JPH11240269A - Photo-sensitive lithographic printing plate, and its development method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve sensitivity, image strength, developing property, gradient property, inking property, printing durability, and halftone dot reproducibility by a method wherein the reflectance of the surface of an aluminum supporting body before a layer of a photo-sensitive composition is provided, is kept within a range of a specified percentage. SOLUTION: For an aluminum supporting body, it is preferable to apply a degreasing treatment in order to remove a rolling oil on the aluminum surface prior to a surface- roughening. As a surface-roughening method, there are a so-called mechanical roughening method wherein the surface is mechanically roughened, and a so-called electro-chemical roughening method wherein the surface is electro-chemically roughened. Then, an anodizing is applied to the surface-roughened aluminum plate, and the aluminum supporting body is obtained. the aluminum supporting body is obtained by performing the surface-roughening treatment and the anodizatin in such manners, and that the reflectance (which is normally an absorption wavelength of the layer of a photo-sensitive composition being applied on the top, and especially is a reflectance when ultraviolet rays of 350-400 nm are used) of the surface of the aluminum supporting body is 50-70%, is an essential requirement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate and a method for developing the photosensitive lithographic printing plate, and more particularly to a negative photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art In general, a photosensitive lithographic printing plate is provided with a photosensitive composition layer (hereinafter also referred to as a photosensitive layer) on a hydrophilic support such as aluminum. In the plate, a photosensitive layer which is insolubilized by exposure to actinic rays such as ultraviolet rays and becomes ink-receptive is formed on an aluminum support. In such a negative-working photosensitive lithographic printing plate, when the photosensitive layer is subjected to image exposure and then developed, the unexposed portion of the photosensitive layer is removed and the surface of the hydrophilic support is exposed, while the exposed portion of the photosensitive layer is exposed. Remains on the support to form an ink receiving layer. In the negative photosensitive lithographic printing plate, the difference in properties between the exposed portion is lipophilic and the unexposed portion is hydrophilic is used.

Conventionally, in an image forming method using a negative photosensitive lithographic printing plate, usually, in a developing process after exposure, an unexposed photosensitive layer is eluted with an organic solvent or an aqueous alkali solution containing the organic solvent. In general, a method of forming an image by using a conventional method is used. However, there is a concern that the use of a developing solution containing an organic solvent may deteriorate the working environment of the plate making process due to the odor of the solvent and adversely affect the health of workers. Was sought.

[0004] In order to solve such problems, several negative photosensitive lithographic printing plates which can be developed with an alkaline aqueous solution substantially containing no organic solvent have been proposed. For example, in a photosensitive system using a diazo resin as a photosensitive component,
A technique of introducing a carboxyl group or a phenolic hydroxyl group into the molecule of a diazo resin (Japanese Patent Application Laid-Open No. 2-189544), and a technique of using a resin having an acid value of 100 or more as a film forming agent (binder resin) (Japanese Patent Application Laid-Open No. 2178
No. 59), and a method of coating and drying using a mixture of a solvent for the photosensitive composition and a solvent having a different boiling point (Japanese Patent Application Laid-Open No. 4-299344).

Further, a technique using a photosensitive microgel as a photosensitive composition for producing a negative photosensitive lithographic printing plate which can be developed with an alkaline aqueous solution substantially free of an organic solvent is disclosed in, for example, 58-174402
Nos. 60-3622, 60-3623, JP-A-2-263805, 3-64755, 3-75
No. 750, No. 3-76704, No. 5-178946
Nos. 5-97915, 6-194837, 8
-160618, 5-150451, 7-11
No. 480, 5-45877, 5-249674
Nos. 5-249675, 6-161101, 8-190197, 8-190192, and 8-2
No. 20,766 and other publications.

[0006]

However, according to these negative-type photosensitive lithographic printing plates, development with an alkaline aqueous solution substantially free of an organic solvent has become possible, but printing durability and developability have been improved. In addition, the dot reproducibility at the high speed of the ink deposition property was insufficient.

Japanese Patent Publication No. 59-26479 discloses an aluminum support having a center line average roughness (Ha) of 0.6.
Japanese Patent Publication No. 5-70813 discloses a technique of coloring a support with an ultraviolet absorbing dye, and a technique of coloring a support with an ultraviolet absorbing dye.
No. 94 discloses a technique for reducing the surface reflectance to 50% or less.
Japanese Unexamined Patent Publication (Kokai) No. 4-91992 proposes techniques for defining the mirror hardness of a support. However, those techniques are still insufficient in printing durability, developability, dot reproducibility at high speed, and the like. there were.

Further, in recent years, high productivity of printed matter has been demanded, and speeding up of printing machines has been spreading. Accordingly, there has been a demand for a photosensitive lithographic printing plate having a surface strength that can withstand the speeding up of the printing press.

The present invention has been proposed in view of the above circumstances, and aims at high sensitivity, image strength, developability, gradation, ink deposition, printing durability, halftone dot. Another object of the present invention is to provide a photosensitive lithographic printing plate excellent in reproducibility and a method for developing the same. Still another object of the present invention is to provide a photosensitive lithographic printing plate having sensitivity, image strength, developability and stability even when developed with an alkaline aqueous solution containing substantially no organic solvent. An object of the present invention is to provide a photosensitive lithographic printing plate excellent in tonality, ink deposition, printing durability, and halftone dot reproducibility, and a method for developing the same.

[0010]

The above object of the present invention is achieved by the following constitution.

1. A photosensitive lithographic printing plate comprising a layer of a photosensitive composition containing a microgel having a photocrosslinkable group on the surface thereof on an aluminum support having been subjected to surface roughening and anodizing treatment, wherein the photosensitive composition A photosensitive lithographic printing plate wherein the reflectance of the surface of the aluminum support before the layer of the object is 50 to 70%.

2. A photosensitive lithographic printing plate comprising a layer of a photosensitive composition containing a microgel having a photocrosslinkable group on the surface thereof on an aluminum support having been subjected to surface roughening and anodizing treatment, wherein the photosensitive composition The hydrogen bonding component γ (H) value of the following relational expression (1) on the surface of the aluminum support before the product layer is provided is 10 to 55 dyn / cm, and the dispersion component γ ( D) Value is 5
A photosensitive lithographic printing plate characterized by being at most 0 dyn / cm.

The hydrogen bond component γ (H) = [｛1.159 + 2.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) 3. Roughened and anodized aluminum support
Contains microgel with photocrosslinkable groups on the surface
To a photosensitive lithographic printing plate comprising a layer of a photosensitive composition
The aluminum before providing the layer of the photosensitive composition
The reflectance of the support surface is 50 to 70%, and the following
The hydrogen bond component γ (H) value represented by the relational expression (1) is 10
~ 55 dyn / cm and the fraction represented by the following relational expression (2):
That the scattered component γ (D) value is 50 dyn / cm or less.
Features a photosensitive lithographic printing plate.

The hydrogen bond component γ (H) = [｛1.159 + 2.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) 4. Roughened and anodized aluminum support
Photopolymerization initiator on the support and addition polymerizable unsaturated bond on the surface
A layer of a photosensitive composition containing a microgel having
In the resulting photosensitive lithographic printing plate, the photosensitive composition
The reflectance of the surface of the aluminum support before providing the layer is 50
A photosensitive lithographic printing plate, characterized in that the content is from 70% to 70%.

[0015] 5. Photosensitive lithographic printing in which a layer of a photosensitive composition containing a photopolymerization initiator and a microgel having an addition-polymerizable unsaturated bond on the surface is provided on a roughened and anodized aluminum support. In the plate, the hydrogen bonding component γ (H) value represented by the following relational expression (1) on the aluminum support surface before providing the layer of the photosensitive composition is 10 to 55 dyn / cm and the following relational expression (2) A photosensitive lithographic printing plate, characterized in that the dispersion component γ (D) value represented by the formula is 50 dyn / cm or less.

The hydrogen bonding component γ (H) = [｛1.159 + 2.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) 6. Roughened and anodized aluminum support
Photopolymerization initiator on the support and addition polymerizable unsaturated bond on the surface
A layer of a photosensitive composition containing a microgel having
In the resulting photosensitive lithographic printing plate, the photosensitive composition
The reflectance of the surface of the aluminum support before providing the layer is 50
７０70% and represented by the following relational expression (1).
Hydrogen bond component γ (H) value is 10 to 55 dyn / cm
And the variance component γ (D) value represented by the following relational expression (2) is
A photosensitive photosensitive layer having a density of 50 dyn / cm or less.
Plate printing plate.

The hydrogen bond component γ (H) = [｛1.159 + 2.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) 7. The photosensitive lithographic printing plate according to any one of the above 1 to 6,
Is developed with an alkaline developer containing substantially no organic solvent
Developing a photosensitive lithographic printing plate.

Hereinafter, the present invention will be described in detail.

[Preparation of aluminum support] The aluminum support of the present invention is preferably subjected to a degreasing treatment, a surface roughening treatment and an anodic oxidation treatment, and if necessary, a sealing treatment.

The aluminum support of the present invention includes a support made of aluminum and an aluminum alloy.
As the aluminum alloy, various ones can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, and iron is used.

The aluminum support is preferably subjected to a degreasing treatment to remove rolling oil on the aluminum surface prior to the surface roughening. The degreasing treatment includes a degreasing treatment using a solvent such as trichlene or a thinner. Kerosene,
Emulsion degreasing treatment using an emulsion such as triethanol is used. In the degreasing treatment, an aqueous solution of an alkali such as caustic soda can be used. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is possible to remove stains and oxide films that cannot be removed only by the degreasing treatment using the above-mentioned solvent system. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is formed on the surface of the support.In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof. It is preferable to perform a desmut treatment.

As the surface roughening method, there are a so-called mechanical surface roughening method in which the surface is mechanically roughened, and a so-called electrochemical surface roughening method in which the surface is electrochemically roughened. There is a law.
Mechanical surface roughening methods include, for example, ball polishing, brush polishing,
There are methods such as blast polishing, buff polishing, and honing polishing. As the electrochemical surface roughening method, there is a method in which the surface is electrolytically treated by an alternating current or a direct current in an acidic electrolytic solution containing, for example, hydrochloric acid or nitric acid. The support can be roughened by using one or two or more of these methods.

The electrolytic surface roughening treatment in the electrochemical surface roughening method is described in, for example, Japanese Patent Publication No. 48-28123, British Patent No. 896,563, and Japanese Patent Application Laid-Open No.
No. 67507, and these methods can be used in the present invention.

