JPH10186639A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive resin composition for a lithographic printing plate free from any ball pen ink residue and any damage due to this ink and superior in resistances to printing and chemicals. SOLUTION: The >=2 photosensitive layers containing a compound to be allowed to release an acid by irradiation with light or activated radiation or electron beams are formed on this photosensitive resin composition and at least one of the photosensitive layers contains a filler having a Moh's hardness of 5-10 and this filler is surface treated with an inorganic or organic oxide or one of vinyl polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive lithographic printing plate, and more particularly to a photosensitive resin composition for a positive photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Lithographic printing is a printing method that skillfully utilizes the property that water and oil are not essentially mixed.

In a positive-working photosensitive lithographic printing plate, when the photosensitive layer is exposed to an image and then developed, the photosensitive layer, which is ink-receptive at the exposed portion, is removed to expose the surface of the hydrophilic support while the unexposed portion is exposed. In the above, a photosensitive layer having an ink receiving property is left on a support to form an ink receiving layer to form a positive printing plate.

In recent years, there has been a demand for a lithographic printing plate to be further improved in performance and to reduce processing waste liquid for rapid processing and environmental protection. Conventionally, as one technique for this purpose, for example, it is well known to reduce the thickness of a photosensitive layer of a printing plate.

However, when the photosensitive layer is made thinner, printing durability, chemical resistance, pressure resistance, and small dot reproducibility are hindered. In addition, during plate making operations, a mark is often made on the plate for registering or marking. The exposed portion of the inscribed portion must of course be developed and hydrophilic.

However, since the ballpoint pen ink remains on the surface of the support, there is a problem that the ink does not become hydrophilic, resulting in printing stains. In addition, the portion of the photosensitive layer drawn with the ballpoint pen ink is removed.

However, since the ballpoint pen ink remains on the surface of the support, there is a problem that the ink does not become hydrophilic, resulting in printing stains.

Conventionally, various proposals have been made as a countermeasure against the ink of the ballpoint pen, and for example, Japanese Patent Application Laid-Open No. 61-205933 using a specific novolak resin is disclosed.

As a means for solving this problem, a method of increasing the developability of the photosensitive layer is also known. For example, if the developability is increased by using a low molecular weight additive, the physical properties of the coating film deteriorate. Problems arise in printing durability. If the printing durability is to be increased, the opposite phenomenon occurs in that the developing property is deteriorated, which is not preferable.

On the other hand, in order to improve the mechanical strength and rebound resilience of a printing plate, Japanese Patent Application Laid-Open No.
JP-A-8-8648 and JP-A-2-175702 and JP-A-8-9-9 using fine particle resins such as a crosslinkable resin and a non-crosslinkable resin.
No. 5237 is disclosed.

However, these prior arts alone are not enough to achieve the object of the present invention, so that the ballpoint pen ink does not remain on the support, and has rapid processing, printing durability, chemical resistance, and pressure resistance. There has been a strong demand for the development of a new technique for improving the reproducibility of small dots.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to prevent the photosensitive layer from being left by the ball-point pen ink residue and the ball-point pen ink, and to be excellent in printing durability, chemical resistance, pressure resistance and small dot reproducibility. To provide a photosensitive resin composition for a lithographic printing plate.

[0013]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
Solved by: That is, (1) two or more layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support; A photosensitive resin composition comprising at least one layer containing a filler having a Mohs hardness of 5 to 10.

(2) At least one of the above photosensitive composition layers
The photosensitive resin composition according to (1), wherein the layer contains two or more fillers having different Mohs hardnesses.

(3) The filler according to item (1), wherein the Mohs hardness of the filler contained in the uppermost photosensitive composition layer is different from the Mohs hardness of the filler contained in at least one layer other than the uppermost layer. (2) The photosensitive resin composition according to the above (2).

(4) Two or more layers containing a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support, and the photosensitive composition layer Wherein at least one layer contains a needle filler having a needle ratio of 2 to 50.

(5) Two or more layers containing a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support, and the photosensitive composition layer Wherein at least one layer contains a plate-like filler having a plate-like ratio of 3 to 500.

(6) The photosensitive resin composition according to (4) or (5), wherein at least one of the photosensitive composition layers contains two or more fillers having different shapes.

(7) Two or more layers containing a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support. Characterized in that at least one layer contains a filler having an average particle diameter of 0.01 to 20 μm in the case of a spherical or plate-like shape, and an average long axis length of 0.03 to 20 μm in the case of a needle-like shape. A photosensitive resin composition.

