such a method is relatively soft and easily abraded as it is, it is then subjected to an anodic oxidation treatment to form an oxide film. The surface of the aluminum plate treated in this way is hard and has excellent wear resistance.

As the positive-working photosensitive lithographic printing plate, one in which a photosensitive layer made of an o-quinonediazide compound is provided on an aluminum plate thus treated is widely known. It is known that o-quinonediazide changes to carboxylic acid upon exposure to ultraviolet light, and when this is developed with an aqueous alkali solution, only the exposed portions of the photosensitive layer are removed and the surface of the support is exposed. Since the surface of the aluminum support is hydrophilic, the portion (non-image area) where the surface of the support is exposed by development receives water and repels the oil-based ink. On the other hand, the portion (image portion) of the photosensitive layer which has not been removed by development is lipophilic and repels water to receive oil-based ink. In general, the higher the sensitivity of a photosensitive lithographic printing plate, the shorter the time required for exposure, and the plate making operation can be performed quickly.

However, in the positive-type photosensitive lithographic printing plate using the above-mentioned o-quinonediazide compound, when the amount of the photosensitive compound in the photosensitive layer is reduced as a means for increasing the sensitivity, the range of appropriate developing conditions becomes narrow. In addition, there is a problem in that the resistance of the image portion to various chemicals used during printing is lowered, causing poor printing durability. The sensitivity can also be increased by a method such as adding an organic acid to the photosensitive layer or adding a cyclic acid anhydride described in JP-A-52-80022 to the photosensitive layer. However, this method also has the same problems as described above. Further, in JP-A-58-205154, o of the upper photosensitive layer is disclosed.
-A technique has been disclosed in which the content of the quinonediazide compound is higher than that of the lower photosensitive layer, but this technique also does not sufficiently solve the above problem.

Further, in the plate making of the photosensitive lithographic printing plate, an exposure operation such as so-called "multi-sided printing", in which the positions of a plurality of film originals are changed and printing is performed, is performed. In such an exposure operation, if the exposed portion and the unexposed portion cannot be discriminated, the position of the exposed portion cannot be confirmed, which makes the exposure operation difficult and results in an erroneous exposure. In order to avoid such an error, it is required that the photosensitive layer has a so-called exposure visible image property in which a visible image that can be confirmed even under a yellow safety light used for an exposure operation is formed by exposure. , The exposure visibility is
It is conventionally known that it can be imparted by including a printout material in the photosensitive layer. The printout material is a material that forms a visible image upon exposure, and contains an organic dye that changes its color tone by interacting with an acid or a compound that forms a free radical upon exposure. Examples of the compound that generates an acid or a free radical upon exposure to light include, for example, JP-A-5-
Trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A-3-36223, JP-A-55-777.
42, halomethyl-vinyl-oxadiazole compounds, diazonium salts and the like.

However, when these printout materials are added to the photosensitive layer, not only there is a problem that the sensitivity is lowered and the proper developing condition range is narrowed, but also after development, there is no color change in the non-image area. The above dye remains on the plate, so-called dye residue occurs, which causes printing stains.

[0008]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a photosensitive lithographic printing plate which has good chemical resistance, high sensitivity and a wide range of applicable development. A second object of the present invention is to provide a photosensitive lithographic printing plate which has a good exposure visible image property, high sensitivity, and a wide applicable developing range.

[0009]

The above-mentioned problems of the present invention are as follows. In a photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on the support, the glass transition temperature (Tg) of the photosensitive layer is the support. A photosensitive lithographic printing plate characterized in that the photosensitive layer on the far side is higher by 5 ° C. or more than the photosensitive layer on the near side,

[0010] 2. In a photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, the content of the o-quinonediazide compound is close to that of the support. The photosensitive layer on the side farther than the photosensitive layer on the side is higher, and the content of the inclusion compound is higher on the photosensitive layer on the side farther than the photosensitive layer on the side closer to the support, or on the support. A photosensitive lithographic printing plate characterized by containing an inclusion compound only in the photosensitive layer on the far side,

3. In a photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, the alkali-soluble resin is at least a novolac resin and an acrylic polymer. Consists of, and

[0012]

[Equation 2] However, the photosensitive lithographic printing plate characterized in that the photosensitive layer on the far side is more than the photosensitive layer on the side closer to the support,

4. In a photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, the solubility in an alkaline aqueous solution is closer to that of the support. A photosensitive lithographic printing plate characterized in that the photosensitive layer on the far side is lower than the photosensitive layer,

5. The alkali-soluble resin is at least a novolac resin, and the weight average molecular weight (Mw) of the novolac resin is 1000 or more higher in the photosensitive layer on the far side than the photosensitive layer on the side closer to the support. The photosensitive lithographic printing plate described,

6. The alkali-soluble resin is composed of at least a novolac resin, and the amount of phenol component (mol%) of the novolac resin is lower than the photosensitive layer on the side closer to the support by 5 mol% or more. 4. The photosensitive lithographic printing plate as described in 4 above,

[7] The o-quinonediazide compound is an o-quinonediazide sulfonic acid ester of a polyhydroxy compound, and the weight average molecular weight (M
5. The photosensitive lithographic printing plate as described in 4 above, wherein w) is 500 or more higher in the photosensitive layer on the side farther than the photosensitive layer on the side closer to the support.

8. The o-quinonediazide compound is an o-quinonediazide sulfonic acid ester of a polyhydroxy compound, and the esterification rate for all hydroxyl groups of the polyhydroxy compound is 5 in the photosensitive layer on the side farther than the photosensitive layer on the side closer to the support. % Or more, the photosensitive lithographic printing plate as described in 4 above,

9. In a photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, o-in the o-quinonediazide compound
A photosensitive lithographic printing plate characterized in that the content of the condensate of quinonediazide-5-sulfonyl chloride is higher in the photosensitive layer on the far side than on the photosensitive layer on the side closer to the support;

10. In a photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, the content of the photo-acid generator and the dye is the support. Is the photosensitive layer on the far side higher than the photosensitive layer on the side closer to?
Alternatively, a photosensitive lithographic printing plate characterized by containing a photoacid generator and a dye only in the photosensitive layer on the side remote from the support.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (Support) The aluminum support used in the present invention includes a support made of pure aluminum and an aluminum alloy. Various aluminum alloys can be used, for example, silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium,
An alloy of aluminum with a metal such as sodium or iron is used.

(Degreasing Treatment) The aluminum support is preferably subjected to a degreasing treatment in order to remove the rolling oil on the aluminum surface prior to roughening. As the degreasing treatment,
Degreasing treatment using a solvent such as trichlene and thinner, emulsion degreasing treatment using an emulsion of kerosene and triethanol, etc. are used. In addition, for degreasing,
An aqueous solution of an alkali such as caustic soda can also be used. When an aqueous solution of an alkali such as caustic soda is used for the degreasing treatment, dirt and oxide films that cannot be removed only by the above degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for degreasing, smut is formed on the surface of the support. In this case, phosphoric acid, nitric acid, sulfuric acid,
Desmutting is preferably performed by immersing in an acid such as chromic acid or a mixed acid thereof.

(Graining treatment) As a graining treatment method for improving the adhesion to the photosensitive layer and improving the water retention property, the surface is mechanically roughened, so-called mechanical roughening. Method, so-called electrochemical surface-roughening method, so-called electrochemical surface-roughening method, and so-called chemical surface-roughening method, roughening the surface with an etching agent composed of alkali or acid or a mixture thereof. There is a law. Also, a method combining these can be used.

Examples of the mechanical surface roughening method include ball polishing, brush polishing, blast polishing, buff polishing, honing polishing and the like. Among them, brush polishing and honing polishing are preferable. Further, it is also possible to attach a sheet having a roughened surface in advance to the surface of the support and apply pressure to transfer the roughened pattern to roughen the surface.

The electrochemical graining method includes, for example, a method of electrolytically treating a support with an alternating current or a direct current in an electrolytic solution containing hydrochloric acid, nitric acid or the like. The support can be grained by using any one of them or a combination of two or more thereof.

Regarding the electrochemical graining method, for example,
Japanese Examined Patent Publication No. 48-28123, British Patent No. 89656.
The method described in the specification No. 3 and JP-A-53-67507 can be used.

The voltage applied in the electrochemical graining is preferably 1 to 50V, more preferably 5 to 30V. The current density is preferably 10 to 200 A / dm ² ,
20 to 150 A / dm ² is more preferable. Electric quantity is 1
00-2000C / dm ² , preferably 200-150
0 C / dm ² , more preferably 200 to 1000 C / d
a m ^2. The temperature is preferably from 10 to 50 ° C, and from 15 to 50 ° C.
45 ° C is more preferred. Hydrochloric acid or nitric acid concentration is 0.1-5
% By weight is preferred. The electrolyte contains nitrates, if necessary.
Chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like can be added.