The voltage applied in the electrochemical graining method is preferably 1 to 50 volts, more preferably 2 to 30 volts. The current density is preferably from 10 to 200 A / dm ^2, more preferably 20 to 150 A / dm ^2. Quantity of electricity is preferably from 100~10000C / dm ^2, more preferably 200~5000C / dm ^2, more preferably from 500~3000C / dm ^2. The temperature is between 10 and
50 ° C is preferable, and 15 to 45 ° C is more preferable. The concentration of hydrochloric acid or nitric acid is preferably 0.01 to 5% by weight. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

When two or more surface roughening methods are combined with the surface roughening treatment, it is preferable to perform a chemical etching treatment by dipping in an aqueous solution of acid or alkali between each treatment. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and examples of the base include sodium hydroxide, potassium hydroxide, and the like. Among these, it is preferable to use an aqueous alkali solution. Specifically, 0.05 to 40% by weight of these acids or alkalis
5 to 300 at a liquid temperature of 40 to 100 ° C using an aqueous solution
It is preferable to perform second processing.

When the immersion treatment is performed with the above-mentioned alkaline aqueous solution, a smut is formed on the surface of the support. In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof. It is preferable to perform a desmut treatment.

The aluminum plate subjected to the surface roughening treatment is then subjected to an anodic oxidation treatment to obtain an aluminum support according to the present invention. As the electrolyte used for the anodic oxidation treatment, any electrolyte can be used as long as it forms a porous oxide film. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, sulfamic acid, benzenesulfonic acid, and the like, or two or more kinds thereof, are used. Is used. Anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be specified unconditionally. In general, however, the concentration of the electrolytic solution is 1 to 80% by weight, the temperature is 5 to 70 ° C, and the current density is 1 to 60%.
A / dm ² , voltage 1-100 volts, electrolysis time 10 seconds-
A range of 5 minutes is appropriate. Preferred is a sulfuric acid method, which is usually treated with a direct current, but an alternating current can also be used. Sulfuric acid concentration is 10-50% by weight, temperature 20-50
It is preferable to carry out electrolytic treatment at a temperature of 1 ° C. and a current density of 1 to 20 A / dm ² for ²⁰ to 250 seconds. Preferably, the electrolyte contains aluminum ions.

The anodized aluminum support may then be subjected to a sealing treatment. The sealing treatment is performed by a known method such as hot water treatment, boiling water treatment, steam treatment, alkali metal silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate salt treatment, fluorinated zirconic acid solution treatment and the like. It can be performed using:

The sealed aluminum support may then be provided with a hydrophilic layer. For forming the hydrophilic layer, alkali metal silicate described in U.S. Pat. No. 3,181,461, hydrophilic cellulose described in U.S. Pat. No. 1,860,426, Amino acids and salts thereof described in JP-A-1491491, JP-A-63-165183, amines having a hydroxyl group and salts thereof described in JP-A-60-232998,
Phosphate described in JP-A-19194, JP-A-59-10
For example, a polymer compound containing a monomer unit having a sulfo group described in JP-A-16551 can be used.

Further, in order to prevent abrasion on the photosensitive layer when the photosensitive lithographic printing plates are overlaid, and to prevent elution of the aluminum component into the developing solution during development, Japanese Patent Application Laid-Open No.
0-151136, JP-A-57-63293, JP-A-60-73538, JP-A-61-67863, JP-A-6-35174, etc. A process of providing a layer can be performed.

<Aluminum Support According to Claims 1 and 4> The aluminum support of the present invention can be obtained by the surface roughening treatment and the anodic oxidation treatment as described above. And 4, the reflectance of the surface of the aluminum support (usually the absorption wavelength of the layer of the photosensitive composition applied thereon, particularly the reflectance when ultraviolet light of 350 to 400 nm is used. rate)
Is 50 to 70%. The reflectance of the aluminum support surface is, for example, a surface roughening method, a chemical etching method, a desmutting method,
It can be controlled by selecting conditions such as an anodizing treatment method. When the reflectance of the aluminum support surface is less than 50%, the sensitivity of a photosensitive lithographic printing plate (hereinafter, also referred to as PS plate) is insufficient, If it exceeds 70%, the halftone dot reproducibility and printing durability of the printed image deteriorate.

<Aluminum support according to claims 2 and 5> In the aluminum support according to claims 2 and 5 of the present invention, the surface of the aluminum support has a hydrogen bond represented by the following relational formula (1): Component γ (H) value is 10 to 55
dyn / cm, a dispersion component γ represented by the following relational expression (2)
(D) It is an essential requirement that the value satisfy 50 dyn / cm or less.

Hydrogen bond component γ (H) = [｛1.159 + 2.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) (contact angle: H on the surface of the aluminum support)_TwoO and contact
Antenna: CH_TwoI_Two) (H) value derived from hydrogen bond component
And the dispersion component γ (D) value are, for example, anodizing treatment method,
Select conditions such as sealing method and hydrophilic treatment method
Can be controlled by The above hydrogen bonding component
When the γ (H) value is less than 10, the developability is deteriorated, and
Beyond the limit, the photosensitive composition is coated on an aluminum support.
Cloth property deteriorates. Further, the dispersion component γ (D) value is 50
In the case of exceeding the same, aluminum
The coatability on the support is poor.

<Aluminum Support According to Claims 3 and 6> In the aluminum support according to claims 3 and 6 of the present invention, the reflectance of the surface of the aluminum support (the aluminum support according to claims 1 and 4). As in the case of the aluminum support, the reflectance when using ultraviolet light of 350 to 400 nm) is 5
0 to 70%, and the surface of the aluminum support has a hydrogen bonding component γ (H) value of 10 to 55 dyn / cm represented by the following relational expression (1), and a dispersion component represented by the following relational expression (2). It is an essential requirement that the γ (D) value satisfy 50 dyn / cm or less.

Hydrogen bond component γ (H) = [｛1.159 + 1.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) reflectance of the surface of the aluminum support, (contact angle: H_Two
O and contact angle: CH_TwoI_Two) Derived from the hydrogen bond component γ
The (H) value and the dispersion component γ (D) value are, for example,
Method, chemical etching method, desmutting method, positive
Articles such as extreme oxidation treatment method, sealing treatment method, and hydrophilic treatment method
It can be controlled by selecting the matter. In addition,
When the reflectance of the surface of the aluminum support is less than 50%
If the sensitivity of the PS plate is insufficient, the print image will be over 70%
Of the hydrogen bond component γ (H)
Is less than 10, the developability deteriorates, and if it exceeds 55,
Poor coatability of photosensitive composition on aluminum support
Become. When the dispersion component γ (D) value exceeds 50,
In the same manner, the above photosensitive composition is placed on an aluminum support.
Of the coating becomes poor.

The hydrogen bond component γ (H) value and the dispersion component γ, which are the surface energy of the aluminum support,
(D) The value is determined by the following measurement method.

<< Hydrogen Bonding Component γ (H) Value and Dispersion Component γ
(D) Method of Measuring Value >> First, the contact angle of the aluminum support is measured. Pure water (H ₂ O) and diiodomethane (CH ₂ I ₂ ) were used for the measurement, and 1.7 μl of pure water and 1.3 μl of diiodomethane were dropped at intervals of 10 mm on the sample surface. The angle between the liquid and the droplet is measured. At this time, the roughness of the sample surface is ignored and the horizontal plane is assumed, and the angle formed by extrapolating the curve formed by the projection plane of the entire droplet and the tangent of the point intersecting with the horizontal plane of the sample surface and the angle of the droplet side formed by the horizontal plane Is the contact angle. A very close part where the sample surface and the droplet are in contact with each other is ignored because of the influence of surface roughness and the like. In the contact measurement, 20 or more points are measured, and an average value thereof is used. Using the obtained contact angle, the hydrogen bond component γ (H) value and the dispersion component γ of the surface energy of the aluminum support surface are calculated from the following equations (1) and (2).
(D) Determine the value.

Hydrogen bond component γ (H) = [｛1.159 + 2.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) [Photosensitive composition of the present invention]
The photosensitive composition is coated and processed on the luminium support.
The desired PS plate is obtained, and the photosensitive composition contains a photosensitive substance.
As a microgel having photocrosslinkable groups on the surface
(Also referred to as crogel A) or photopolymerization initiator
Microgels having polymerizable unsaturated groups (hereinafter referred to as microgels)
Le B). In addition, the above photosensitive composition
In some cases, diazo resin and film can be formed if necessary
Compound, a substance that generates an acid upon exposure, a sensitizer, an acid
(Organic acids, inorganic acids or acid anhydrides), surfactants,
Dyes, solvents and the like can be contained.

<Microgel A having a photocrosslinkable group on the surface according to claims 1 to 3> The microgel A having a photocrosslinkable group on the surface is described in, for example, JP-A-3-64755 and JP-A-6-161101. And other publications, specifically, those described below are preferred.

For example, a latex polymer chemically modified with a diazonium compound, in which the diazonium compound and the latex polymer are bonded by an ionic bond or a covalent bond, may be mentioned. Examples of the compound bonded by the ionic bond include a reaction product of a cationic latex polymer having a quaternary nitrogen atom and an anionic diazo compound, or an anionic latex having a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, or the like. Reaction products of a polymer and a cationic diazo compound are exemplified.

(1) A microgel wherein the counter anion of the diazonium salt is a cationic latex polymer.

The cationic latex polymer is prepared by emulsion polymerization of vinylbenzyl chloride with another monomer as described in Examples of JP-A-51-73440, followed by quaternization with a tertiary amine. There is known a technology for converting the data. In particular, a cationic latex polymer produced by quaternizing a latex polymer having a tertiary amine obtained by emulsion polymerization with a quaternizing agent is preferable. No., published in Japanese Unexamined Patent Publication No.

Another particularly preferred cationic latex polymer having a quaternary nitrogen atom is a latex polymer produced by emulsion-polymerizing a quaternary nitrogen-containing monomer with a lipophilic monomer. The synthesis method is described, for example, in JP-A-56-17352.

Next, diazo compounds having an anionic group which reacts with the cationic latex polymer are described in Japanese Patent Publication Nos. 2-77338, 4-172353 and 57-43890. A compound in which an anionic group has been further introduced into the diazo compound described above can be used. Specific examples include, for example, sodium 4-diazostilbene-2-sulfonate, 4-diazo-1
Sodium phenylamino-2-sulfonate, 4,
Sodium 4'-diadiazostilbene-2-sulfonate, sodium 4-diazobenzophenone-4'-carboxylate, sodium 1-diazopyrene-6-sulfonate, 4,4'-diadiazophenylazonaphthalene-5-
Examples thereof include sodium sulfonate, sodium diazonaphthalene-4-sulfonate, sodium diazobenzene-m-carboxylate and the like.