(8) The photosensitive resin composition according to (7), wherein at least one of the photosensitive composition layers contains two or more kinds of fillers having different particle diameters.

(9) Two or more layers containing a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support, and the uppermost photosensitive layer The weight% of the filler contained in the binder resin contained in the uppermost layer is defined as (A)%, and at least one layer other than the uppermost layer does not contain the filler, or when contained, the binder contained in the filler in the layer (A) and (B) are different when the weight% with respect to the resin is (B)%, a photosensitive resin composition.

(10) Two or more layers containing a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support, and the photosensitive composition layer The photosensitive resin composition according to (1) or (7), wherein the filler contained in at least one layer contains a filler surface-treated with an inorganic or organic oxide.

(11) Two or more layers containing a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support, and the photosensitive composition layer The photosensitive resin composition according to (1) or (7), wherein the filler contained in at least one layer of (1) is surface-treated with a vinyl polymer compound.

(12) Two or more layers containing a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support, and the photosensitive composition layer Wherein at least one layer contains 0.1 to 5.0 parts by weight of a needle-like or plate-like filler based on 100 parts by weight of the solid content of the layer.

(13) In the case of a needle-like filler, the average major axis length is 0.03 to 20 μm, and in the case of a plate-like filler, the particle diameter is 0.01 to 20 μm.
2) The photosensitive resin composition according to the above.

(14) Two or more layers containing a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam are provided on a support, and the photosensitive composition layer Wherein at least one layer of the photosensitive resin composition contains uniaxially oriented tabular fine particles.

(15) The uniaxially oriented tabular fine particles are used in an amount of 0.1 to 5.0 based on 100 parts by weight of the solid content of the photosensitive composition layer.
(14) The photosensitive resin composition according to (14), which is contained by weight.

(16) The surface of the uniaxially oriented tabular fine particles is surface-treated with an inorganic oxide or an organic oxide having a Mohs hardness of 5 to 10 (14).
The photosensitive resin composition as described in the above.

(17) The photosensitive resin composition according to (14), wherein the average elastic modulus of the uniaxially oriented tabular fine particles is from 550 kg to 850 kg / mm ² .

(18) The photosensitive resin composition layer has a dry thickness of 1 to 18 mg / dm ^2.
(17) The photosensitive resin composition according to any one of the above (17).

(19) The uppermost photosensitive layer or at least one photosensitive layer other than the uppermost layer is coated by a wet-on-wet method (1) to (17).
The photosensitive resin composition according to any one of the above.

Hereinafter, the present invention will be described in detail.

The present invention is a photosensitive resin composition having a photosensitive layer containing a compound capable of generating an acid and / or a radical by light, actinic radiation or an electron beam, for example, o-quinonediazide, wherein the photosensitive layer comprises two or more layers. And preferably has 2 to 4 photosensitive layers. Further, in addition to the photosensitive layer, it may have a mat layer, an overcoat layer (protective layer), and a back coat layer.

The photosensitive layer in the present invention has a Mohs hardness of 5
Contains 10 to 10 fillers. More preferably, a filler having a Mohs hardness of 6 to 9 is contained.

The filler herein refers to an inorganic or organic filler. Examples of the inorganic filler include TiO.
₂ , talc, mica, glass flake, synthetic hydrotalcite, barium sulfate, ZnS, MgCO ₃ , CaC
O ₃ , ZnO, CaO, tungsten disulfide, molybdenum disulfide, boron nitride, MgO, SnO ₂ , SiO ₂ , C
There are r ₂ O ₃ , α-Al ₂ O ₃ , corundum and the like, and examples of the organic filler include Teflon powder, polyethylene, benzoguanamine, melamine, phthalocyanine and the like. Of these, preferred are TiO ₂ , SnO ₂ , Si
O ₂ , α-Al ₂ O ₃ and Cr ₂ O ₃ .

In the present invention, a plurality of fillers each having a different Mohs hardness may be used as these fillers, and it is preferable to use two kinds of fillers having a Mohs hardness different by one or more. Preferably, the Mohs hardness of the filler contained in the uppermost photosensitive layer is higher than the Mohs hardness of the filler contained in at least one photosensitive layer other than the uppermost layer. In order to improve the pressure resistance, the average major axis length is 0.03 to 20 μm, preferably 0.5 to 10 μm, and more preferably 1 to 5 μm in the case of a needle-like filler. In the case of a plate-like filler, in order to improve pressure resistance, the particle diameter is 0.01 to 20 μm, preferably 0.1 to 20 μm.
The thickness is preferably 20 μm, more preferably 0.5 to 10 μm.