When two or more surface-roughening treatments are combined, the surface is preferably etched by dipping in an acid or alkali aqueous solution between the treatments. The acid includes, for example, sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and the base includes, for example, sodium hydroxide, potassium hydroxide, and the like. Among these, it is preferable to use an aqueous alkali solution. Using a 0.05 to 40% by weight aqueous solution of these acids or alkalis, a treatment is carried out at a liquid temperature of 40 to 100 ° C. for 5 to 300 seconds. When the above is immersed in an aqueous solution of alkali, smut is formed on the surface of the support, and in this case, phosphoric acid, nitric acid, sulfuric acid, acid such as chromic acid or a mixed acid thereof, It is preferable to apply a desmut treatment. The surface-roughening treatment may be performed on the back surface in order to impart slipperiness to prevent scratches on the photosensitive layer during transportation.

(Anodizing Treatment) The roughened support is then subjected to anodizing treatment. As the electrolytic solution used for the anodizing treatment, any one can be used as long as it forms a porous oxide film, and in general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, sulfamic acid, benzenesulfonic acid or two or more kinds of these A mixed acid that is a combination of The anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be specified unconditionally. However, generally, the concentration of the electrolytic solution is 1 to 80% by weight, the temperature is 5 to 70 ° C,
Current density 1 to 60 A / dm ^2, voltage 1 to 100 V, is suitably electrolysis time of 10 seconds to 5 minutes. The sulfuric acid method is preferred, and the treatment is usually performed with a direct current, but an alternating current can also be used. The concentration of sulfuric acid is 10 to 50% by weight, the temperature is 20 to 50 ° C, and the current density is 20 to 20 A / dm ² .
Preferably, the electrolytic treatment is performed for 250 seconds. It is preferable that the electrolytic solution contains aluminum ions.

(Sealing treatment) The support may be subjected to sealing treatment after the anodizing treatment. Examples of the sealing treatment include hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

(Hydrophilic treatment) Further, the support is preferably subjected to an anodizing treatment (further after the pore-sealing treatment), and then subjected to a hydrophilic treatment, that is, a hydrophilic layer is provided.
Examples of the hydrophilic layer include alkali metal silicates described in US Pat. No. 3,181,461 and US Pat.
Hydrophilic cellulose described in JP-A No. 0,426, amino acids and salts thereof described in JP-A-60-149491 and 63-165183, JP-A-60-2329.
No. 98, hydroxyl group-containing amines and salts thereof, JP-A-62-19494, phosphate salts, and polymer containing a sulfo group-containing monomer unit, described in JP-A-59-101651. A compound etc. are mentioned.

Further, in order to prevent scratches on the photosensitive layer when the photosensitive lithographic printing plates are superposed, and to prevent the elution of the aluminum component into the developing solution at the time of development, JP-A-50-50
-151136, 57-63293, 60-7.
No. 3538, No. 61-67863, JP-A-6-351.
The treatment of providing a protective layer on the back surface of the support described in No. 74 etc. can be performed. On the back surface of the support, arbitrary patterns, figures, characters, etc. for realizing the design and barcodes may be formed by an inkjet method, a printing method, or the like.

(Photosensitive Layer) Next, a photosensitive lithographic printing plate is obtained by coating the following photosensitive layer on the surface-treated aluminum support. The photosensitive lithographic printing plate of the present invention is one in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided, and between the upper layer and the lower layer, or on the upper layer. There may be a third photosensitive layer underneath or underneath. As described above, when the photosensitive layer is composed of three or more layers, it is only necessary that at least one set of the upper layer and the lower layer satisfies the respective constitutional requirements of the present invention. In this specification,
The photosensitive layer on the side closer to the support may be referred to as the lower photosensitive layer, or simply the lower layer, and the photosensitive layer on the far side may be referred to as the upper photosensitive layer, or simply the upper layer.

The constitution of the photosensitive layer will be described in detail below.
The details of each compound described in each of the following constitutions will be described later.

In the present invention according to claim 1, the glass transition temperature (Tg) of the photosensitive layer is higher by 5 ° C. or more in the upper photosensitive layer than in the lower photosensitive layer, and the preferable Tg (each single layer). When it is provided on the support), the upper layer is 80 to
150 ° C, the lower layer is in the range of 70 to 140 ° C.

In the present invention as defined in claim 2, the content of the o-quinonediazide compound in the upper photosensitive layer is higher than that in the lower photosensitive layer, and the content of the inclusion compound is higher than that in the lower photosensitive layer. Or the inclusion compound is contained only in the upper photosensitive layer. When the lower layer does not contain the o-quinonediazide compound, it is included in the present invention by including the o-quinonediazide compound in the upper layer.
The proportion of the o-quinonediazide compound in the photosensitive layer component is preferably 20 to 90% by weight in the upper layer, preferably 5 to 40% by weight in the lower layer, and more preferably 10 to 30% by weight.
When both the upper layer and the lower layer contain an o-quinonediazide compound, the difference in the content of the o-quinonediazide compound between the upper layer and the lower layer is preferably 1% by weight or more,
More preferably, it is 5% by weight or more. The ratio of the clathrate compound in the photosensitive layer component is preferably 0.
01 to 10% by weight, more preferably 0.01 to 5% by weight, lower layer preferably 0 to 5% by weight, more preferably 0.
Is in the range of 3 wt%.

In the present invention as set forth in claim 3, the alkali-soluble resin comprises at least a novolac resin and an acrylic polymer, and

[0037]

(Equation 3) However, the photosensitive layer on the far side is more than the photosensitive layer on the side closer to the support, and the proportion of the acrylic polymer in the photosensitive layer component is preferably 5 to 95% by weight in the upper layer. ,
It is more preferably in the range of 10 to 95% by weight, preferably in the range of 0.5 to 20% by weight in the lower layer, and the ratio of the novolak resin in the photosensitive layer component is preferably 0.5 to 2 in the upper layer.
The amount of the lower layer is 0% by weight, preferably 5 to 95% by weight, more preferably 10 to 95% by weight.

In the present invention as defined in claim 4, the upper photosensitive layer has a lower solubility in an aqueous alkaline solution than the lower photosensitive layer, specifically, the following constitutions.

The alkali-soluble resin comprises at least a novolac resin, and the weight average molecular weight (Mw) of the novolac resin is 10 in the upper photosensitive layer than in the lower photosensitive layer.
The composition of the novolak resin has a weight average molecular weight of 1000 to 30,000 Mw in the upper layer.
The range is more preferably 3000 to 20000 Mw, and the lower layer is preferably 1000 to 25000 Mw, more preferably 1000 to 20000 Mw.

The alkali-soluble resin is composed of at least a novolac resin, and the phenol component amount (mol%) of the novolac resin in the upper photosensitive layer is lower than the lower photosensitive layer by 5 mol% or more. The amount of components is preferably 0 to 80 mol% in the upper layer, more preferably 0 to 60 mol%, and preferably 5 to 90 in the lower layer.
Mol%, and more preferably 5 to 80 mol%.

The o-quinonediazide compound is an o-quinonediazidesulfonic acid ester of a polyhydroxy compound, and the weight average molecular weight (M
w) is 500 or more higher in the upper photosensitive layer than in the lower photosensitive layer, the polyhydroxy compound is preferably a polycondensation resin of phenols and aldehydes or ketones, and the weight average molecular weight of the upper layer is preferably 1000- 2000
0 Mw, more preferably 1500 to 10000 Mw, lower layer preferably 500 to 10000 Mw, more preferably 1000 to 8000 Mw.

The o-quinonediazide compound is an o-quinonediazide sulfonic acid ester of a polyhydroxy compound, and the esterification rate of the polyhydroxy compound with respect to all hydroxyl groups in the upper photosensitive layer is 5% or more higher than in the lower photosensitive layer. The esterification rate of the upper layer is preferably 5 to 80%, more preferably 10 to 50%, and the lower layer is preferably 5 to 60%, more preferably 5 to 45%.

In the present invention according to claim 9, the content of the condensate of o-quinonediazide-5-sulfonyl chloride (hereinafter sometimes referred to as 5Q ester) in the o-quinonediazide compound is higher than that of the lower photosensitive layer. Has a higher configuration. When the lower layer does not contain the 5Q ester, it is included in the present invention by including the 5Q ester in the upper layer. That is, the lower layer contains, for example, a condensate of o-naphthoquinonediazide-4-sulfonyl chloride (hereinafter sometimes referred to as 4Q ester),
When the ester is not contained, it is included in the present invention by including the 5Q ester in the upper layer. The proportion of the 5Q ester in the photosensitive layer component is preferably 20 to 90% by weight, more preferably 25 to 85% by weight in the upper layer, and preferably 0 to 40% by weight, more preferably 0 to 30% by weight in the lower layer. And when both upper and lower layers contain 5Q ester,
The difference in content of 5Q ester between the upper layer and the lower layer is preferably 1% by weight or more, and more preferably 5% by weight or more.

In the present invention according to claim 10, the content of the photoacid generator and the dye is higher in the upper photosensitive layer than in the lower photosensitive layer, or only the upper photosensitive layer contains the photoacid generator and the dye. The ratio of the photo-acid generator to the photosensitive layer component is preferably 0.01 to 30% by weight in the upper layer,
The range is more preferably 0.1 to 10% by weight, the lower layer is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and the proportion of the dye in the photosensitive layer component is preferably 0. 01-10% by weight, more preferably 0.02-
5% by weight, preferably 0 to 5% by weight in the lower layer, more preferably 0 to 2% by weight.