In order to synthesize a microgel in which the counter anion of the cationic latex polymer is a diazo compound having an anionic group, an aqueous solution of the diazo compound having an anionic group is mixed with an aqueous dispersion of the cationic latex polymer. The precipitate obtained by mixing the above is collected by suction filtration and washed with water to obtain the desired product.

(2) A microgel in which the counter anion of the diazonium salt is an anionic latex polymer.

As the diazonium salt, a photosensitive diazo compound commonly used as a photosensitive component in a photosensitive layer of a PS plate is used. In general, such diazo compounds are diazo-aromatics, more particularly diazo-arylamines, preferably p-diazo-diphenylamine and its derivatives, which can be substituted on the aromatic nucleus or on the amino-nitrogen. For example, condensation products using organic condensing agents containing reactive carbonyl groups such as aldehydes and acetals, especially condensates with compounds such as formaldehyde zinc chloride and paraformaldehyde. The preparation of such highly suitable condensation products is described in U.S. Pat.
922,715 and 2,946,683.

The anionic latex polymer has an acrylic group or a methacryl group as a monomer unit of the polymer, and the acrylic group or the methacryl group has a carboxylic acid group, a sulfonic acid group or a phosphonic acid group. Is used, and as a specific example of such a monomer unit,
The following compounds are mentioned.

[0049]

Embedded image

[0050]

Embedded image

It is preferable that the above-mentioned monomer unit is usually contained in the photocrosslinkable group-introduced microgel of the present invention in an amount of 0.5 to 50% by weight, particularly 2 to 30% by weight.

The above-mentioned anionic latex polymer can be synthesized by copolymerizing the above-mentioned monomer and a non-anionic monomer. Examples of the non-anionic monomer used include acrylic acid, methacrylic acid ester, and the like.
Examples thereof include styrene, alkylene, ether, vinyl acetate, acrylonitrile and the like, which are preferably crosslinked with a monomer having two or more functional groups such as divinylbenzene and dimethacrylate. Such a non-ionic monomer is preferably contained in the microgel of the present invention in which the photocrosslinkable group is introduced in an amount of 5 to 95% by weight, and a monomer such as divinylbenzene dimethacrylate is preferably contained in the microgel. It is contained in an amount of 1 to 10% by weight.

The anionic latex polymer of the present invention is described, for example, in JP-A-51-73440 and JP-A-55-2.
It can be synthesized according to the emulsion polymerization method described in No. 2766 and the like.

As a method for synthesizing a microgel in which the counter anion of the diazonium salt is an anionic latex polymer, a precipitation method obtained by mixing the aqueous solution of the diazonium salt and the aqueous dispersion of the anionic latex polymer is used. The product can be collected by suction filtration and washed with water to obtain the desired product.

(3) As a method for synthesizing a microgel in which a diazonium compound and a latex polymer are covalently bonded, the amino group of a latex polymer having an amino group on the particle surface is diazotized with sodium nitrite under acidic conditions. Obtained.

A latex polymer having an amino group is usually produced by emulsion polymerization using a monomer having an amino group. Generally, a latex polymer having an amino group is composed of 99 to 99.5% by weight of a polymer component and 10% by weight of a crosslinking agent.
~ 0.5% by weight. The polymer components can be varied in the course of the polymerization to produce a latex polymer having a core and shell having different compositions on the inside and the outside. When a binder is used in the polymer,
The weight ratio of latex polymer to binder is from 1:20 to 1:
It can be changed widely within the range of 1.

The latex polymer can be made from a variety of starting materials, but usually one monomer having one ethylenically unsaturated bond is used to make up the majority of the latex polymer and the crosslinking agent is at least It has two double bonds.

Examples of the monomer having an amino group as a starting material of the latex polymer include acrylamide,
Methacrylamide, 2-aminoethyl vinyl ether,
p-Aminostyrene and the like.

Preferred monomers copolymerized with these are methyl methacrylate, ethyl acrylate,
Methacrylic acid, butyl methacrylate, ethyl methacrylate, glycidyl methacrylate, styrene and allyl methacrylate; other useful monomers include acrylonitrile, methacrylonitrile,
Acrylic acid, methacrylic acid and 2-methyl-hexyl acrylate are included.

Preferred crosslinking agents include butanediol diacrylate, and others include ethylene glycol dimethacrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, tetraethylene glycol dimethacrylate, methylene Bisacrylamide, methylenebismethacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl benzene, glycerin trimethacrylate, pentaerythritol tetramethacrylate, triallyl cyanurate, divinyl acetylene, divinyl ethane , Divinyl sulfide, divinyl sulfone, hexatriene, triethylene glycol dimeta Relate, diallyl cyanamide,
Glycol diacrylate, ethylene glycol divinyl ether, diallyl phthalate, divinyl dimethyl silane, glycerol trivinyl ether and the like.

In producing a microgel in which the diazonium compound and the latex polymer are covalently bonded, one or several monomers and a crosslinking agent are dispersed in water together with a suitable emulsifier and an initiator. . Usually anionic, cationic or nonionic emulsifiers and water-soluble initiators are used. Examples of emulsifiers include sodium lauryl sulfate, lauryl pyridine chloride, polyoxyethylene, polyoxypropylene, colloidal silica, anionic organic phosphate, magnesium montmorillonite,
And reaction products of 1 mol of octylphenol and 12 to 13 mol of ethylene oxide, sodium dialkyl sulfate and mixtures thereof. Examples of initiators are potassium persulfate, sodium persulfate, ammonium persulfate, t-butyl hydroperoxide, hydrogen peroxide, azobis (isobutyronitrile), azobis (isobutyromidine hydrochloride), hydrogen peroxide-sulfuric acid Various redox (oxidation-reduction) systems such as ferrous iron and the well-known persulfate-bisulfite combination. Usually 0.05 to 5% by weight of initiator is used, based on the weight of the monomers to be copolymerized.

Another method for introducing a hydroxyl group or an amino group into the particle surface is described in, for example, “Chemical reaction of polymer (above)
(Below) "(Nobuo Ogawara, Kagaku Doujin, 1972)," Polymer Fine Chemicals "(Ryohei Oda, Kodansha, 197)
6), a method based on a polymer reaction described in “Reactive polymer” (Keita Kurita, Yoshio Iwakura, Kodansha, 1977) can also be used. For example, after a microgel having a reactive group is synthesized, it has an amino group. A method of chemically modifying a reactive group with a compound or graft-polymerizing a reactive group as a starting point with a polymerizable monomer having an amino group is used.

In order to synthesize a microgel in which a diazo compound and a latex polymer are bonded by a covalent bond, an aqueous dispersion of the above-mentioned amino group-containing latex polymer is made acidic with sulfuric acid, hydrochloric acid or the like, and cooled to about 0 ° C. Then, a concentrated aqueous solution of sodium nitrite is added dropwise with stirring, and after the addition, it is confirmed that the solution is acidic. Then, stirring is continued for 30 minutes to complete the diazotization. A salt of a desired counter anion (for example, zinc chloride or ammonium hexafluorophosphate) is added to this solution, shaken well, and allowed to stand, whereby a microgel having a desired diazo group is obtained by precipitation.

(4) Polymerization reaction between a compound having a photocrosslinkable group represented by the following general formula (1) and a polymerizable ethylenically unsaturated bond, and another compound having a polymerizable ethylenically unsaturated bond: The microgel obtained by the above.

[0065]

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In the formula, R ¹ and R ² are each a hydrogen atom, a halogen atom, an alkyl group or an aryl group;
R ¹ and R ² may form a ring.

The compound having a photocrosslinkable group represented by the general formula (1) and a polymerizable ethylenically unsaturated bond is preferably contained in the microgel described in the above item (4) in an amount of 10 to 99 mol%. .

In the compound having a photocrosslinkable group represented by the general formula (1) and a polymerizable ethylenically unsaturated bond,
As the compound particularly preferably used in the present invention, for example, compounds represented by the following general formulas (2) to (7) are preferable.

[0069]

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In the above general formulas (2) to (7), R ¹ and R ²
Has the same meaning as in the above formula (1), and R ³ and R ⁴ represent a hydrogen atom or an alkyl group (for example, —CH ₃ );
Represents -O- or -NH-. Further, n ^{1 to} n ⁹ represent one or more integers.

Among the compounds having a photocrosslinkable group and an ethylenically unsaturated group represented by the above general formula (1), another preferred compound is a compound described in JP-A-52-988. Are also preferably used in the present invention.

<Photopolymerization Initiator According to Claims 4 to 6> The photopolymerization initiator used in the present invention is not particularly limited, and conventionally known photopolymerization initiators can be used. Examples thereof include benzoin, benzoin alkyl ether, and benzophenone. , Anthraquinone compounds, Michler's ketone, trihalomethyl-s-
Triazine compounds, oxadiazole compounds, biimidazole compounds, thioxanthone compounds, aromatic tertiary amines and the like are preferably used.

Specific examples of these photopolymerization initiators include “UV
/ EB Curing Handbook -Raw Materials- ", Kato Kiyomi (ed. By Polymer Publishing Association), pp. 67 to 73," UV / EB
Application and Market of Curing Technology ”, edited by Radotech Kenkyukai, supervised by Yoneho Tabata, pages 64 to 82,
JP-B-6-42074, JP-A-62-61044,
These are described in JP-A-60-35725 and JP-A-2-28747, and these photopolymerization initiators can be used in the present invention.

Further, the compounds capable of generating an acid upon irradiation with actinic rays described in JP-A-4-362543 and JP-A-4-362644 may also be used as a photopolymerization initiator in the present invention. Can be.

As the other photopolymerization initiator, a compound having a structure represented by the following general formula (8) can be used.

[0076]

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[Wherein R ⁵ and R ⁶ represent an alkyl group or a halogen atom, and f and g represent an integer of 0-4. Specific examples of the compound having a structure represented by the general formula (8) include 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and isopropylthioxanthone. Can be mentioned.

The photopolymerization initiator is added to the photosensitive composition
It is preferably contained in the range of 0.2 to 15% by weight, and more preferably in the range of 0.5 to 10% by weight.