In the layer according to the present invention, preferably the photosensitive layer,
Needle ratio of 2 to 50 (usually 2 to 20), preferably 5 to 5
15, more preferably containing a filler having an acicular ratio of 8 to 15.

The photosensitive layer according to the present invention has a tabular ratio of 3-5.
No. 00 plate-like filler. In order to improve small point reproducibility, usually, a plate-like filler having a plate-like ratio of 3 to 15 is used, preferably, a plate-like ratio of 4 to 12, more preferably 5 to 12.
10 to 10 plate-like fillers.

The acicular ratio here means (average major axis length) / (average minor axis length), and the plate ratio is (the length of the longest diagonal line on the plate-like surface of the plate-like powder). / (Thickness of plate-like powder)
And can be easily determined from an electron micrograph.

The photosensitive layer according to the present invention contains a plurality of fillers having different shapes. In the case of a sphere or plate, the average particle size is usually 0.03 to 20 μm, preferably 15 to 450 μm.
nm, more preferably 20 to 400 nm, for improving the reproducibility of small dots.

The composition layer of the present invention may contain two or more fillers having different average particle diameters. In this case, the difference in particle diameter may be 5 nm, more preferably 10 nm. In the case of an acicular filler, the average major axis length is preferably 40 to 30.
The thickness may be 00 nm, more preferably 50 to 2000 nm, for improving the reproducibility of small points.

It is preferable that at least one photosensitive layer according to the present invention contains two or more fillers having different average particle diameters. In the case of a sphere or a plate, the average particle size is preferably different by 10 nm or more, more preferably 20 nm or more. In the case of an acicular filler, the average major axis length may preferably differ by 10 nm or more, more preferably 20 nm or more.

In the photosensitive resin composition of the present invention, the photosensitive layer comprises two or more layers, and the ratio of the weight of the filler contained in the uppermost photosensitive layer to the weight of the binder resin contained in the uppermost layer is (A) (A) and (B) are different when the ratio of the weight of the filler contained in the photosensitive layer other than the uppermost layer to the weight of the binder resin contained in the photosensitive layer other than the uppermost layer is (B)%. It is characterized by.

In the above, (A) and (B) may differ by 5% by weight or more, more preferably by 10% by weight or more.

In the above, (A) and (B) are 2 to
50, more preferably 5 to 30, and (A) is preferably larger than (B).

The filler according to the present invention is surface-treated with an inorganic or organic oxide. The metal component is
Preferably 0.1-20% by weight, more preferably 1-1.
0% by weight. Oxides preferably used for the surface treatment of the filler include SiO ₂ , Al ₂ O ₃ , ZrO ₂ and Sr.
nO ₂ , Sb ₂ O _{5 and the} like.

The filler according to the present invention may be subjected to surface treatment using a compound containing Si or Al alone or in combination.
Here, specific compounds of Si or Al include SiO ₂ ,
α-Al ₂ O _{3 and the} like.

The filler according to the present invention may be surface-treated with a vinyl polymer compound such as an acrylic polymer compound. Preferred acrylic polymer compounds include acrylic polymer compounds containing a phenolic hydroxyl group.

As a surface treatment method for the filler, the filler is dispersed in a solution containing a vinyl polymer compound,
For example, there is a method such as attaching to the filler surface.

The filler used in the photosensitive layer is pH
It is preferably at most 6, but more preferably at most 5.5. The pH can be measured according to JIS-K5101 (room temperature method).

In the present invention, at least one of the plurality of layers is used.
Needle-like or plate-like fillers are contained in the layer to obtain a solid content of 10%.
0.1 to 5.0 parts by weight based on 0 parts by weight, preferably 0.2 to 3.0 parts by weight, more preferably 0.1 to 5.0 parts by weight.
5 to 2.0 parts by weight.

The tabular fine particles in the present invention are not particularly limited as long as they satisfy the following conditions (A), (A) and (C).

(A) Flat plate shape: The ratio of the major axis diameter passing through the center of gravity of the main plane to the thickness (long axis diameter /
Thickness) is 8 or more on average, and the ratio of the short axis diameter passing through the center of gravity of the main plane to the thickness (short axis diameter / thickness) is 3 or more.

(A) Fine particles: The average particle size is 20 μm or less.

(C) Being non-photosensitive.