The upper layer and / or the lower layer of the present invention may contain two or more kinds of o-quinonediazide compounds. The upper layer and the lower layer may be mixed to some extent as long as the effects of the present invention are not lost. That is, the present invention also includes a photosensitive lithographic printing plate having a gradient composition in which conditions satisfying the respective constituent requirements of the present invention such as the glass transition temperature, the content rate and the solubility change as the distance from the support increases.

There are no particular restrictions on the other conditions for the photosensitive substance used in the photosensitive layer, and various conditions generally used for positive-working photosensitive lithographic printing plates can be used. Hereinafter, this point will be described.

(Photosensitive composition containing o-quinonediazide compound) The o-quinonediazide compound used in the present invention is a compound having an o-quinonediazide compound in its molecule.

Examples of the o-quinonediazide compound include ester compounds of o-quinonediazide sulfonic acid and various aromatic polyhydroxy compounds, or polycondensation resins of phenols and aldehydes or ketones.

Examples of the phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, and dihydric compounds such as catechol, resorcinol and hydroquinone. Examples include trihydric phenols such as phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred of these are formaldehyde and benzaldehyde. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m- and p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin. To be

The condensation rate of o-quinonediazidesulfonic acid with respect to the OH group of the phenol of the o-quinonediazide compound (reaction rate with respect to one OH group) is preferably 5 to 80%, more preferably 10 to 45%. is there.

Further, as the o-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example,
2-benzoquinonediazidesulfonic acid ester, 1,2
-Naphthoquinonediazidesulfonic acid ester, 1,2-
Known 1,2 such as benzoquinonediazidesulfonic acid amide and 1,2-naphthoquinonediazidosulfonic acid amide
-Quinonediazide compounds, more specifically "Light-Sensitive Systems" by J. Kosar (Light-Sensitive Systems)
tems) 339-352 (1965), John Willie and Sons (John Willley)
& Sons, Inc. (New York) and W.S.
"Photoresist" by WS De Forest, No. 50
(1975), McCraw Hill (Mc Graw)
Hill, Inc. (New York)
-Benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,
2-benzoquinonediazide-4- (N-ethyl-N-β
-Naphthyl) -sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1
-(1,2-naphthoquinonediazide-5-sulfonyl)
-3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfone-4'-hydroxydiphenyl-4'-azo-β-naphthol-ester, N, N-di- (1,2-naphthoquinonediazide- 5-sulfonyl)
-Aniline, 2 '-(1,2-naphthoquinonediazide-
5-sulfonyloxy) -1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide-5-sulfone-
2,4-dihydroxybenzophenone ester, 1,2
-Naphthoquinonodiazide-5-sulfonic acid-2,3,4
Trihydroxybenzophenone ester, condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4'-diaminobenzophenone,
Condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride with 1 mol of 4,4'-dihydroxy-1,1'-diphenylsulfone, 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride And 1,2-quinonediazide compound such as 1,2-naphthoquinonediazide-5- (N-dihydroabiethyl) -sulfonamide. In addition, Japanese Examined Patent Publications No. 37-1953 and 37-3627
Nos. 37-13109, 40-26126, 40-3801, 45-5604, and 45-27
No. 345, No. 51-13013, JP-A-48-965.
The 1,2-quinonediazide compounds described in JP-A No. 75, 48-63802 and 48-63803 can also be mentioned.

Of the above o-quinonediazide compounds,
An o-quinonediazide ester compound obtained by reacting 1,2-benzoquinonediazidosulfonyl chloride or 1,2-naphthoquinonediazidosulfonylchloride with a pyrogallol-acetone condensed resin or 2,3,4-trihydroxybenzophenone is particularly preferred. As the o-quinonediazide compound used in the present invention, the above compounds may be used alone or in combination of two or more. The proportion of the o-quinonediazide compound in the photosensitive composition is preferably from 6 to 60% by weight, and particularly preferably from 10 to 50% by weight.

(Inclusion Compound) The inclusion compound that can be used in the present invention is not particularly limited as long as it is a compound capable of incorporating (inclusion) a chemical species.
Organic compounds soluble in the solvent used for preparing the composition are preferred. Examples of such organic compounds include, for example,
Books such as “Host Guest Chemistry” (Michio Hiraoka et al., Kodansha 1984, Tokyo) and “Tetrahedron Report” (No. 226 (1987) P5725A. Co.)
llet et al.), "Chemical Industry April Issue" ((1991) P2
78 Shinkai et al.), “Chemical Industry April Issue ((1991) P28
8 Hiraoka et al.) And the like.

Inclusion compounds which can be preferably used in the present invention include, for example, cyclic D-glucans, cyclophanes, neutral polyligands, cyclic polyanions, cyclic polycations, cyclic peptides and SPHERANDS, CAVITAND
NDS) and their acyclic analogs. Among these, cyclic D-glucans and their non-cyclic analogs, cyclophanes, and neutral polyligands are more preferred. Examples of the cyclic D-glucans and non-cyclic analogs thereof include compounds in which α-D-glucopyranose is linked by a glycooxide bond.

Examples of the compound include starch, amylose, amylopectone, and other sugars composed of D-glucopyranose groups, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and D-glucopyranose group. A cyclodextrin having a degree of 9 or more, and SO ₃ C ₆ H ₄ CH ₂ C and the like.
₆ H ₄ SO ₃ group, NHCH ₂ CH ₂ NH group, NHCH ₂
CH ₂ NHCH ₂ CH ₂ NH group, SC ₆ H ₅ group, N ₃
Group, NH ₂ group, NEt ₂ group, SC (NH ₂ ⁺ ) NH
₂ group, SH _group, SCH 2 _CH 2 NH ₂ group, an imidazole group, modifications of the introduced D- glucans substituents such as ethylene diamine group. In addition, the following general formula [I]
And cyclodextrin derivatives represented by the general formula [II], branched cyclodextrins, cyclodextrin polymers and the like.

[0057]

Embedded image

In the general formula [I], R _{1 to} R ₃ may be the same or different and each represents a hydrogen atom, an alkyl group or a substituted alkyl group. In particular, those in which R _{1 to} R ₃ are a hydrogen atom, a hydroxyethyl group, or a hydroxypropyl group are preferable, and those in which the content of the substituted alkyl group in one molecule is 15% to 50% are more preferable.
n ₂ represents a positive integer of 4-10.

[0059]

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[0060] In the general formula [II], R represents a hydrogen ^{_{atom, -R 2 -CO 2 H, -R}} 2 -SO 3 H, -R 2 -N
H ₂ or —N— (R ³ ) ₂ (R ² represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R ³ represents a linear or branched alkyl group having 1 to 5 carbon atoms. Represents a group.

The branched cyclodextrin used in the present invention is a known cyclodextrin in which a water-soluble substance such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine, or a water-soluble substance such as disaccharide is branched or added. And preferably,
Maltosylcyclodextrin in which maltose is bound to cyclodextrin (the number of molecules bound to maltose may be one, two or three) or glucosylcyclodextrin in which glucose is bound to cyclodextrin (the number of molecules bound to glucose) Is one molecule, two molecules,
Or any of three molecules).

As the cyclodextrin polymer used in the present invention, those represented by the following general formula [III] are preferable.

[0063]

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The cyclodextrin polymer has a water solubility, that is, a solubility in water of 100 ° C at 25 ° C.
Preferably there is at least 20g to milliliters, therefore the above-mentioned general formula [III] Polymerization degree n ₂ 3-4 Tosureba well in the variable of the water-soluble and the material of the cyclodextrin polymer itself smaller the value High solubilizing effect.

Cyclophanes are cyclic compounds having a structure in which aromatic rings are connected by various bonds, and many compounds are known.
These known compounds can be mentioned.

The bond connecting the aromatic rings is, for example, a single bond,-(CR ₁ R ₂ ) _m -bond or -O (CR ₁ R ₂ ) _m.
O-bond, -NH (CR ₁ R ₂ ) _m NH-bond,-(C
R ₁ R ₂ ) _p NR ₃ (CR ₄ R ₅ ) _q -bond,-(CR
₁ R ₂ ) _pN ⁺ R ₃ R ₄ (CR ₅ R ₆ ) _q -bond,-
(CR ₁ R ₂ ) _p S ⁺ R ₃ (CR ₄ R ₅ ) _q -bond,
—CO ₂ — bond, —CONR— bond (where R ₁ , R
₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m, p and q may be the same or different Often, an integer of 1 to 4 is shown. ) And the like. Neutral polyligands include crown compounds, cryptands, cyclic polyamines and their acyclic analogs. The compound is known to effectively incorporate metal ions, but can also effectively incorporate cationic organic molecules.

Other clathrates include urea, thiourea, deoxycholic acid, dinitrodiphenyl, hydroquinone, o-trithymotide, oxyflavan, dicyanamine nickel, dioxytriphenylmethane, triphenylmethane, methylnaphthalene, spirochroman, Examples include perhydrotriphenylene, viscous mineral, graphite, zeolite (faujasite, chabazite, mordenite, levynite, montmorillonite, halosite, etc.), cellulose, amylose, protein and the like.