<Microgel B Having Addition-Polymerizable Unsaturated Bonds on the Surface According to Claims 4 to 6> The microgel B having addition-polymerizable unsaturated bonds on the surface of the present invention is described in, for example, JP-A-2-263805. No., JP-A-3-7670
4, JP-A-3-75750, JP-A-5-97915
JP-A-5-150451, JP-A-5-17894
6, JP-A-6-194837, JP-A-7-1141
No. 80, JP-A-8-160618, etc., which are well known. Microgels B suitable for the present invention are preferably those having the following addition-polymerizable unsaturated bonds.

The microgel B having an addition polymerizable unsaturated bond is obtained by using a compound having two or more polymerizable ethylenically unsaturated bonds as a cross-linking agent, and using the cross-linking agent and another polymerizable ethylenically unsaturated bond. It is obtained by an addition polymerization reaction with a compound having an unsaturated bond.

The compounds having two or more polymerizable ethylenically unsaturated bonds as the crosslinking agent include butadiene, isoprene, 1,3-pentadiene, 2,3-
Dimethylbutadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, 2,3-dichlorobutadiene, 1,3-cyclopentadiene, ethylene glycol di (meth) acrylate, butane Diol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, methylenebis (meth) acrylamide, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate, pentaerythritol tetra (meth) acrylate, 1,4-butanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) Acrylate, neopentyl glycol di (meth) acrylate,
Glycerol di (meth) acrylate, glycerol allyloxydi (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate, 1,
1,1-trishydroxymethylethanetri (meth) acrylate, 1,1,1-trishydroxymethylpropanedi (meth) acrylate, 1,1,1-trishydroxymethylpropanetri (meth) acrylate, triallyl cyanu And diallyl terephthalate, diallyl phthalate, triallyl trimellitate, triallyl isocyanate, divinylbenzene and the like. These components in the polymer are usually 1 to 50% by weight, preferably 1 to 30% by weight. If it is less than 1 wt%, the strength after curing is insufficient, and if it exceeds 50 wt%, the developability is reduced.

Other compounds having a polymerizable ethylenically unsaturated bond capable of forming a microgel by an addition polymerization reaction with the crosslinking agent include generally known olefins, acrylics, styrenes and styrene-acrylic compounds. Compounds having an ethylenically unsaturated bond are widely used.

<< Synthesis Method of Microgel Having Addition-Polymerizable Unsaturated Bond on Surface >> The microgel having an addition-polymerizable unsaturated bond on the surface of the present invention is preferably obtained by emulsion polymerization or dispersion polymerization. The method is described in U.S. Pat. No. 3,895,082, U.S. Pat.
Nos. 67,051 and Immunological Communications 12 (5), 509-517 (198)
There are many documents including 3).

As the above-mentioned synthesis method, for example, microgel fine particles synthesized by emulsion polymerization of two or more compounds having a polymerizable ethylenically unsaturated bond using a tertiary ammonium salt-containing compound as an emulsifier, A method comprising reacting an epoxy group capable of reacting with a tertiary ammonium salt and a compound having at least one polymerizable ethylenically unsaturated bond in one molecule, the above two or more polymerizable ethylenically unsaturated bonds Is a microgel fine particle synthesized by emulsion polymerization using a quaternary ammonium salt-containing compound as an emulsifier, an epoxy group which reacts with the quaternary ammonium salt in one molecule, and at least one polymerizable ethylenically unsaturated compound. A method comprising reacting a compound having a saturated bond with the above two or more polymerizable ethylenically unsaturated compounds. Compounds having binding, and microgels microparticles carboxyl group-containing compound was synthesized by emulsion polymerization using as an emulsifier,
A method in which an epoxy group which reacts with a carboxyl group and a compound having at least one polymerizable ethylenically unsaturated bond in one molecule is reacted is also exemplified.

When a microgel is prepared by emulsion polymerization, it is usually necessary to convert the microgel into a dry powder before preparing the photosensitive composition. Known techniques of flocculation, filtration, washing and drying can be used for this purpose. Alternatively, a dispersion liquid of an organic solvent can be obtained by using an appropriate organic solvent without azeotropic distillation to form a powder from a microgel aqueous dispersion liquid.

The photosensitive composition of the present invention contains the above-mentioned photopolymerization initiator together with the above-mentioned microgel B having an addition-polymerizable unsaturated bond, thereby imparting photosensitivity. The amount contained in it is 5-70wt%
If it is less than 5 wt%, the strength of the cured photosensitive layer is insufficient, and if it exceeds 70 wt%, the developability is reduced.

Next, the photosensitive composition of the present invention may contain, if necessary, a diazo resin described later, a polymer compound capable of forming a film, a compound capable of generating an acid upon exposure, a sensitizer, an organic or inorganic acid anhydride. Substances, surfactants, dyes, solvents and the like.

<Diazo resin> The diazo resin optionally contained in the photosensitive composition of the present invention is, for example, a condensate of an aromatic diazonium salt and formaldehyde or acetaldehyde, and particularly preferably p-diazophenylamine And salts of condensates with formaldehyde or acetaldehyde, such as hexafluoroborate, tetrafluoroborate, perchlorate or periodate or a diazo resin inorganic salt which is a reaction product of the condensate, Examples thereof include an organic salt of a diazo resin which is a reaction product of the condensate and a sulfonic acid as described in US Pat. No. 3,300,309. Furthermore, diazo resin is
It is preferably used with a binder. As such a binder, various polymer compounds can be used. Preferably, a monomer having an aromatic hydroxyl group as described in JP-A-54-98613, for example, N-
(4-hydroxyphenyl) acrylamide, N- (4
-Hydroxyphenyl) methacrylamide, o-, m
-Or p-hydroxystyrene, o-, m- or p
Copolymers of hydroxyphenyl methacrylate or the like with other monomers, a main repeating unit of a hydroxyethyl acrylate structural unit or a hydroxyethyl methacrylate structural unit as described in US Pat. No. 4,123,276. Polymers containing as units, natural resins such as shellac and rosin, polyvinyl alcohol, linear polyurethane resins as described in US Pat. No. 3,751,257, phthalated resins of polyvinyl alcohol, bisphenol A and Epoxy resins condensed from epichlorohydrin, cellulose derivatives such as cellulose acetate and cellulose acetate phthalate are included.

The diazo resin is preferably a co-condensation resin of diazodiphenylamine and an aromatic compound having at least one group selected from a carbonyl group and a sulfonyl group in the molecule. The cocondensation ratio is a diazodiphenylamine / aromatic compound = 30/70 to 95/5 in a molar ratio, particularly preferably a cocondensate of diazodiphenylamine and p-hydroxybenzoic acid, and a molar ratio of 50/70. 50 to 80/20.

Further, a preferred diazo resin in the present invention is a condensation resin of an aromatic diazonium compound and a carbonyl compound.

In this condensation resin, it is preferable to use a diazo resin having a structure represented by the following general formula (9) or (10).

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(Wherein, R represents a hydrogen atom, an alkyl group or a phenyl group, R ⁷ , R ⁸ and R ⁹ each represent a hydrogen atom, an alkoxy group or an alkyl group, and X ⁻ represents a counter anion. Y represents -NH-, -O- or -S-, and n represents an integer.)

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Wherein A represents a condensable aromatic group, and R, R ⁷ , R ⁸ , R ⁹ , X ⁻ , Y and n have the same meanings as those used in formula (6). As the aromatic diazonium compound as a structural unit constituting the diazo resin represented by the general formulas (9) and (10), for example, a diazonium salt as described in JP-B-49-48001 is exemplified. Can be used,
Particularly, diphenylamine-4-diazonium salts are preferred. Diphenylamine-4-diazonium salts are derived from 4-aminodiphenylamines, and such 4-aminodiphenylamines include 4-aminodiphenylamine, 4-amino-3-methoxydiphenylamine, and 4-amino-2-methoxy. Diphenylamine,
4'-amino-2-methoxydiphenylamine, 4'-
Amino-4-methoxydiphenylamine, 4-amino-
3-methyldiphenylamine, 4-amino-3-ethoxydiphenylamine, 4-amino-3- (β-hydroxyethoxy) diphenylamine, 4-aminodiphenylamine-2-sulfonic acid, 4-aminodiphenylamine-2-carboxylic acid, 4- Aminodiphenylamine-2 '
-Carboxylic acids and the like. Of these, particularly preferred are 4-aminodiphenylamine and 4-amino-3-methoxydiphenylamine.

In the above formula (10), specific examples of the aromatic compound which can be used to give the aromatic group represented by A include m-chlorobenzoic acid, diphenylacetic acid, phenoxyacetic acid, -Methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4- (m-methoxyanilino) benzoic acid, 4- (p-methylbenzoyl) benzoic acid, 4- (p-methylanilino) benzoic acid, phenol, cresol, xylenol, resorcin, 2-methylresorcin, methoxyphenol, ethoxyphenol, catechol, phloroglucin, p-hydroxyethylphenol, Naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl Alcohol, 4-chloro resorcinol, biphenyl-4,4'-diol, 1,2,
4-benzenetriol, bisphenol A, 2,4-
Dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, p-hydroxyacetophenone,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dimethoxydiphenylether, 4,4'-dihydroxydiphenylamine, 4,4'-dihydroxydiphenylsulfide, cumylphenol, chlorophenol, bromophenol, salicylic acid, p-hydroxybenzoic acid, 2-methyl-4-hydroxybenzoic acid, , 4
-Dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-chloro-2,
6-dihydroxybenzoic acid, 4-methoxy-2,6-dihydroxybenzoic acid, gallic acid, phloroglysin carboxylic acid, N- (4-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) acrylamide,
Cinnamic acid, methyl cinnamate, ethyl cinnamate, p-hydroxycinnamic acid, styrene, hydroxystyrene, stilbene,
4-hydroxystilbene, 4,4'-dihydroxystilbene, 4-carboxystilbene, 4,4'-dicarboxystilbene, diphenol ether, diphenylamine, diphenylthioether, 4-methoxydiphenylether, 4-methoxydiphenylamine, 4-methoxydiphenylamine
Methoxydiphenylthioether and the like can be mentioned.

In the above formula (10), particularly preferred specific examples of the aromatic compound which can be used to give the aromatic group represented by A are p-hydroxybenzoic acid and p-methoxy. Examples include benzoic acid, p-hydroxycinnamic acid, and phenoxyacetic acid.