The particle size and the volume fraction were measured by the following method using a laser microsizer LMS-24 manufactured by Seishin Enterprise. A sample is added to 300 to 400 ml of the dispersing medium in an amount within a concentration of 500 to 250 mV for measurement. The particle size at a cumulative volume of 50 vol% was defined as the average particle size.

Examples of such tabular fine particles include talc, mica, glass flake, and synthetic hydrotalcite.

Talc is called “hydrated magnesium silicate” and can be represented by 4SiO ₂ .3MgO.H ₂ O. The crystal structure is a three-layer structure in which silicic acid is present on the surface, magnesium oxide having a hydroxyl group is in the second layer, and silicic acid is in the third layer. In fact, dozens of these crystals overlap.

[0059] The mica, in one family of layered silicate minerals, the general formula of natural _{mica, A lx B 2 ~ 3 [} (OH, F) 2 X 4 O 10] (A = K, Na, Ca, Ba, NH ₄ , H ₃ O, B = A
1, FeIII, Mg, FeII, Mn, Li, Zn, VII
I, CrIII, T, X = Si, Al, Be, FeIII, x
= 0 to 0.5).

In the crystal structure, A is located between the octahedral and tetrahedral layers constituting the layered structure and is called an interlayer cation.

B is called an octahedral cation constituting a layer composed of an octahedron of BO ₆ .

X forms a so-called tetrahedral layer and is called a tetrahedral cation.

These form a unit having an octahedral layer on both sides of a tetrahedral layer, which are connected by interlayer ions.

As described above, there is synthetic mica in addition to natural mica. Synthetic mica generally has the same crystal structure as natural mica, and is generally the same as that of natural mica in which crystallization water is replaced by F.

[0065] As a general formula as synthetic hydrotalcite, in _{[Mg lx Al x (OH)} 2] x + [Y n- x / n · m H 2 O] x- ( this formula, 0 <x ≦ 0. 33, 0 <m <2, Y
^n- represents an n-valent anion. ).

The crystal structure has a layered structure in which a positively charged magnesium hydroxide type basic layer and a negatively charged intermediate layer comprising anions and interlayer water are alternately stacked.

The uniaxial orientation (flat fine particles) of the present invention means that the orientation ratio is 70% (number) or more, preferably 80%.
It is a tabular fine particle of (number) or more.

The orientation ratio mentioned here can be determined by the following method.

That is, a mixed aqueous solution (total binder concentration of 10 w / g) of 7 g of gelatin / 3 g of fine particles (for example, mica treated with SnO ₂ surface) / glyoxal (1 wt% based on gelatin)
t%) on a support provided with an undercoat layer at 10 ° C. and a relative humidity of 40% to a dry film thickness of 10 μm.
The cross section of the sample obtained by drying is scanned with a scanning electron microscope (SE
M), and refers to the ratio of tabular fine particles oriented in a direction of -10 ° to 10 ° with respect to a direction perpendicular to the film thickness direction as a center relative to all tabular fine particles.

The uniaxially oriented tabular fine particles are not particularly limited as long as they are formed under the above conditions.

The use of such uniaxially oriented tabular fine particles can particularly improve the pressure resistance. The above uniaxially oriented tabular fine particles may be used alone or in combination of two or more.

The average elastic modulus of the uniaxially oriented tabular fine particles of the present invention is from 550 kg / mm ^{2 to} 850 in view of improving pressure resistance.
It is preferably kg / mm ² .

The average elastic modulus of the tabular fine particles was measured by the following method. That is, a mixed aqueous solution (total binder concentration: 10 wt%) of 7 g of gelatin / 3 g of uniaxially oriented tabular fine particles (for example, mica treated with SnO ₂ ) / glyoxal (1 wt% with respect to gelatin) at 10 ° C. and 40% relative humidity. A sample obtained by coating and drying a support having no undercoat layer so as to have a dry film thickness of 10 μm was 9 cm × 1 cm.
The elastic modulus was determined from the slope of a stress-strain curve obtained by using a tensile tester at 23 ° C. and a relative humidity of 55% at a tensile speed of 40 mm / min.
The average value of the elastic modulus of the 20 samples measured by the above method was defined as the average elastic modulus.

The above uniaxially oriented tabular fine particles may be surface-treated with a surfactant, a silane coupling agent, or a metal oxide.

Examples of the metal oxide include the following.

Examples of preferred metal oxides are shown below.