Although these clathrate compounds may be added as a simple substance, they improve the solubility of the clathrate compound itself or the clathrate compound incorporating the molecule in a solvent and the compatibility with other additives. For this reason, a polymer in which a substituent having an inclusion ability is suspended as a pendant substituent may be added together with the polymer.

Among the above inclusion compounds, cyclic and acyclic D-
Glucans, cyclophanes, and acyclic cyclophane analogs are preferred. More specifically, cyclodextrin, calixarene, resorcinol-aldehyde cyclic oligomer, and para-substituted phenols acyclic oligomer are preferred. Most preferred are cyclodextrin and its derivatives, and among them, β-cyclodextrin and its derivatives are more preferred.

The content of these clathrate compounds in the photosensitive composition is preferably 0.01 to 10% by weight, and 0.1 to 10% by weight.
5% by weight is more preferred.

(Alkali-Soluble Resin) Examples of the alkali-soluble resin include novolac resins, acrylic polymers, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. .

The novolak resin used in the present invention includes, for example, phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55-5784.
Phenol / cresol / formaldehyde copolymer resin as described in JP-A No. 1-55, JP-A-55-12
Examples thereof include copolymer resins of p-substituted phenol and phenol or cresol and formaldehyde as described in Japanese Patent No. 7553.

The molecular weight (polystyrene standard) of the novolac resin is preferably 3.00 × in terms of number average molecular weight Mn.
10 ^{2 to} 7.50 × 10 ³ , and a weight average molecular weight Mw of 1.
00 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn
Is 5.00 × 10 ^{2 to} 4.00 × 10 ³ , and Mw is 3.0
It is 0 × 10 ^{3 to} 2.00 × 10 ⁴ . The novolak resins may be used alone or in combination of two or more. The proportion of the novolak resin in the photosensitive composition is preferably from 5 to 95% by weight.

(Acrylic Polymer) The acrylic polymer used in the present invention is a polymer obtained by polymerizing acrylic acid and its derivative, and the polymer is other than acrylic acid and its derivative. The thing which copolymerized the monomer of is also included.

Examples of acrylic acid and its derivatives include acrylic acids such as acrylic acid, methacrylic acid and α-chloroacrylic acid; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl ethacrylate,
Acrylic acid esters such as p-aminosulfonylphenyl methacrylate; nitriles such as acrylonitrile and methacrylonitrile; acrylamide, N- (p-
Aminosulfonylphenyl) methacrylamide, N-
Amides such as (p-methylaminosulfonylphenyl) methacrylamide; anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide; p-aminosulfonylphenylmethacrylate, etc. .

Monomers other than acrylic acid and its derivatives used as a copolymerization component include unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride; monomethyl itaconate, dimethyl maleate, Esters of unsaturated aliphatic dicarboxylic acids such as diethyl maleate; ethylene, propylene, isobutylene,
Ethylenically unsaturated olefins such as butadiene and isoprene; styrenes such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene; imides such as N-phenylmaleimide; vinyl acetate, vinyl propionate, benzoe Vinyl esters such as vinyl acetate and vinyl butyrate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether; vinyl chloride; vinylidene chloride; vinylidene cyanide; 1-methyl-
1-methoxyethylene, 1,1-dimethoxyethylene,
Ethylene derivatives such as 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene and 1-methyl-1-nitroethylene; N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene, Examples thereof include vinyl monomers such as N-vinyl compounds such as N-vinylpyrrolidone. These vinyl-based monomers have a structure in which unsaturated double bonds are cleaved and are present in the polymer compound.

Monomers other than acrylic acid and its derivative and acrylic acid and its derivative used as a copolymerization component may be bonded to the above-mentioned polymer compound in either a block or random state. The above polymers may be used alone or in combination of two or more. It can also be used in combination with other polymer compounds. The acrylic polymer of the present invention is preferably an acrylic polymer having a phenolic hydroxyl group.

(Vinyl Copolymer Having Phenolic Hydroxyl Group) In the acrylic polymer having a phenolic hydroxyl group, the phenolic hydroxyl group is represented by the following general formula [IV] to
It is preferably contained as a structural unit represented by [IX].

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In the general formulas [IV] to [IX], R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R
₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an optionally substituted alkylene group which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, and m is 0 to 1
Represents an integer of 0, and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. In the present invention, among these, a copolymer containing at least one structural unit represented by the general formula [V] is preferable.

As the copolymerization component of the acrylic polymer having the structural units represented by the general formulas [IV] to [IX],
Ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, for example, styrene, α-methylstyrene, p-methylstyrene, p
-Styrenes such as chlorostyrene, acrylic acids such as acrylic acid and methacrylsan, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, such as methyl acrylate, ethyl acrylate, acrylic acid-n -Α-methylene aliphatic monocarboxylic acid such as butyl, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl ethacrylic acid , Nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, and acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide and the like. Anilides, for example vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and other vinyl esters, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether and other vinyl ethers, vinyl chloride, vinylidene chloride, Vinylidene cyanide, for example 1-methyl-1-methoxyethylene, 1,
Ethylene derivatives such as 1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, Examples thereof include N-vinyl-based monomers such as N-vinylpyrrolidene and N-vinylpyrrolidone.

The copolymerization component of the acrylic polymer having the structural units represented by the general formulas [IV] to [IX] is
Among the above-mentioned monomers, acrylic acids, methacrylic acids, esters of aliphatic monocarboxylic acids, and nitrites are preferable because they show comprehensively excellent performance. More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate and the like.

The general formula [I
The content of the structural unit represented by each of V] to [IX] is preferably 5 to 70 mol%, particularly 10 to 40 mol%.
Is preferred. The proportion of the acrylic polymer in the photosensitive composition is preferably 5 to 95% by weight.

(Ultraviolet Absorbing Dye) The photosensitive composition used in the present invention may contain an ultraviolet absorbing dye in order to prevent halation.

Examples of such compounds include DIARESIN BRILLIANT, yellow 6G, DIARESIN yellow 3G, DIARESIN yellow F, DIARESIN red Z, DIARESIN yellow H2G, manufactured by Mitsubishi Kasei.
DIARESIN YELLOW HG, DIARESIN YELLOW HC, DIARESIN YELLOW HL, DIARESIN ORANGE HS, DIARESIN ORANGE G, DIARESIN RED GG, DIARESIN YELLOW GR, DIARESIN RED S, DIARESIN RED HS, DIARESIN RED A, Dialesin Red H, Diasid Ride Yellow 2G, Kayaset manufactured by Nippon Kayaku Co., Ltd.
Yellow K-RL, Kayaset Yellow K-CL, Kayaset Yellow E-G, Kayaset Yellow E-
AR, Kayaset Yellow AG, Kayaset Yellow GN, Kayaset Yellow 2G, Kayaset Yellow SF-G, Kayaset Orange K-RL, Kayaset Orange G, Kayaset Orange A-N, Kayaset Orange SF- R, Kayaset Flavin F
N, Kayaset Flavin FG, Kayaset Red K
-BL, Kayacryl Golden Yellow
A yellow or orange dye such as wGL-ED may be used.

The content of the above-mentioned UV absorbing dye is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight in the photosensitive composition. Further, two or more kinds may be used in combination within the above range.

(Organic Acid / Inorganic Acid / Anhydride) The photosensitive composition may contain an organic acid / inorganic acid / anhydride.
Examples of the acid used in the present invention include those disclosed in JP-A-60-8.
No. 8942, organic acids described in JP-A-2-137850, and "Chemical Handbook New Edition" edited by The Chemical Society of Japan (Maruzen Publishing) No. 92.
To 158 pages. Examples of organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid,
Sulfonic acids such as ethanesulfonic acid, benzylsulfonic acid and m-benzenedisulfonic acid, p-toluenesulfinic acid, benzylsulfinic acid, sulfinic acids such as methanesulfinic acid, phenylphosphonic acid, methylphosphonic acid,
Phosphonic acid such as chloromethylphosphonic acid, formic acid, acetic acid,
Propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid, aliphatic monocarboxylic acids such as heptanoic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid,
o-, m-, p-hydroxybenzoic acid, o-, m-, p
And aromatic monocarboxylic acids such as -methoxybenzoic acid, o-, m-, p-methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysine carboxylic acid, gallic acid, and 3,5-dimethylbenzoic acid. . Also, saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, itaconic acid and malic acid , Tetrahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid,
Alicyclic dicarboxylic acids such as 2-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, phthalic acid,
Aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid can be mentioned.

Among the above organic acids, more preferred are p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
Examples include sulfonic acid such as mesitylene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, benzene sulfonic acid, and m-benzene disulfonic acid, cis-1,2-cyclohexane dicarboxylic acid, and syringic acid. Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, silicic acid, phosphoric acid and the like, more preferably sulfuric acid and phosphoric acid.