The diazo resin can be prepared by a known method, for example,
Photographic Science and Engineering (Photo. Sci. Eng.) Vol. 17, p. 33 (1973), U.S. Pat. No. 2,063,631,
2,679,498, JP-B-49-480
No. 01, aromatic diazonium salt, optionally an aromatic compound giving an aromatic group represented by A in the above general formula (10) and an active carbonyl compound in sulfuric acid, phosphoric acid or hydrochloric acid For example, paraformaldehyde, acetaldehyde, benzaldehyde,
It is obtained by polycondensing acetone, acetophenone, or the like.

The aromatic compound, the aromatic diazo compound and the active carbonyl compound which give an aromatic group represented by A in the general formula (10) can be freely combined with each other. And condensed.

In the condensation, the number of moles of the charged aromatic compound which gives the aromatic group represented by A is preferably 0.1 to 0.1 with respect to the number of moles of the aromatic diazonium compound.
It is 10 times, more preferably 0.2 to 2 times, and still more preferably 0.2 to 1 times. In this case, the active carbonyl compound is usually preferably 0.5 to 1.5 times the total number of moles of the aromatic compound giving the aromatic group represented by A and the aromatic diazonium compound, More preferably, the diazo resin is obtained by charging at a ratio of 0.6 to 1.2 times and reacting at a low temperature for a short time, for example, for about 3 hours.

Means for synthesizing a diazo resin having a carboxyl group in the molecule, which can be more preferably used in the present invention, is optional.
(A) polycondensation reaction of aromatic diazonium compound, aromatic carboxylic acid and active carbonyl compound, (B) polycondensation reaction of aromatic diazonium compound having carboxyl group and active carbonyl compound, (C) aromatic diazonium compound and carboxyl compound There are three types of polycondensation reaction of an active carbonyl compound having a group. Of these methods,
The means (A) is preferable in terms of the synthesis technique and the ease of obtaining the synthesis raw materials.

The counter anion of the diazo resin is preferably an anion which forms a salt with the diazo resin stably and makes the resin soluble in an organic solvent. Examples of the acid forming such an anion include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and organic sulfonic acids.Typical examples include methanesulfonic acid, chloroethanesulfonic acid, Aliphatic sulfonic acids such as dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, methylenesulfonic acid, anthraquinonesulfonic acid, naphthylsulfonic acid, alkyl-substituted naphthylsulfonic acid, and aromatic sulfonic acids, hexafluorophosphoric acid, tetrafluoroboric acid, etc. And perhalic acids such as perchloric acid and periodic acid. However, it is not limited to this. Among them, particularly preferred are hexafluorophosphoric acid, tetrafluoroboric acid, and methylenesulfonic acid.

The molecular weight of the diazo resin used in the present invention is not particularly limited. For example, the above diazo resin can be obtained by variously changing the molar ratio of each monomer and the condensation conditions.
Although the molecular weight can be obtained as an arbitrary value, it is generally preferred in the present invention that the molecular weight is 400 to 10,
000 can be used effectively, more preferably 800
~ 5,000 is suitable.

The amount of these diazo resins contained in the photosensitive composition is preferably 0.5 to 30% by weight.
More preferably, it is 0.5 to 20% by weight.

<Polymer compound capable of forming a film> The polymer compound capable of forming a film used in the photosensitive composition of the present invention is a copolymer of a monomer selected from the following monomer groups (1) to (16). Can be used.

(1) Monomers having an aromatic hydroxyl group, for example, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxystyrene, p-hydroxystyrene, m-hydroxystyrene , O-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate,
m-hydroxyphenyl acrylate and the like.

(2) Monomers having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide,
N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

(3) Monomers having an aminosulfonyl group, for example, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate,
m-aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like.

(4) Monomers having an unsaturated sulfonamide, for example, N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

(5) α, β-unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.

(6) Substituted or unsubstituted alkyl acrylates, for example, methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, acrylic acid -2-chloroethyl, N, N-dimethylaminoethyl acrylate, glycidyl acrylate and the like.

(7) Substituted or unsubstituted alkyl methacrylates, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacrylic acid Decyl, undecyl methacrylate, dodecyl methacrylate,
Benzyl methacrylate, cyclohexyl methacrylate,
2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like.

(8) Acrylamide or methacrylamides, for example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N -Phenylacrylamide and the like.

(9) Monomers containing a fluorinated alkyl group, for example, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl acrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl Methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

(10) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(11) Vinyl esters of vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(12) Styrenes such as styrene, methylstyrene and chloromethylstyrene.

(13) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(14) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine.

(16) A cyano group-containing monomer, for example,
Acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethylacrylate, o-cyanostyrene, m-cyanostyrene, p-cyanostyrene and the like.

Further, a monomer copolymerizable with the above-mentioned monomer may be copolymerized.

The molecular weight of these polymer compounds capable of forming a film is usually from 5,000 to 2,000 in terms of weight average molecular weight.
00, preferably 20,000 to 160,000.

The amount used is 5 to 95% by weight, preferably 10 to 90% by weight, based on all components.

<Compound that Generates Acid upon Exposure> In the photosensitive composition, a compound that generates an acid or a free radical upon exposure can be used. For example, a halomethyloxadiazole compound, a halomethyl-s-triazine compound, or the like is used.

A halomethyloxadiazole compound is
Oxadiazoles are compounds having a halomethyl group, preferably a trichloromethyl group.

These compounds are known. For example, JP-B-57-6096 and JP-B-61-51788,
-28369, JP-A-60-138439, JP-A-60-138439
177340 and 60-241049.

The halomethyl-s-triazine compound is a compound having at least one halomethyl group, preferably a trichloromethyl group, on the s-triazine ring.

The amount of the compound capable of generating an acid or a free radical upon exposure to light in the photosensitive composition is from 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.

Further, a printout material for forming a visible image upon exposure can be added to the photosensitive composition. The printout material is composed of an organic dye which changes its color tone by interacting with a compound which generates an acid upon exposure. Examples of the compound which generates an acid upon exposure include those described in JP-A-50-36209. −
Naphthoquinonediazide-4-sulfonic acid halogenide, an ester compound of o-naphthoquinonediazide-4-sulfonic acid chloride and a phenol having an electron-withdrawing substituent or ananilic acid described in JP-A-53-36223 or Amide compounds, JP-A-55-777
No. 42, and a halomethylvinyloxadiazole compound and a diazonium salt described in JP-A-57-148784 and the like.

<Oil Sensitizing Agent> The photosensitive composition of the present invention may contain an oil sensitizing agent. The sensitizing agent enhances the lipophilicity of the photosensitive layer surface, and includes, for example, an ester of p-hydroxystyrene and a fatty acid, a half-ester compound of a styrene-maleic anhydride copolymer with an alcohol, and a long-chain alkyl group-containing compound. Novolak resins, fluorine-based surfactants, etc. are preferred, and preferred are esters of p-hydroxystyrene and a fatty acid, half-ester compounds of styrene-maleic anhydride copolymer with alcohols, and novolak resins containing a long-chain alkyl group. Among them, a long-chain alkyl group-containing novolak resin (alkyl-substituted phenol resin) is particularly preferable. The amount added varies depending on the intended use and purpose, but is generally 0.01 to
30% by weight.

The above-mentioned alkyl-substituted phenol resin is a resin obtained by polycondensation of an alkyl-substituted phenol with an aldehyde.

The position of the alkyl-substituted phenol and the number of substituents in the alkyl-substituted phenol used herein are arbitrary, but a particularly preferred example is a structure having one alkyl group at the 4-position. The structure of the alkyl group may be linear, branched or cyclic, and the alkyl group may have any number of carbon atoms, but preferably an alkyl group having 1 to 20 carbon atoms. These alkyl-substituted phenols may have other substituents on the aromatic ring.

In the polycondensation of an alkyl-substituted phenol and an aldehyde, cocondensation can be preferably carried out by adding an unsubstituted phenol.

<Organic acid / inorganic acid / acid anhydride> The photosensitive composition may contain an organic acid / inorganic acid / acid anhydride. Examples of the acid used in the present invention include, for example,
No.-88942, Japanese Patent Application No. 63-293107, and an organic acid described in Chemical Society of Japan, edited by The Chemical Society of Japan, Maruzen Publishing.
Inorganic acids described on pages 92 to 158; Examples of the organic acid include sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and m-benzenedisulfonic acid, and p-toluenesulfonic acid. , Sulfinic acid such as benzylsulfinic acid, methanesulfinic acid, etc. Alicyclic monocarboxylic acids such as aliphatic monocarboxylic acids and cyclohexanecarboxylic acids, benzoic acid, o-, m-, p-hydroxybenzoic acid, o-, m
-, P-methoxybenzoic acid, o-, m-, p-methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysin carboxylic acid, gallic acid, 3,5-dimethylbenzoic acid,
And aromatic monocarboxylic acids such as syringic 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, 1,2-cyclohexanedicarboxylic acid, 1,3
-Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid.

Of the above organic acids, more preferred are p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
Sulfonic acids such as methylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and m-benzenedisulfonic acid; and 1,2-cyclohexanedicarboxylic acid and syringic acid.

Examples of the inorganic acids include nitric acid, sulfuric acid, hydrochloric acid,
Examples thereof include silicic acid and phosphoric acid, and 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, and benzoic anhydride, 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. It is.

<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.

As anionic surfactants, fatty acid salts,
Alkyl sulfate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl allyl sulfate, naphthalene Sulfonic acid formalin condensate,
And polyoxyethylene alkyl phosphates.

Examples of the cationic surfactant include an alkylamine salt, a quaternary ammonium salt, and an alkyl betaine.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene. Examples include sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, alkylalkanolamides, and the like.

Examples of the fluorine-based surfactant include acrylate or methacrylate containing a fluoroaliphatic group and a copolymer of (polyoxyalkylene) acrylate or (polyoxyalkylene) methacrylate. These compounds can be used alone or in combination of two or more. Particularly preferred is FC-430.
(Sumitomo 3M Co., Ltd.) Fluorinated polyethylene glycol # -2000 (Kanto Chemical Co., Ltd.). The proportion occupying in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight.

<Dye> A dye can be further used in the photosensitive composition. The dye is used for the purpose of obtaining a visible image by exposure (exposure visible image) and a visible image after development.

As the dye, those which change color tone by reacting with a free radical or acid 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 that form a salt with an acid to change the color tone. For example, Victoria Pure Blue BOH (made by Hodogaya Chemical Co., Ltd.), Oil Blue #
603 (manufactured by Orient Chemical Industries), patent pure blue (manufactured by Sumitomo Mikuni Chemicals), crystal violet,
Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Paysic Fuchsin, Malachite Green, Oil Red, m
-Cresol purple, rhodamine B, auramine, 4
Triphenylmethane, diphenylmethane represented by -p-diethylaminophenyliminaphthoquinone, cyano-p-diethylaminophenylacetanilide and the like;
Oxazine, xanthene, iminonaphthoquinone,
The azomethine-based or anthraquinone-based dye is mentioned as an example of a color-changing agent that changes from colored to colorless or a different colored tone.