SO-1 SiO ₂ SO-2 TiO ₂ SO-3 ZnO SO-4 SnO ₂ SO-5 MnO ₂ SO-6 Fe ₂ O ₃ SO-7 ZnSiO ₄ SO-8 Ai ₂ O ₃ SO-9 BeSiO _{4 SO-10 Al 2 SiO 5} SO-11 ZrSiO 4 SO-12 CaWO 4 SO-13 CaSiO 3 SO-14 InO 2 SO-15 SnSbO 2 SO-16 Sb 2 O 5 SO-17 Nb 2 O 5 SO-18 Y ₂ O ₃ SO-19 CeO ₂ SO-20 Sb ₂ O ₃ Of these, tin oxide is particularly preferred. Tin oxide may be a solid solution with, for example, antimony. A preferred surface treatment method is disclosed in
No. 50813, a method of treating a flat particle with antimony-doped tin oxide for surface treatment.

The flat fine particles of the present invention have a total projected area of 60
% Or more, preferably 80% or more, has a ratio of the major axis diameter to the thickness passing through the center of gravity of the main plane and the thickness (major axis diameter / thickness) of 8 or more, preferably 10 or more, more preferably 20 or more, and preferably The ratio between the minor axis diameter passing through the center of gravity of the main plane and the thickness (minor axis diameter / thickness) is 3 or more, preferably 5 or more, and more preferably 300 or less. The average particle size of the tabular fine particles is 20 μm or less, but preferably 1 μm.
0 to 15 μm.

The uniaxially oriented tabular fine particles are preferably contained in an amount of 0.1 to 5.0 parts by weight, more preferably 0.2 to 2.0 parts by weight, based on 100 parts by weight of the solid content of the photosensitive layer. is there.

The Mohs hardness of the inorganic oxide or organic oxide used for the surface treatment is preferably 5 or more, more preferably 6 to 10.

The thickness of the photosensitive resin composition layer according to the present invention is 1 to 18 mg / dm ² , more preferably 5 to 1 mg / dm ^2.
4 mg / dm ² .

As the photosensitive resin composition layer according to the present invention, any support can be used.
Supports comprising pure aluminum and aluminum alloys are included. Various aluminum alloys 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 prior to the surface roughening in order to remove grease, rust, dust and the like on the aluminum surface. As the degreasing treatment, solvent degreasing using a solvent such as trichlene or thinner, emulsion degreasing treatment using an emulsion of kerosene, triethanol or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used to remove stains and natural oxide films that cannot be removed only by the above degreasing treatment.

When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, a smut is formed on the surface of the support. In this case, an acid such as phosphoric acid, nitric acid, sulfuric acid or chromic acid is used.
Alternatively, it is preferable to perform a desmut treatment by immersing in a mixed acid thereof.

Prior to such a degreasing treatment, mechanical roughening may be performed. The mechanical surface roughening method is not particularly limited, but brush polishing and honing polishing are preferable. In brush polishing, for example, a cylindrical brush on which bristles having a bristle diameter of 0.2 to 1 mm are planted is rotated, and a slurry in which an abrasive is dispersed in water is supplied to a contact surface and pressed against the surface of a support to roughen the surface. I do. In the honing polishing, a slurry in which an abrasive is dispersed in water is ejected under pressure from a nozzle and collides obliquely with the surface of a support to roughen the surface.

Further, mechanical roughening can be carried out by bonding a previously roughened sheet to the surface of the support and transferring the rough surface pattern by applying pressure.

After performing the desmutting treatment, the surface of the aluminum support is electrolytically roughened in an acidic electrolytic solution by using an alternating current. Hydrochloric acid, nitric acid or the like is used as the electrolytic solution at this time, but hydrochloric acid is more preferable. The electrolyte may contain nitrates, chlorides, amines, aldehydes, phosphoric acid,
Chromic acid, boric acid, acetic acid, oxalic acid and the like can be added.

The electrolytic surface roughening treatment is described in, for example, Japanese Patent Publication No. 48-28123, British Patent No. 896563, Japanese Patent Application Laid-Open No. 53-67507, Japanese Patent Application No. 8-151036, and the like. Although these methods can be used, the method of Japanese Patent Application No. 8-151,036 is more preferable.

The voltage applied in the electrochemical graining is preferably 1 to 50 V, more preferably 5 to 30 V. The current density is preferably 10 to 200 A / dm ² ,
0 to 150 A / dm ² is more preferable. Electricity is 100
２０００2000 C / dm ² , preferably 200 to 1500 C
/ Dm ² , more preferably 200 to 1000 C /
dm ² . The temperature is preferably from 10 to 50 ° C, and from 15 to 50 ° C.
45 ° C is more preferred.