When an acid anhydride is used, the type of the acid anhydride is also arbitrary, and those derived from aliphatic / aromatic monocarboxylic acids such as acetic anhydride, propionic anhydride, benzoic anhydride and the like, and succinic anhydride , Maleic anhydride, glutaric anhydride, phthalic anhydride, etc., and those derived from aliphatic / aromatic dicarboxylic acids. Preferred acid anhydrides are glutaric anhydride and phthalic anhydride. These compounds can be used alone or in combination of two or more. The content of these acids is generally from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight, based on the total solids of the entire photosensitive composition.

(Surfactant) The photosensitive composition may contain a surfactant. Examples of the surfactant include an amphoteric surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a fluorine-based surfactant.

Examples of the amphoteric surfactant include lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl, imidazolinium betaine and the like.
Examples of anionic surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates,
Examples thereof include alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl allyl sulfate, naphthalene sulfonic acid formalin condensate, and polyoxyethylene alkyl phosphate. Examples of the cationic surfactant include an alkylamine salt, a quaternary ammonium salt, and an alkyl betaine. As the nonionic surfactant, polyoxyethylene alkyl ether,
Polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxy Examples include ethylene alkylamines and alkyl alkanolamides.

Examples of the fluorine-based surfactant include acrylate or methacrylate containing a fluoroaliphatic group and a copolymer of (polyoxyalkylene) acrylate or (polyoxyalkylene) methacrylate. For example, JP-A Nos. 62-170950 and 62-2.
26143, U.S. Pat. No. 3,787,351 and the like (for example, Megafac F-171,173,1).
77, Defencer MCF300, 312, 313 (all manufactured by Dainippon Ink and Chemicals, Inc.), Modiper F-10
0, 102, 110 (manufactured by NOF CORPORATION) and the like. These compounds can be used alone or in combination of two or more. The proportion occupying in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight.

(Printout Material) A printout material capable of forming a visible image upon exposure can be added to the photosensitive composition. The printout material is composed of an organic dye that changes its color tone by interacting with a compound that generates an acid or a free radical upon exposure. O described in JP-A-36209
-Naphthoquinonediazide-4-sulfonic acid halogenide,
An ester compound or amide compound of o-naphthoquinonediazide-4-sulfonic acid chloride and an electron-withdrawing substituent phenol or aniline acid described in JP-A-53-36223, JP-A-55-
Examples include halomethylvinyloxadiazole compounds and diazonium salts described in 77742, JP-A-57-148784, and the like.

(Photo-acid generator) Examples of the photo-acid generator capable of generating an acid or a free radical upon exposure include, for example,
Halomethyl oxadiazole compound, halomethyl-s-
A triazine compound or the like is used. A halomethyloxadiazole compound is a compound having a halomethyl group, preferably a trichloromethyl group, in oxadiazoles.

These compounds are known, for example, Japanese Patent Publication Nos. 57-6096 and 61-51788,
JP-B-1-28369, JP-A-60-13853
No. 9, No. 60-177340, No. 60-24
No. 1049, for example. In addition, the halomethyl-s-triazine compound is a compound having one or more halomethyl groups, preferably a trichloromethyl group, in the s-triazine ring.

The amount of the compound which forms an acid or a free radical upon exposure to light in the photosensitive composition is 0.01 to 3
It is preferably 0% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.2 to 3% by weight. These compounds can be used alone or in combination of two or more.

(Dye) The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development. As the dye, those which change color tone by reacting with free radicals or acids can be preferably used. Here, "change in color tone" includes both a change from colorless to a color tone and a change from color to colorless or a different color tone. Preferred dyes are those which form a salt with an acid to change the color tone. For example, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue # 603 (Orient Chemical Co., Ltd.), Patent Pure Blue (Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl. Triphenylmethane typified by green, erythrosine B, peisic fuchsin, malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminafutoquinone, cyano-p-diethylaminophenylacetanilide and the like. -Based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based colorants that change from colored to colorless or to different colored tones It is mentioned as examples.

On the other hand, as a discoloring agent that changes from colorless to colored, there are leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p. ′ -Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ′,
p "-tris-dimethylaminotriphenylmethane,
p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, Primary or secondary arylamine dyes represented by p ', p "-triaminotriphenylmethane are exemplified. The proportion of the above-mentioned color changing agent in the photosensitive composition is preferably from 0.01 to 10% by weight, more preferably from 0.02 to 10% by weight.
Used at 5% by weight. These compounds can be used alone or in combination of two or more. Particularly preferred pigments are Victoria Pure Blue BOH and Oil Blue # 6.
It is 03.

(Oil Sensitizer) An oil sensitizer for improving the oil sensitivity of the image area (for example, a half-esterified product of an alcohol of a styrene-maleic anhydride copolymer described in JP-A-55-527). , Pt-butylphenol-
Novolak resins such as formaldehyde resins, or partially esterified products thereof with o-quinonediazide compounds, fluorine surfactants, p-hydroxystyrene
0% fatty acid ester) is preferably used. The amount of these additives varies depending on the object and purpose of use, but is generally 0.01 to 30% by weight based on the total solid content. Dissolve each of these components in the following solvent,
By coating on the surface of the support and drying, a photosensitive layer can be provided to produce the photosensitive lithographic printing plate of the invention. There is no special limitation on the usage of the solvent.

(Solvent) As a solvent which can be used for dissolving the photosensitive composition used in the present invention, methanol,
Ethanol, n-propanol, i-propanol, n
-Aliphatic alcohols such as butanol, n-pentanol and hexanol, allyl alcohol, benzyl alcohol, anisole, phenetole, n-hexane, cyclohexane, heptane, hydrocarbons such as octane, nonane and decane, diacetone alcohol, 3 -Methoxy-1
-Butanol, 4-methoxy-1-butanol, 3-ethoxy-1-butanol, 3-methoxy-3-methyl-
1-butanol, 3-methoxy-3-ethyl-1-1-pentanol-4-ethoxy-1-pentanol, 5-methoxy-1-hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, Methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone, 4-hydroxy-2-butanone, 4-hydroxy-2- Pentanone, 5-hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-
Pentanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, ethylene glycol alkyl ethers and their acetates (MC, EC , Butyl cellosolve,
Phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, MC acetate, EC acetate), diethylene glycol monoalkyl ethers and their acetates (diethylene glycol monomethyl ether, monoethyl ether, mono i-propyl ether, monobutyl ether, Diethylene glycol monomethyl ether acetate, etc.), diethylene glycol dialkyl ethers (DMDG, DEDG, D
BDG, MEDG), triethylene glycol alkyl ethers (monomethyl ether, monoethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, etc.), propylene glycol alkyl ethers and their acetates (monomethyl ether, monoethyl ether, n-propyl ether) , Monobutyl ether, dimethyl ether, diethyl ether, monomethyl ether acetate, monoethyl ether acetate, etc.), dipropylene glycol alkyl ethers (monomethyl ether, monoethyl ether, n-propyl ether, monobutyl ether, dimethyl ether, diethyl ether), ethyl formate , Propyl formate,
Carboxylic esters such as butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran, methyl lactate ,
Examples thereof include ethyl lactate, methyl benzoate, ethyl benzoate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more.

The solvent which can be used for dissolving the photosensitive composition preferably contains at least one solvent selected from propylene glycol monomethyl ether, methyl ethyl ketone, methyl lactate and diethyl carbitol.

(Coating) The present invention has a constitution in which at least two photosensitive layers each having a photosensitive composition are provided as described above. As a method for applying the two layers, a method in which a solution (photosensitive solution) in which the lower layer component of the photosensitive layer is dissolved is dried and then a solution (photosensitive solution) in which the upper layer component is continuously applied and dried, Examples include a method of applying the upper layer component photosensitive liquid by a wet-on-wet method while the dry component photosensitive liquid is in a wet state.

As the coating method, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, electrostatic air spray coating, roll coating, blade coating and curtain coating. And the like, and then a solution (photosensitive solution) in which the upper layer component is dissolved is applied and dried by the same known method. In addition, it is also preferable to adopt the simultaneous multilayer coating method. Further, the upper photosensitive layer component may be dispersed in water, hydrocarbon, alcohol or the like and applied. A method such as a ball mill, a sand grinder, a roll mill or a three roll mill can be used for the dispersion.

Further, in a photosensitive solution in which the upper layer component and the lower layer component are dissolved, a solvent in which the upper layer component is easily dissolved, the lower layer component is difficult to dissolve, and a lower layer component is easily dissolved, and the upper layer component is difficult to be dissolved, and the former There may be mentioned a method in which two or more different solvents having a boiling point of at least 10 ° C. higher than the boiling point of the latter are used and the upper layer and the lower layer are separated (or incompletely separated) during coating and drying.

The film thickness of the photosensitive layer is not particularly limited, but the total film thickness is preferably 5 to 30 mg / dm ² .

(Coating Layer) In the photosensitive lithographic printing plate according to the present invention, a coating layer composed of a water-insoluble organic solvent-soluble polymer compound having a film-forming ability can be formed on the photosensitive layer. As a coating method of the coating layer, a conventionally known method as in the coating of the photosensitive composition layer, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like. Used.