On the other hand, examples of the color changing agent which changes from colorless to colored include 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, p, Primary or secondary arylamine dyes represented by p ', p "-triaminotriphenylmethane are exemplified.

The proportion of the above color changing agent in the photosensitive composition is preferably from 0.01 to 10% by weight, more preferably from 0.02 to 5% by weight.

These compounds can be used alone or as a mixture of two or more. Particularly preferred dyes are Victoria Pure Blue BOH and Oil Blue # 603.

<Solvent> Solvents that can be used for dissolving the photosensitive composition include methanol, ethanol, n-propanol, iso-propanol, n-butanol,
aliphatic alcohols such as n-pentanol and hexanol, allyl alcohol, benzyl alcohol, anisole, phenetole, n-hexane, cyclohexane, heptane, octane, nonane, hydrocarbons such as 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-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 (methyl cellosolve, ethyl cellosolve) , Butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Distearate ether, methyl cellosolve acetate, ethyl cellosolve acetate), diethylene glycol monoalkyl ethers and acetates thereof (diethylene glycol monomethyl ether, monoethyl ether, mono-i- propyl ether,
Monobutyl ether, diethylene glycol monomethyl ether acetate, etc.), diethylene glycol dialkyl ethers (DMDG, DEDG, DBDG, ME
DG), 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, Butyl 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, formic acid Propyl, butyl formate,
Amyl formate, methyl acetate, ethyl acetate, propyl acetate,
Carboxylic esters such as butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate, dimethylformamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, methyl benzoate, ethyl benzoate, propylene carbonate, etc. Is mentioned.

These solvents can be used alone or in combination of two or more.

Next, the following coating layer or mat layer can be provided on the photosensitive layer surface of the PS plate of the present invention, if necessary.

<Coating Layer> A photosensitive layer is formed on an aluminum support by using the above photosensitive composition to form the P layer of the present invention.
Although an S plate is obtained, a coating layer made of a polymer having excellent oxygen barrier properties, such as polyvinyl alcohol and acidic celluloses, is provided on the PS plate for the purpose of preventing oxygen inhibition of photopolymerization, if necessary. Can be.

<Matte layer> By improving the vacuum adhesion between the image film and the PS plate in the contact exposure, it is possible to shorten the evacuation time and to prevent the collapse of minute dots during exposure due to poor adhesion. For the purpose, a mat layer can be formed on the photosensitive layer. As a method of applying the mat layer, JP-A-50-125805, JP-B-57
No. 6,658, and No. 61-28986, a method of providing a mat layer as described in JP-B-62-6.
2337, a method of thermally fusing a solid powder as described in JP-A No. 2337, a method of thermally fusing a powdered solid powder described in JP-A-55-12974, and JP-A-58-182636. There is a method of spraying and drying the polymer-containing water described in Japanese Patent Application Laid-Open No. H10-209, and any method may be used. However, it is preferable that the mat layer itself dissolves in the alkali developer or can be removed by this.

<Coating method> As a coating method, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, electrostatic spray coating, roll coating, blade coating Coating and drying are performed by a coating and curtain coating method, and then a solution (photosensitive solution) in which the upper layer component is dissolved is coated and dried by a similar known method.

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

<Exposure> In the use of the photosensitive lithographic printing plate thus obtained, a conventionally used method can be applied. For example, a transparent original having a line image, a halftone image or the like is applied to the photosensitive surface. Exposure is performed in close contact, and then the photosensitive layer is removed from the non-image area using a suitable developer to obtain a relief image. Light sources suitable for exposure include mercury lamps, metal halide lamps, xenon lamps,
Chemical lamps, carbon arc lamps and the like are used.

<Development> The exposed PS plate is developed with an alkaline developer to remove the photosensitive layer in the non-image area to obtain a printing plate.

The alkaline developer is an alkaline developer containing substantially no organic solvent, and may contain a small amount of an anionic surfactant if necessary. Further, the temperature of the developing treatment with the developer is preferably from 10 to 30C.

[0161] The phrase "contains substantially no organic solvent" means that
The organic solvent is not contained at all, or even if it is contained, it is 1% by weight or less in the developer.
-After propyl alcohol and benzyl alcohol, alcohols and glycol ethers such as phenylcellosolve.

PH of the above alkaline developer (25 ° C.)
Is preferably in the range of 8.0 to 15.0.

As the alkaline agent of the alkaline developer, for example, potassium hydroxide, sodium hydroxide or the like is used. The alkaline developer may optionally contain an anionic surfactant in the range of 0.1 to 1.0%. It is preferable to include them. As the anionic surfactant, for example,
Alkyl sulfate salts such as sodium lauryl sulfate,
For example, alkyl allyl sulfonates such as sodium dodecylbenzenesulfonate, and sulfonates of dibasic fatty acid esters such as sodium di (2-ethylhexyl) sulfosuccinate, and alkylnaphthalene sulfonic acids such as sodium n-butylnaphthalenesulfonate Salts and the like can be used, and among them, alkyl naphthalene sulfonates such as sodium n-butyl naphthalene sulfonate are preferably used.

[0164]

EXAMPLE <Preparation of Support 1> An aluminum plate (material: 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 10% aqueous sodium hydroxide solution kept at 85 ° C., and degreased for 1 minute. And then washed with water. The degreased aluminum plate was immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 1 minute, desmutted, and then washed with water. Next, this aluminum plate is placed in a 2.0% hydrochloric acid aqueous solution.
The surface was roughened at a temperature of 30 ° C. and a current density of 80 A / dm ² for 30 seconds. Then, it was immersed in a 1% aqueous solution of sodium hydroxide maintained at 70 ° C. for 10 seconds and washed with water. Next, it was immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 10 seconds and washed with water. Next, in a 30% aqueous sulfuric acid solution, anodizing treatment was performed for 2 minutes at a temperature of 45 ° C. and a current density of 3 A / dm ² , followed by washing with water. Then, it was immersed in a 3.0% aqueous ammonium acetate solution maintained at 80 ° C. for 1 minute to perform a pore-sealing treatment, and washed with water. Then, after immersing in a 1.0% aqueous solution of sodium silicate kept at 80 ° C. for 30 seconds,
For 5 minutes to obtain an aluminum support 1. The surface of the obtained aluminum support was measured at arbitrary 20 points and the average value was determined. The reflectance was 53% and the γ (H) value was 5%.
0.2 dyn / cm, γ (D) value is 27.4 dyn / c
m.

<Preparation of Support 2> An aluminum plate (material: 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 10% aqueous sodium hydroxide solution kept at 85 ° C.
After performing degreasing treatment for a minute, it was washed with water. The degreased aluminum plate was immersed in a 10% aqueous sulfuric acid solution kept at 25 ° C. for 1 minute, subjected to desmut treatment, and washed with water. Next, the aluminum plate was roughened in a 2.0% nitric acid aqueous solution at a temperature of 30 ° C. and a current density of 120 A / dm ² for 60 seconds. Then, it was immersed in a 1% aqueous solution of sodium hydroxide maintained at 70 ° C. for 10 seconds and washed with water. Then, 1% sulfuric acid aqueous solution maintained at 25 ° C.
After immersion for 0 second, it was washed with water. Next, in a 30% sulfuric acid aqueous solution, anodizing treatment was performed for 1 minute at a temperature of 35 ° C. and a current density of 3 A / dm ² , followed by washing with water. Then, after immersing in a 0.01% carboxymethylcellulose aqueous solution maintained at 80 ° C. for 30 seconds, it was dried at 80 ° C. for 5 minutes to obtain an aluminum support 2. When an average value was obtained by measuring the obtained aluminum support surface at arbitrary 20 points,
The reflectance is 45%, the γ (H) value is 38.5 dyn / cm,
The γ (D) value was 32.3 dyn / cm.

<Preparation of Support 3> An aluminum plate (material: 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 10% aqueous sodium hydroxide solution kept at 85 ° C.
After performing degreasing treatment for a minute, it was washed with water. The degreased aluminum plate is placed in a 10% sulfuric acid aqueous solution maintained at 25 ° C.
After immersion for a minute and desmutting treatment, it was washed with water. Next, this aluminum plate was placed in a 3.0% hydrochloric acid aqueous solution at a temperature of 30 ° C. and a current density of 100 A / dm ² for 4 hours.
The surface was roughened for 5 seconds. Then, it was immersed in a 1% aqueous solution of sodium hydroxide maintained at 70 ° C. for 10 seconds and washed with water.
Next, it was immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 10 seconds and washed with water. Next, in a 30% sulfuric acid aqueous solution, anodizing treatment was performed for 1 minute at a temperature of 35 ° C. and a current density of 3 A / dm ² , followed by washing with water. Thereafter, the film was immersed in a 0.01% carboxymethylcellulose aqueous solution maintained at 80 ° C. for 20 seconds, and dried at 80 ° C. for 5 minutes to obtain an aluminum support 3. The surface of the obtained aluminum support was measured at arbitrary 20 points and the average value was determined. The reflectance was 51%, the γ (H) value was 55.0 dyn / cm, and γ
(D) The value was 52.3 dyn / cm.

<Preparation of Support 4> An aluminum plate (material: 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 10% aqueous sodium hydroxide solution kept at 85 ° C.
After performing degreasing treatment for a minute, it was washed with water. The degreased aluminum plate is placed in a 10% sulfuric acid aqueous solution maintained at 25 ° C.
After immersion for a minute and desmutting treatment, it was washed with water. Next, the aluminum plate was placed in a 3.0% aqueous nitric acid solution at a temperature of 30 ° C. and a current density of 120 A / dm ² for 6 hours.
The surface was roughened for 0 seconds. Then, it was immersed in a 1% aqueous solution of sodium hydroxide maintained at 70 ° C. for 10 seconds and washed with water.
Next, it was immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 10 seconds and washed with water. Next, in a 30% sulfuric acid aqueous solution, anodizing treatment was performed for 1 minute at a temperature of 35 ° C. and a current density of 3 A / dm ² , followed by washing with water. Then, 30% in a 0.01% aqueous solution of polyvinyl phosphonic acid maintained at 80 ° C.
After immersion for 2 seconds, it was dried at 80 ° C. for 5 minutes to obtain an aluminum support 4. The surface of the obtained aluminum support was measured at arbitrary 20 points and the average value was determined. The reflectance was 43%, the γ (H) value was 59.1 dyn / cm, and γ (D)
The value was 55.2 dyn / cm.