(Mat Agent) It is preferable to further provide a mat layer on the surface of the photosensitive layer provided as described above. The matte layer shortens the vacuuming time during contact exposure using a vacuum baking frame, and prevents the collapse of fine halftone dots and exposure blurring during exposure due to poor adhesion. Specifically, JP-A-50-125805, JP-B-57-6582,
Examples thereof include a method of providing a mat layer as described in JP-A No. 61-28986 and a method of heat-bonding a solid powder as described in JP-B-62-62337. The purpose of the matte layer is to improve the vacuum adhesion between the image film and the photosensitive lithographic printing plate during contact exposure, thereby shortening the vacuuming time and preventing the collapse of fine halftone dots during exposure due to poor adhesion. Is.
As a coating method of the matte layer, there is disclosed in JP-A-55-12974.
There is a method of heat-sealing powdered solid powder described in JP-A No. 58-182636, a method of spraying polymer-containing water described in JP-A No. 58-182636 and drying, and any method may be used. It is desirable that the matte layer itself be soluble in an alkaline developer or be removable by this.

The matte layer may be applied by a known method similar to the method for applying the photosensitive composition layer, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating and curtain coating. Coating or the like is used.

(Exposure) In using the photosensitive lithographic printing plate thus obtained, a conventionally used method can be applied. For example, a transparent original image having a line image, a halftone image or the like can be applied to the photosensitive surface. A relief image is obtained by exposing the film in close contact with it and then removing the photosensitive layer in the non-image area with a suitable developing solution. Light sources suitable for exposure include mercury lamps, metal halide lamps, xenon lamps,
Chemical lamps, carbon arc lamps and the like are used.

(Processing) In the present invention, the developing solution and the developing replenishing solution used for the developing process of the photosensitive lithographic printing plate both contain an alkali metal silicate. The alkali metals of alkali metal silicates include lithium, sodium,
Potassium is included, of which potassium is most preferred. At the time of development, it is preferable that a development replenisher is appropriately replenished in accordance with the development processing amount of the photosensitive lithographic printing plate.

Preferred developing solutions and developing replenishers are [SiO 2
₂ ] / [M] (in the formula, [SiO ₂ ] represents the molar concentration of SiO ₂ and [M] represents the molar concentration of alkali metal), and the SiO ₂ concentration is It is an aqueous solution of an alkali metal silicate that is 0.5 to 5.0% by weight based on the total weight. Further, it is particularly preferable that the developing solution [SiO
₂ ] / [M] is 0.25 to 0.75, the SiO ₂ concentration is 1.0 to 4.0% by weight, and the development replenisher [SiO ₂ ]
/ [M] is 0.15 to 0.5, and the SiO ₂ concentration is 1.0 to 3.0% by weight.

The above developing solution and developing replenishing solution may contain water-soluble or alkali-soluble organic and inorganic reducing agents. Examples of the organic reducing agent include phenol compounds such as hydroquinone, methol and methoxyquinone, and amine compounds such as phenylenediamine and phenylhydrazine.Examples of the inorganic reducing agent include sodium sulfite and potassium sulfite. Sulfites such as ammonium sulfite, sodium bisulfite, potassium bisulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, potassium dihydrogen phosphite Phosphites, hydrazine, sodium thiosulfate, etc.
And sodium dithionite. These water-soluble or alkali-soluble reducing agents are preferably contained in the developing solution and the developing replenishing solution in an amount of 0.05 to 10% by weight. Further, the developing solution and the developing replenishing solution may contain an organic acid carboxylic acid.

These organic acid carboxylic acids include aliphatic carboxylic acids having 6 to 20 carbon atoms, and aromatic carboxylic acids having a benzene ring or naphthalene ring substituted with a carboxyl group.

The aliphatic carboxylic acid has 6 to 2 carbon atoms.
The alkanoic acid of 0 is preferable, and specific examples thereof include caproic acid, enantiic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mystyric acid, palmitic acid,
Stearic acid and the like are particularly preferable.
~ 12 alkanoic acids. Further, the aliphatic carboxylic acid may be a fatty acid having a double bond in a carbon chain or a fatty acid having a branched carbon chain. The aliphatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

Specific examples of the aromatic carboxylic acid include benzoic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, p-tert-butylbenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5
-Dihydroxybenzoic acid, gallic acid, 1-hydroxy-
2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2
-Hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-
Naphthoic acid and the like.

The above aromatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt. The content of the aliphatic carboxylic acid or aromatic carboxylic acid can be at least 0.1 to 30% by weight. The developer and development replenisher may contain various anionic, nonionic and cationic surfactants and organic solvents. Furthermore, the developer and development replenisher should be
Known additives can be added.

[0117]

EXAMPLES The present invention will be described more specifically with reference to the following examples. (Preparation of support) An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was kept at 85 ° C for 10%.
It was immersed in a sodium hydroxide aqueous solution, degreased for 1 minute, and then washed with water. This degreased aluminum plate
Immerse in 10% sulfuric acid aqueous solution kept at 25 ° C for 1 minute,
After the desmut treatment, it was washed with water. Then, the aluminum plate was placed in a 2.0% aqueous nitric acid solution at a temperature of 30%.
The surface was roughened under conditions of a temperature of 80 ° C., a current density of 80 A / dm ² , and a treatment time of 30 seconds. Then, it was immersed in a 1% sodium hydroxide aqueous solution kept at 70 ° C. for 10 seconds and then washed with water.
Next, the substrate was immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 10 seconds, and then washed with water. Then, after anodizing treatment in a 30% sulfuric acid aqueous solution at a temperature of 35 ° C. and a current density of 3 A / dm ² for 1 minute, it was washed with water. Then, after immersing in a 0.01% polyvinylphosphonic acid aqueous solution kept at 80 ° C. for 30 seconds, it was dried at 80 ° C. for 5 minutes.

Then, a JIS No. 3 sodium silicate aqueous solution (10 g / l) was applied to the back surface of the aluminum plate treated as described above using a wire bar, and the temperature was adjusted to 80 ° C.
And dried for 3 minutes to obtain an aluminum support having a coating layer on the back surface. The coating layer was applied so that the dry weight was 10 mg / m ² .

Example 1 The surface of the aluminum support prepared as described above was coated with a photosensitive composition coating liquid 1 having the following composition using a wire bar and dried at 85 ° C. for 2 minutes to form a lower photosensitive layer. Next, a photosensitive composition coating liquid 2 having the following composition was applied using a wire bar and dried at 85 ° C. for 2 minutes to form an upper photosensitive layer 2
A photosensitive lithographic printing plate sample having a layer structure was obtained. The coating amount of the photosensitive composition coating liquid at this time was 10 mg / dm ² for each of the lower layer and the upper layer in terms of dry weight.

Photosensitive Composition Coating Liquid 1 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 3000) 6.70 g Pyrogallol acetone resin (Mw 3000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.00 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.13 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Photosensitive composition coating liquid 2 Hydroxypropyl-β-cyclodextrin 0.20 g Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 3000) 6.70 g Condensation product of pyrogallol acetone resin (Mw 3000) and o-naphthoquinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.00 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexane Dicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol Glycol monomethyl ether = 3/7 100 ml

Example 2 A two-layered photosensitive material was prepared in the same manner as in Example 1 except that the photosensitive composition coating liquid 2 for the upper photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 3 having the following composition. A lithographic printing plate sample was obtained.

Photosensitive Composition Coating Liquid 3 β-Cyclodextrin 0.20 g Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 3000) 6.70 g Pyrogallol acetone resin (Mw 3000) and o-naphthoquinonediazide-5-sulfonyl chloride condensate (esterification rate 30%) 1.00 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4 -Bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0 .20 g methyl ethyl ketone / propylene glycol monomethyl ether Tel = 3/7 100ml

Comparative Example 1 A two-layered photosensitive material was prepared in the same manner as in Example 1 except that the photosensitive composition coating liquid 2 for the upper photosensitive layer of Example 1 was replaced with a photosensitive composition coating liquid 4 having the following composition. A lithographic printing plate sample was obtained.

Photosensitive Composition Coating Liquid 4 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 3000) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.00 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Comparative Example 2 The surface of the aluminum support prepared as described above was coated with a photosensitive composition coating liquid 5 having the following composition using a wire bar and dried at 85 ° C. for 2 minutes to form a single-layer photosensitive material. A lithographic printing plate sample was obtained. The coating amount of the photosensitive composition coating liquid at this time was set to be 20 mg / dm ² in terms of dry weight.

Photosensitive composition coating liquid 5 Hydroxypropyl-β-cyclodextrin 0.20 g Novolac resin (molar ratio of phenol / m-cresol / p-cresol of 10/54/36, Mw of 3000) 6.70 g Condensation product of pyrogallol acetone resin (Mw3000) and o-naphthoquinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexane Dicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol Glycol monomethyl ether = 3/7 100 ml

Comparative Example 3 A photosensitive lithographic printing plate sample having a one-layer structure in the same manner as Comparative Example 2 except that the photosensitive composition coating liquid 5 of Comparative Example 2 was replaced with a photosensitive composition coating liquid 6 of the following composition. Got

Photosensitive Composition Coating Liquid 6 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 3000) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Example 3 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 7 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. Composition of photosensitive composition coating liquid 8
A photosensitive lithographic printing plate sample having a two-layer structure was obtained in the same manner as in Example 1 except that the above was used.

Photosensitive Composition Coating Liquid 7 Polymer Compound 1 1.00 g Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 3000) 5.70 g Pyrogallolacetone resin (Mw 3000) and o-naphthoquinonediazide-5-sulfonyl chloride condensate (esterification rate 30%) 1.65 g polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4 -Bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0 .20 g methyl ethyl ketone / propylene glycol monomethyl ether = / 7 100ml

[0132]

Embedded image

Photosensitive composition coating liquid 8 Polymer compound 1 5.70 g Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 3000) 1.00 g pyrogallolacetone resin (Mw 3000) and o-naphthoquinonediazide-5-sulfonyl chloride condensate (esterification rate 30%) 1.65 g polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4 -Bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0 .20 g methyl ethyl ketone / propylene glycol monomethyl ether = / 7 100ml

Example 4 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 9 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. Composition of photosensitive composition coating liquid 1
A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that 0 was used.

Photosensitive composition coating liquid 9 Polymer compound 2 1.00 g Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 5.70 g Pyrogallolacetone resin (Mw 3000) and o-naphthoquinonediazide-5-sulfonyl chloride condensate (esterification rate 30%) 1.65 g polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4 -Bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0 .20 g methyl ethyl ketone / propylene glycol monomethyl ether = / 7 100ml

[0136]

[Chemical 6]

Photosensitive composition coating liquid 10 Polymer compound 2 5.70 g Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 1.00 g pyrogallolacetone resin (Mw 3000) and o-naphthoquinonediazide-5-sulfonyl chloride condensate (esterification rate 30%) 1.65 g polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4 -Bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0 .20 g methyl ethyl ketone / propylene glycol monomethyl ether 3/7 100ml

Comparative Example 4 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 11 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 12 having the composition was used.

Photosensitive Composition Coating Liquid 11 Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Photosensitive composition coating liquid 12 Polymer compound 1 6.70 g Pyrogallol acetone resin (Mw 3000) and o-naphthoquinonediazide-5-sulfonyl chloride condensate (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC- 430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml

Comparative Example 5 A photosensitive lithographic printing plate sample having the same one-layer structure as in Comparative Example 2 was obtained except that the photosensitive composition coating liquid 5 of Comparative Example 2 was replaced with the photosensitive composition coating liquid 12. Note that the coating amount of the photosensitive composition coating liquid at this time was set to 20 mg / dm ^{2 in} terms of dry weight, as in the case of Comparative Example 2, since it had a one-layer structure.

Example 5 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 11 described above, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following composition. A two-layered photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 13 was used.

Photosensitive Composition Coating Liquid 13 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 3500) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Comparative Example 6 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 11 described above, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following composition. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the coating liquid 14 for the photosensitive composition was used.

Photosensitive Composition Coating Liquid 14 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, Mw is 2500) 6.70 g Pyrogallolacetone resin (Mw3000) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Example 6 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 15 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layered photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 16 having the composition was used.

Photosensitive Composition Coating Liquid 15 Novolak resin (phenol / m-cresol / p-cresol molar ratio 15/51/34, Mw 2000) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Photosensitive Composition Coating Liquid 16 Novolac resin (phenol / m-cresol / p-cresol molar ratio 5/57/38, Mw 2000) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphthoquinonediazide Condensation product of -5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl) -6 -(P-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml

Comparative Example 7 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 11 described above, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following composition. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 17 was used.

Photosensitive Composition Coating Liquid 17 Novolak resin (phenol / m-cresol / p-cresol molar ratio 8 / 55.2 / 36.8, Mw 2000) 6.70 g Pyrogallol acetone resin (Mw 3000) Condensation product of o-naphthoquinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloro) Methyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (manufactured by Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g methyl ethyl ketone / Propylene glycol monomethyl ether = 3/7 100 ml

Example 7 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 18 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 19 having the composition was used.

Photosensitive Composition Coating Liquid 18 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, Mw is 2000) 6.70 g Pyrogallolacetone resin (Mw2500) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Photosensitive Composition Coating Liquid 19 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, Mw is 2000) 6.70 g Pyrogallolacetone resin (Mw3500) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Comparative Example 8 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 20 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 21 having the composition was used.

Photosensitive Composition Coating Liquid 20 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Pyrogallolacetone resin (Mw 2800) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Photosensitive Composition Coating Liquid 21 Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Pyrogallolacetone resin (Mw 3200) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Example 8 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 22 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layered photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 23 having the composition was used.

Photosensitive Composition Coating Liquid 22 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Pyrogallol acetone resin (Mw 2000) and o-naphtho Condensate of quinonediazide-5-sulfonyl chloride (esterification rate: 25%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Photosensitive Composition Coating Liquid 23 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, Mw is 2000) 6.70 g Pyrogallolacetone resin (Mw2000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 35%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Comparative Example 9 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 24 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 25 having the composition was used.

Photosensitive Composition Coating Liquid 24 Novolak resin (phenol / m-cresol / p-cresol molar ratio is 10/54/36, Mw is 2000) 6.70 g Pyrogallolacetone resin (Mw2000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate: 28%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Photosensitive Composition Coating Liquid 25 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, Mw is 2000) 6.70 g Pyrogallolacetone resin (Mw2000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 32%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Example 9 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 26 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was prepared as described above. Photosensitive composition coating liquid 11
Example 1 except that the coating was applied for the lower layer in Comparative Example 4 but is applied for the upper layer in Example 9).
A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as described above.

Photosensitive Composition Coating Liquid 26 Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Novolac resin (p-cresol formaldehyde resin Mw is 2000) and o-naphthoquinonediazide-4-sulfonyl chloride condensate (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2, 4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20g methyl ethyl ketone / propylene glycol monomethyl ether Tel = 3/7 100ml

Example 10 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 27 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 28 having the composition was used.

Photosensitive Composition Coating Liquid 27 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, Mw is 2000) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 0.65 g Condensation product of novolak resin (p-cresol-formaldehyde resin with Mw of 2000) and o-naphthoquinonediazide-4-sulfonyl chloride (esterification rate) 30%) 1.00 g polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15g Fluorine-based surfactant FC-430 ( Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml

Photosensitive Composition Coating Liquid 28 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, Mw is 2000) 6.70 g Pyrogallolacetone resin (Mw3000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.00 g Novolak resin (p-cresol-formaldehyde resin with Mw of 2000) and o-naphthoquinonediazide-4-sulfonyl chloride condensate (esterification rate) 30%) 0.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.06 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15g Fluorine-based surfactant FC-430 ( Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml

Comparative Example 10 1 was prepared in the same manner as Comparative Example 2 except that the photosensitive composition coating liquid 5 of Comparative Example 2 was replaced with a photosensitive composition coating liquid 29 of the following composition.
A photosensitive lithographic printing plate sample having a layer structure was obtained.

Photosensitive Composition Coating Liquid 29 Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Novolac resin (p-cresol formaldehyde resin Mw is 2000) and o-naphthoquinonediazide-4-sulfonyl chloride condensate (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.06 g 2, 4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20g methyl ethyl ketone / propylene glycol monomethyl ether Tel = 3/7 100ml

The photosensitive lithographic printing plate samples of Examples 1 to 10 and Comparative Examples 1 to 10 prepared as described above were evaluated for sensitivity, printing durability, developability and chemical resistance based on the following evaluation methods. . The results are shown in Table 1.

<Evaluation Method> (Evaluation of Sensitivity) A step tablet for sensitivity measurement (Eastman Kodak No. 2, 21-step gray scale with a density difference of 0.15) was adhered to each of the obtained samples. , Using a 4 kW metal halide lamp as the light source,
It was exposed by irradiation with 8 mW / cm ² . The exposed sample is a commercially available developer (SDR-1, 6 manufactured by Konica Corporation).
Development processing was carried out at a doubling dilution, a developing time of 20 seconds and a developing temperature of 27 ° C. The sensitivity was defined as the exposure time at which 3.0 steps of the step tablet were completely cleared.

(Evaluation of Printing Durability) Each of the obtained samples was 8 mW / power using a 4 kW metal halide lamp as a light source.
Exposure was carried out by irradiating with cm ² for 60 seconds. The exposed sample is a commercially available developer (SDR-1, 6 manufactured by Konica Corporation).
Development processing was carried out at a doubling dilution, a developing time of 20 seconds and a developing temperature of 27 ° C. The obtained lithographic printing plate was applied to a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), and coated paper, dampening water (etching solution SG-51 manufactured by Tokyo Ink Co., concentration 1.5%), ink (Toyo Ink Mfg. Co., Ltd.) Printing is performed by using Hiplus M Beni (manufactured by Mfg. Co., Ltd.), and printing is performed until ink inking defects appear in the image area of the printed matter or ink adheres to the non-image area. It was evaluated.

(Evaluation of Developability) Each of the obtained samples was used as a light source using a 4 kW metal halide lamp, and 8 mW /
Exposure was carried out by irradiating with cm ² for 60 seconds. This exposed sample was printed under the same printing conditions (developing time 20 seconds, developing temperature 27 ° C.) as the evaluation of printing durability described above by increasing the dilution ratio of a commercially available developing solution (SDR-1 manufactured by Konica). When it was carried out, the developability was evaluated by the dilution ratio at which the photosensitive layer was not completely removed even after the exposure / development treatment and the non-image area was stained.