<Preparation of Photosensitive Microgel (a)> An emulsion polymerization apparatus was equipped with a stirring stirrer, a 1-liter addition funnel,
It consists of a 5-liter four-necked flask equipped with a thermometer, a nitrogen gas inlet tube and a water-cooled condenser, and a heating mantle of the four-necked flask. 3360 g of deionized water and 20 g of a 30% aqueous solution of sodium lauryl sulfonate were added to the four-necked flask, and the activator system was heated to 80 ° C. under a nitrogen atmosphere. At this temperature, 420 g of methyl methacrylate and 240 g of ethyl acrylate
g, 165 g of styrene sulfonic acid, 16 g of allyl methacrylate and 16 g of 1,4-butanediol diacrylate, 25% of the monomer mixture were added at once.
To this was immediately added 10 ml of a 5% aqueous solution of potassium persulfate and 10 ml of a 7% aqueous solution of potassium phosphate. The reaction mixture became milky and exothermic to 85 ° C. The remainder of the monomer mixture was added over a period of 90 minutes while maintaining the temperature between 80-88 ° C. When the addition was completed, the reaction mixture was heated at 80-85 ° C for another 2 hours. The bluish emulsion was cooled to room temperature and coagulated by addition of methanol. The resulting slurry was filtered, washed twice with water, sucked dry and the resulting fine powder dried in a 100 ° C. oven for 4 hours. The spherical shape of the powder particles was confirmed by microscopy.

A precipitate obtained by mixing a solution in which 57 g of this microgel was dispersed in water and a solution in which 26.8 g of p-diazodiphenylamine sulfate was dissolved in water was collected by suction filtration, collected by washing with water, and then reduced in pressure. And dried to obtain a photosensitive microgel (a) having a photocrosslinking group.

<Preparation of Photosensitive Microgel (b)> A 1-liter flask equipped with a stirrer and a condenser was charged with 126 g (1 mol) of 2,3-dimethylmaleic anhydride, 131 g (1 mol) of 6-aminocaproic acid and 600 ml of toluene. While stirring at 100 ° C. for 1 hour. next,
A Dean-Stark water separator was attached, and the mixture was stirred for 3 hours while removing water under reflux of toluene. After the reaction was completed, the mixture was cooled and then crystallized in 1.5 l of hexane. The resulting solid was reslurried in 1.5 l of water by filtration and drying. By filtering and drying, 231 g of the following compound (i) as a white solid was obtained.

[0171]

Embedded image

Next, 300 ml equipped with a stirrer and a cooling pipe
57.4 g of compound (i) (0.24 mol
l) and 29.7 g (0.25 mol) of thionyl chloride were added, and the mixture was stirred at room temperature for 1 hour. Further, the mixture was stirred for 1 hour while heating to 80 ° C. After the completion of the reaction, the mixture was cooled and 150 ml of ether was added. Next, a dropping funnel was attached to the flask, and while the reaction mixture was cooled in an ice water bath, 26.0 g of 2-hydroxyethyl methacrylate (0.2 mol) was added.
A mixture of 1) and 31.6 g (0.4 mol) of pyridine was dropped by a dropping funnel over about 30 minutes. After completion of the dropwise addition, the mixture was stirred in an ice water bath for 1 hour, and further stirred for 2 hours while heating to 50 ° C. After completion of the reaction, the reaction mixture was cooled, and the reaction mixture was put into a separating funnel together with 400 ml of ethyl acetate.
Washed with water, 1N hydrochloric acid, water, a saturated aqueous solution of sodium hydrogen carbonate and water in that order. After drying this solution over sodium sulfate, the solvent is distilled off under reduced pressure to give the following compound (ii)
59 g of a liquid was obtained.

[0173]

Embedded image

Next, 68.52 g (0.195 mol) of the compound (ii) was placed in a 1 l flask equipped with a stirrer and a condenser.
l), ethylene glycol dimethacrylate, 2.97
g (0.015 mol), 20.72 g of hydrogen (2-methacryloyloxy) ethyl succinate (0.09 mol)
l), 9.22 g of sodium dodecyl sulfate and 800 of water
Then, the mixture was heated to 50 ° C. under a nitrogen stream. 0.58 g of potassium persulfate and 0.54 g of sodium thiosulfate pentahydrate were added to the mixed solution, and the mixture was stirred for 5 hours. After completion of the reaction, salting out and centrifugation were performed, followed by drying under reduced pressure to obtain 85 g of a white powder (the photosensitive microgel (b) of the present invention).
The spherical shape of the powder particles could be confirmed with a microscope.

<Preparation of Microgel (c)> In a 1-liter flask equipped with a stirrer and a condenser, 25.38 g (0.195 mol) of 2-hydroxyethyl methacrylate, 4.27 g (0.03 mol) of n-butyl methacrylate, ethylene 2.97 g of glycol dimethacrylate (0.0
15 mol), 13.81 g (0.06 mol) of ethyl (2-methacryloyloxy) ethyl hydrogen succinate, 4.63 g of sodium dodecyl sulfate and 750 ml of water were added and heated to 50 ° C. under a nitrogen stream. 0.58 g of potassium persulfate and 0.5% of sodium thiosulfate pentahydrate were added to this mixed solution.
4 g was added and the mixture was stirred for 5 hours. After completion of the reaction, salting out and centrifugation were performed, followed by drying under reduced pressure to obtain 43 g of a white powder.

The obtained white powder (10 g) and pyridine (10)
0 ml was placed in a 200 ml flask equipped with a stirrer and a condenser, and stirred in an ice water bath. 10 g of methacrylic acid chloride was slowly added to this mixture, and the mixture was allowed to stand in an ice water bath for 30 minutes.
Stirred for minutes. Furthermore, it heated at 50 degreeC and stirred for 2 hours.

After completion of the reaction, this mixture was poured into 1 liter of ice water with stirring, and acidified with hydrochloric acid. The precipitate was collected by filtration, washed well with an aqueous sodium chloride solution, and dried under reduced pressure to obtain 9 g of a white powder (microgel (c) of the present invention). The spherical shape of the powder particles could be confirmed with a microscope.

<Preparation of Microgel (d)> Allyl methacrylate was placed in a 1-liter flask equipped with a stirrer and a condenser.
38 g (0.225 mol), 2.97 g (0.015 mol) of ethylene glycol dimethacrylate, 12.85 g of 2-acetoacetoxyethyl methacrylate
(0.06 mol), sodium dodecyl sulfate 4.52
g and 750 ml of water were added and heated to 50 ° C. under a nitrogen stream. 0.58 g of potassium persulfate and 0.54 g of sodium thiosulfate pentahydrate were added to the mixed solution, and the mixture was stirred for 5 hours. After completion of the reaction, salting out and centrifugation were performed, followed by drying under reduced pressure to obtain 41 g of a white powder (microgel (d) of the present invention). The spherical shape of the powder particles could be confirmed with a microscope.

<Synthesis of diazo resin> Ice-cooled concentrated sulfuric acid 20
0 g of 12.7 g of p-hydroxybenzoic acid (0.092
mol) and 40.5 g of 4-diazophenylamine sulfate
(0.138 mol) was stirred and dissolved while taking care that the liquid temperature did not exceed 5 ° C. Next, 6.22 g (0.207 mol) of paraformaldehyde was slowly added over 1 hour with stirring to carry out a condensation reaction. At this time, care was taken that the reaction solution did not exceed 5 ° C. After the addition of paraformaldehyde, stirring was continued at 5 ° C. or lower for 30 minutes. After the completion of the reaction, the reaction solution was slowly poured into 1600 ml of ethanol cooled to 0 ° C., whereby a precipitate was formed. At this time, care was taken that the liquid temperature did not exceed 40 ° C.
The precipitate was collected by suction filtration and washed with 300 ml of ethanol to obtain a reaction intermediate a (diazosulfate).

The reaction intermediate a taken out was mixed with 240 m of water.
1) and then zinc chloride dissolved in 90 ml of water.
When 04 g (0.14 mol) was added, a precipitate was formed again. The precipitate was collected by suction filtration to obtain Reaction Intermediate b (diazo resin zinc chloride double salt). After dissolving the reaction intermediate b taken out in 1000 ml of water, 24.8 g of ammonium hexafluorophosphate dissolved in 180 ml of water.
(0.15 mol), a precipitate was formed.

The precipitate was collected by suction filtration, washed with 300 ml of ethanol, and dried at 30 ° C. for 3 days to obtain 32.4 g of a diazo resin.

<Preparation of photosensitive lithographic printing plate>
The photosensitive composition coating liquids (1 to 6) having different compositions are applied to each of the above four types of supports (1 to 4) using a wire bar, and dried at 85 ° C. for 2 minutes to form a photosensitive layer. Was. At this time, the photosensitive composition coating solution was 1.6 g as a dry weight.
/ M ² . Next, from the back surface of the support, the surface of the photosensitive layer was heated to 80 ° C., pulverized and classified, and the styrene-acrylic acid-butyl acrylate having a fixed direction diameter of 0.5 to 40 μm (ratio: 45:30:25) ) Printing plate surface 1 using a separator feeder that feeds a fixed amount of copolymer powder
uniformly sprayed adheres such that m ² per 0.05 g,
24 types of negative photosensitive lithographic printing plates shown in Table 1 (photosensitive lithographic printing plates 1 to 24) were obtained.