(Evaluation of chemical resistance) Each of the obtained samples was subjected to 50% by using a 4 kW metal halide lamp as a light source.
The flat screen original was brought into close contact and exposed by irradiating at 8 mW / cm ² for 60 seconds. The exposed sample was diluted with a commercially available developer (SDR-1 manufactured by Konica, 6 times dilution, development time 20 minutes).
For 2 seconds at a developing temperature of 27 ° C.). The lithographic printing plate thus obtained was immersed in an ultra plate cleaner (manufactured by ABC Chemical Co.), and the chemical resistance was evaluated based on the time at which the image area started to be damaged.

[0175]

[Table 1]

Example 11 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 30 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 31 having the composition was used.

Photosensitive Composition Coating Liquid 30 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexane Dicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml

Photosensitive Composition Coating Liquid 31 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Pyrogallol acetone resin (Mw 3000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.12 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.30 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Example 12 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 32 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 33 having the composition was used.

Photosensitive Composition Coating Liquid 32 Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, Mw 2000) 6.70 g Pyrogallol acetone resin (Mw 3000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.04 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.10 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Photosensitive Composition Coating Liquid 33 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, Mw is 2000) 6.70 g Pyrogallolacetone resin (Mw 3000) and o-naphtho Condensation product of quinonediazide-5-sulfonyl chloride (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl)- 6- (p-methoxystyryl) -s-triazine 0.20 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl Ether = 3/7 100 ml

Comparative Example 11 The photosensitive composition coating liquid 5 of Comparative Example 2 was applied to the photosensitive composition coating liquid 11 (in Comparative Example 4, the lower layer was applied.
In Comparative Example 11, a photosensitive lithographic printing plate sample having the same single-layer structure as in Comparative Example 2 was obtained except that the single-layer coating was used instead of the single-layer coating). Note that the coating amount of the photosensitive composition coating liquid at this time was set to 20 mg / dm ^{2 in} terms of dry weight, as in the case of Comparative Example 2, since it had a one-layer structure.

Examples 11 and 12 prepared as described above
And for each photosensitive lithographic printing plate sample of Comparative Example 11,
The sensitivity, developability, and exposure visual imageability were evaluated based on the following evaluation methods. Table 2 shows the results.

<Evaluation method> (Evaluation of sensitivity) As described above (Evaluation of developability) As described above

(Evaluation of Visibility of Exposure Visibility) The obtained sample was
Using a 4kW metal halide lamp as a light source, 30
Exposure was performed by irradiating for 2 seconds. Next, the density difference ΔD between the unexposed area and the exposed area is measured by a densitometer (Sakura densitometer P
DA-65, Red filter) was used to evaluate the exposure visibility.

[0186]

[Table 2]

Example 13 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 34 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 35 having the composition was used.

Photosensitive Composition Coating Liquid 34 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 0/60/34, Mw is 2700) 6.70 g Pyrogallolacetone resin (Mw3000) and o-naphthoquinonediazide Condensation product of -5-sulfonyl chloride (esterification rate 30%) 1.65 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -S-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml Tg: 82 ° C

Photosensitive Composition Coating Liquid 35 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 0/60/34, Mw is 3000) 6.70 g Pyrogallolacetone resin (Mw3200) and o-naphthoquinonediazide -5-Sulfonyl chloride condensate (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6 -(P-Methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g Methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml Tg: 89 ° C.

Example 14 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 36 having the following composition, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was changed to the following. A two-layer photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the photosensitive composition coating liquid 37 having the composition was used.

Photosensitive Composition Coating Liquid 36 Novolac resin (molar ratio of phenol / m-cresol / p-cresol is 0/60/40, Mw is 3200) 6.70 g Pyrogallolacetone resin (Mw3000) and o-naphthoquinonediazide Condensation product of -5-sulfonyl chloride (esterification rate 30%) 1.65 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -S-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.20 g Methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml Tg: 88 ° C

(Measurement of Tg) Vibron DDV-II-EA (manufactured by Toyo Baldwin Co., Ltd.) was used as a measuring device, and a sample having a thickness of 30 μm, a width of 10 mm and a length of 25 mm was measured at 50 ° C./minn in the range of 50 to 100 ° C. A temperature at which a sine wave expansion / contraction strain having a frequency of 10 Hz is applied to the edge in the width direction while heating and a maximum tan δ of the phase difference δ of both vectors of the sine wave stress appearing at the other end is given is Tg (glass transition temperature).

Photosensitive Composition Coating Liquid 37 Novolac resin (phenol / m-cresol / p-cresol molar ratio 5/57/38, Mw 4700) 6.70 g Pyrogallolacetone resin (Mw 3200) and o-naphthoquinonediazide -5-Sulfonyl chloride condensate (esterification rate 30%) 1.65 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6 -(P-Methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.05 g Methyl ethyl ketone / propylene glycol monomethyl ether = 3/7 100 ml Tg: 9 ℃

Comparative Example 12 The photosensitive composition coating liquid 1 for the lower photosensitive layer of Example 1 was replaced with the photosensitive composition coating liquid 36, and the photosensitive composition coating liquid 2 for the upper photosensitive layer was replaced with the photosensitive liquid. A photosensitive lithographic printing plate sample having a two-layer structure was obtained in the same manner as in Example 1 except that the composition coating liquid 35 was used.

Examples 13 and 14 prepared as described above
And for each photosensitive lithographic printing plate sample of Comparative Example 12,
The sensitivity, printing durability, developability, and chemical resistance were evaluated based on the following evaluation methods. The results are shown in Table 3.

<Evaluation method> (Evaluation of sensitivity) As described above (Evaluation of printing durability) As described above (Evaluation of developability) As described above (Evaluation of chemical resistance) As described above

[0197]

[Table 3]

[0198]

According to the present invention as set forth in claims 1 to 9, it is possible to provide a photosensitive lithographic printing plate having good chemical resistance, high sensitivity, and a wide applicable developing range. According to the present invention as defined in claim 10, it is possible to provide a positive-working photosensitive lithographic printing plate which has good exposure visible image property, high sensitivity, and a wide applicable development range.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuhiko Higashino 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company

Claims (10)

[Claims] 1. A photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, and the glass transition temperature of the photosensitive layer ( A photosensitive lithographic printing plate characterized in that the photosensitive layer on the far side is higher by 5 ° C. or more than the photosensitive layer on the side closer to the support. 2. A photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, and the content of the o-quinonediazide compound is Is higher in the photosensitive layer on the side farther than the photosensitive layer on the side closer to the support, and the content rate of the inclusion compound is higher on the photosensitive layer on the side farther than the photosensitive layer on the side close to the support. Or a photosensitive lithographic printing plate containing an inclusion compound only in the photosensitive layer remote from the support. 3. A photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, and the alkali-soluble resin is at least a novolak resin. And an acrylic polymer, and However, the photosensitive lithographic printing plate is characterized in that the photosensitive layer on the far side is more than the photosensitive layer on the side closer to the support. 4. A photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, and solubility in an alkaline aqueous solution is supported. A photosensitive lithographic printing plate characterized in that the photosensitive layer on the far side is lower than the photosensitive layer on the side closer to the body. 5. The alkali-soluble resin comprises at least a novolac resin, and the weight-average molecular weight (Mw) of the novolac resin is 1000 or more higher in the photosensitive layer on the far side than on the photosensitive layer on the side closer to the support. Claim 4 characterized by the above-mentioned.
The photosensitive lithographic printing plate described. 6. The alkali-soluble resin is composed of at least a novolac resin, and the photosensitive layer on the far side is 5 mol% or more as compared with the photosensitive layer on the side where the phenol component amount (mol%) of the novolac resin is closer to the support. The photosensitive lithographic printing plate according to claim 4, which is low. 7. The o-quinonediazide compound is an o-quinonediazidesulfonic acid ester of a polyhydroxy compound, and the polyhydroxy compound has a weight average molecular weight (Mw).
5. The photosensitive lithographic printing plate according to claim 4, wherein the photosensitive layer on the far side is higher than the photosensitive layer on the side closer to the support by 500 or more. 8. An o-quinonediazide compound is an o-quinonediazide sulfonic acid ester of a polyhydroxy compound, and the photosensitivity of the polyhydroxy compound on the side farther than the photosensitive layer on the side closer to the support is higher than the photosensitive layer. The layer is higher than the layer by 5% or more.
The photosensitive lithographic printing plate described. 9. A photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, and an o-in the o-quinonediazide compound is A photosensitive lithographic printing plate wherein the content of a quinonediazide-5-sulfonyl chloride condensate in the photosensitive layer on the far side is higher than that on the side closer to the support. 10. A photosensitive lithographic printing plate in which at least two photosensitive layers having a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin are provided on a support, and a photo-acid generator and a dye are included. The content is higher in the photosensitive layer on the side farther than the photosensitive layer on the side closer to the support, or the photosensitive layer characterized in that only the photosensitive layer on the side far from the support contains a photoacid generator and a dye. Sex lithographic printing plate.