<Preparation of Photosensitive Composition Coating Solution 1> Photosensitive microgel (a) 2.05 g 2-hydroxyethyl methacrylate / acrylonitrile / methyl acrylate / methyl methacrylate (molar ratio: 25/30/25/20) Coalescing (Mw = 50,000) 2.50 g Tartaric acid 0.05 g Dye (Victoria Pure Blue BOH, manufactured by Hodogaya Chemical Co., Ltd.) 0.10 g Fluorosurfactant (Fluorard FC-430, manufactured by Sumitomo 3M Co., Ltd.) 0.025 g Methyl lactate / propylene glycol monomethyl ether (8/2) 100 ml <Preparation of photosensitive composition coating liquid 2> Photosensitive microgel (b) 2.05 g 2-hydroxyethyl methacrylate / acrylonitrile / methyl acrylate / methyl methacrylate (Mol ratio: 25/30/2 / 20) Copolymer (Mw = 50000) 2.50 g Tartaric acid 0.05 g Dye (Victoria Pure Blue BOH, manufactured by Hodogaya Chemical Co., Ltd.) 0.10 g Fluorinated surfactant (Fluorard FC-430, Sumitomo 3M) 0.025 g Methyl lactate / propylene glycol monomethyl ether (8/2) 100 ml <Photosensitive composition coating solution 3> Microgel (c) 2.05 g 2,4-bis (trichloromethyl) -6 (P-methoxystyryl) -s-triazine 0.25 g 2-hydroxyethyl methacrylate / acrylonitrile / methyl acrylate / methyl methacrylate (molar ratio: 25/30/25/20) copolymer (Mw = 50,000) 2.50 g tartaric acid 0.05g pigment (Victoria Pure Blue BOH, Hodogaya Chemical Co., Ltd.) 0.10 g Fluorosurfactant (Fluorade FC-430, manufactured by Sumitomo 3M Co., Ltd.) 0.025 g Methyl lactate / propylene glycol monomethyl ether (8/2) 100 ml <Photosensitive composition coating solution 4> Microgel ( d) 2.00 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.25 g 2-hydroxyethyl methacrylate / acrylonitrile / methyl acrylate / methyl methacrylate (molar ratio: 25) / 30/25/20) Copolymer (Mw = 50,000) 2.50 g Tartaric acid 0.05 g Dye (Victoria Pure Blue BOH, manufactured by Hodogaya Chemical Co., Ltd.) 0.10 g Fluorinated surfactant (Fluorard FC- 430, manufactured by Sumitomo 3M Co., Ltd.) 0.025 g methyl lactate / propylene glycol Lumonomethyl ether (8/2) 100 ml <Photosensitive composition coating solution 5> Diazo resin 2.05 g 2-hydroxyethyl methacrylate / acrylonitrile / methyl acrylate / methyl methacrylate (molar ratio: 25/30/25/20) Coalescing (Mw = 50,000) 2.50 g Tartaric acid 0.05 g Dye (Victoria Pure Blue BOH, manufactured by Hodogaya Chemical Co., Ltd.) 0.10 g Fluorosurfactant (Fluorard FC-430, manufactured by Sumitomo 3M Co., Ltd.) 0.025 g Methyl lactate / propylene glycol monomethyl ether (8/2) 100 ml <Photosensitive composition coating solution 6> Pentaerythritol triacrylate 2.05 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) ) -S-Triazine 0.25 g 2-hydroxy Siethyl methacrylate / acrylonitrile / methyl acrylate / methyl methacrylate (molar ratio: 25/30/25/20) copolymer (Mw = 50,000) 2.50 g tartaric acid 0.05 g Dye (Victoria Pure Blue BOH, Hodogaya Chemical Co., Ltd.) ) 0.10 g Fluorosurfactant (Fluorard FC-430, manufactured by Sumitomo 3M Co., Ltd.) 0.025 g Methyl lactate / propylene glycol monomethyl ether (8/2) 100 ml 24 types of negative photosensitive obtained Through a lithographic printing plate, pass an Eastman Kodak step tablet (one step transmission density difference 0.15) and a negative image film original,
Using a PS plate printer, exposure was performed for 30 seconds at 8 mW / m ² using a 2KW metal halide lamp as a light source, immersed for 30 seconds in a developing solution having the following composition adjusted to 25 ° C., and then gently rubbed the surface with a sponge. To obtain 24 types of planographic printing plates (Samples 1 to 12 and Comparative Samples 1 to 12).

(Developer) PH = 12.7 A potassium silicate A (manufactured by Nippon Chemical Co., Ltd.) 1160 g caustic potassium 133 g pure water 5133 g <Evaluation method> Sensitivity and image of the above samples 1 to 12 and comparative samples 1 to 12 The vignetting (image strength), printing durability, gradation, ink deposition and halftone dot reproducibility were evaluated by the following evaluation methods, and the results are shown in Table 1.

<< Sensitivity >> Sample 1 obtained by the above development processing
In each of the negative images of the step tablets obtained as inverted images of Sample Nos. To 12 and Comparative Samples 1 to 12, the maximum number of steps that did not cause film thinning was read, and the sensitivity was evaluated.

<< Image part vignetting >> The damage state of each step tablet negative image obtained as an inverted image of Samples 1 to 12 and Comparative Samples 1 to 12 obtained by the development processing was evaluated based on the following evaluation criteria. And evaluation of image portion vignetting.

：: No scratch on image portion Δ: Slight scratch on image surface ×: Damage on image portion to expose support.

<< Printing Durability >> Samples 1 to 12 and Comparative Samples 1 to 12 obtained by the above-mentioned development were subjected to a printing machine “DAIYA”.
1F-1 "(manufactured by Mitsubishi Heavy Industries, Ltd.), coated paper, dampening solution" etch solution SG-51, concentration 1.5% "(manufactured by Tokyo Ink Co., Ltd.), ink" Hi-Echo Beni "(manufactured by Toyo Ink Manufacturing Co., Ltd.) Printing), and printing is performed until ink deposition failure occurs in the image area of the printed matter or ink adheres to the non-image area. It was evaluated.

<< Gradation >> Samples 1 to 12 and Comparative Samples 1 to 12 obtained by the above-mentioned development processing were printed under the same conditions as in the above-mentioned printing durability section to obtain inverted images. In the negative image of the step tablet on the paper surface, the maximum number of steps until the ink was deposited was read, and the value obtained by subtracting the number of steps of sensitivity from the value was used as the evaluation of gradation.

<< Ink Adhesion Property >> Samples 1 to 12 and Comparative Samples 1 to 12 obtained by the above-mentioned development were printed under the same conditions as in the above-mentioned printing durability, and a normal printed matter was obtained. The number of printed sheets until it was obtained was evaluated as the ink deposition property.

<< Dot Reproducibility >> Samples 1 to 12 and Comparative Samples 1 to 12 obtained by the development processing were printed under the same conditions as those in the printing durability section, and a screen ruling of 15 was obtained.
The area of halftone dots of the printed matter of 50% halftone of 0 line / inch was measured to evaluate the halftone dot reproducibility. The area was measured with a Macbeth densitometer. Here, the dot reproducibility is better when the dot area ratio of the printed matter is closer to 50%.

[0192]

[Table 1]

From Table 1, it can be seen that the PS plate of the present invention and the developing method thereof all have sensitivity, gradation, image area vignetting (image intensity),
Excels in ink deposition, printing durability and dot reproducibility.
It can be seen that all of the comparative PS plates are insufficient in the above-mentioned various properties and are not practical.

[0194]

As demonstrated by the examples, the PS plate of the present invention and the method for developing the same have high sensitivity, high image strength,
It has excellent effects such as excellent developability, gradation, ink deposition, printing durability, dot gain and halftone dot reproducibility, and stably obtaining high quality printed images.

Claims (7)

[Claims] 1. A photosensitive lithographic printing plate comprising a layer of a photosensitive composition containing a microgel having a photocrosslinkable group on the surface thereof on an aluminum support having been subjected to surface roughening and anodic oxidation. A photosensitive lithographic printing plate wherein the reflectance of the surface of the aluminum support before the layer of the photosensitive composition is 50 to 70%. 2. A roughened and anodized aluminum alloy.
Micro-structure with photo-crosslinkable groups on the surface on a minium support
Photosensitive layer provided with a layer of a photosensitive composition containing a gel
In the printing plate, the step before providing the layer of the photosensitive composition is performed.
The surface of the luminium support is represented by the following relational expression (1).
A hydrogen bond component γ (H) value of 10 to 55 dyn / cm and
The variance component γ (D) value represented by the following relational expression (2) is 50:
a photosensitive lithographic printing plate characterized by being at most dyn / cm
Printing plate. Hydrogen bond component γ (H) = [｛1.159 + 1.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) 3. An aluminum alloy having been subjected to surface roughening and anodizing treatment.
Micro-structure with photo-crosslinkable groups on the surface on a minium support
Photosensitive layer provided with a layer of a photosensitive composition containing a gel
In the printing plate, the step before providing the layer of the photosensitive composition is performed.
The reflectance of the surface of the luminium support is 50 to 70%,
And a hydrogen bond component γ represented by the following relational expression (1):
(H) Value is 10 to 55 dyn / cm and the following relational expression
The variance component γ (D) value shown in (2) is 50 dyn / c
m or less. Hydrogen bond component γ (H) = [｛1.159 + 1.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) 4. A layer of a photosensitive composition containing a photopolymerization initiator and a microgel having an addition-polymerizable unsaturated bond on the surface is provided on a roughened and anodized aluminum support. Wherein the reflectance of the surface of the aluminum support before providing the layer of the photosensitive composition is 50 to 70%. 5. An aluminum alloy having been subjected to surface roughening and anodic oxidation treatment.
Photoinitiator on minium support and addition polymerization on surface
Compositions Containing Microgels with Hydrophilic Unsaturation
Photosensitive lithographic printing plate provided with a layer of
Below the surface of the aluminum support before providing the layer of the conductive composition
The hydrogen bond component γ (H) value represented by the above relational expression (1) is
10 to 55 dyn / cm and the following relational expression (2)
Dispersion component γ (D) value is 50 dyn / cm or less.
And a photosensitive lithographic printing plate. Hydrogen bond component γ (H) = [｛1.159 + 1.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) 6. An aluminum alloy having been subjected to surface roughening and anodizing treatment.
Photoinitiator on minium support and addition polymerization on surface
Compositions Containing Microgels with Hydrophilic Unsaturation
Photosensitive lithographic printing plate provided with a layer of
Of the surface of the aluminum support before providing the layer of the conductive composition
The emissivity is in the range of 50 to 70%, and the following relational expression
The hydrogen bond component γ (H) value shown in (1) is 10 to 55.
dyn / cm and a dispersion component represented by the following relational expression (2):
The γ (D) value is 50 dyn / cm or less.
Photosensitive lithographic printing plate. Hydrogen bond component γ (H) = [｛1.159 + 1.159 × cos (contact angle: H_TwoO) -cos (contact angle: CH_TwoI_Two)｝ / 0.379]^Two (1) Dispersion component γ (D) = [｛3.371 + 4.371 × cos (contact angle: CH _Two I_Two) -Cos (contact angle: H_TwoO)｝ / 1.082]^Two (2) 7. The development of a photosensitive lithographic printing plate according to claim 1, wherein the photosensitive lithographic printing plate is developed with an alkaline developer substantially free of an organic solvent. Method.