The current waveform used for the electrolysis is appropriately selected depending on the roughened shape to be obtained, such as a sine wave, a rectangular wave, a trapezoidal wave, and a sawtooth wave, but a sine wave is particularly preferable.

The support having been subjected to the electrolytic surface roughening treatment is immersed in an aqueous alkali solution to remove the surface smut and the like and control the pit shape of the rough surface, and the surface is etched. Examples of the alkaline agent include sodium hydroxide, potassium hydroxide and the like. As these alkaline aqueous solutions, 0.05 to 40% aqueous solutions are used.
The treatment is performed at a liquid temperature of 0 to 90 ° C for 5 seconds to 5 minutes.

After the surface is etched with an aqueous alkali solution, the surface is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof for neutralization. When anodizing treatment is performed after the neutralization treatment, it is particularly preferable to match the acid used for the neutralization with the acid used for the anodization treatment.

In the present invention, water washing is performed following the neutralization treatment, and then anodizing treatment is further performed. 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. The anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be specified unconditionally.
° C, current density 1-60A / dm ² , voltage 1-100V,
An electrolysis time of 10 seconds to 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.

The concentration of sulfuric acid is 10 to 50% by weight and the temperature is 20
The electrolytic treatment is preferably performed at 〜50 ° C. and a current density of 1-20 A / dm ² for 10 seconds to 5 minutes. Preferably, the electrolyte contains aluminum ions.

The anodized aluminum support may be subjected to a sealing treatment as required. The sealing treatment can be performed by a known method such as a hot water treatment, a boiling water treatment, a steam treatment, a sodium silicate treatment, a dichromate aqueous solution treatment, a nitrite treatment, and an ammonium acetate treatment. The aluminum support having been subjected to the sealing treatment may be provided with a hydrophilic layer. For the formation of the hydrophilic layer, US Pat.
81,461, the hydrophilic metal cellulose described in U.S. Pat. No. 1,860,426, the amino acids described in JP-B-6-94234, JP-A-6-2436, etc., or the salt thereof. Amines having a hydroxyl group and salts thereof described in JP-A-5-32238.
Phosphate described in 19494 and polymer compounds containing a monomer unit having a sulfo group described in 59-101651 can be used.

Further, the support of the present invention may be coated with a photosensitive lithographic printing plate in order to prevent abrasion of the photosensitive layer when the photosensitive lithographic printing plate is overlaid, or to prevent elution of the aluminum component into the developing solution during development. Showa 50-151136, 57-6
No. 3293, No. 60-73538, No. 61-6786
No. 3, JP-A-6-35174 and the like, a process of providing a protective layer on the back surface of the support can be performed.

In the present invention, other conditions of the photosensitive substance used in the photosensitive layer are not particularly limited, and various kinds of substances which are usually used for a positive photosensitive lithographic printing plate are used. be able to. Hereinafter, this point will be described.

(Photosensitive composition containing o-quinonediazide compound) The o-quinonediazide compound used in the present invention is a compound having an o-quinonediazide compound in a molecule. Examples of the o-quinonediazide compound include ester compounds of o-quinonediazidesulfonic acid with various aromatic polyhydroxy compounds or polycondensation resins of phenols and aldehydes or ketones.

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

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

The condensation rate of o-quinonediazide sulfonic acid to OH groups of phenols of the o-quinonediazide compound (reaction rate per OH group) is preferably 5 to 80%, more preferably 10 to 45%. is there.

As the o-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can be used.

For example, known 1,2-benzoquinonediazidosulfonic acid esters, 1,2-naphthoquinonediazidosulfonic acid esters, 1,2-benzoquinonediazidosulfonic acid amides, and 1,2-naphthoquinonediazidosulfonic acid amides. -Quinonediazide compounds, specifically "Light-Sensitive Systems" by J. Kosar (Light-Sens)
active Systems) pp. 339-352 (1
965), John Willie and Sons (Jo)
hn Willey & Sons, Inc. (New York) and W.S.D.Forest (WSD)
e Forest), "Photoresist" (Photo)
resist, vol. 50 (1975), 1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di-, described in McGraw Hill (New York).
(Benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2-benzoquinonediazide-4-
(N-ethyl-N-β-naphthyl) -sulfonamide,
1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1- (1,2-naphthoquinonediazide-5-sulfonyl) -3,5-dimethylpyrazole,
1,2-naphthoquinonediazide-5-sulfone-4'-
Hydroxydiphenyl-4'-azo-β-naphthol-
Ester, N, N-di- (1,2-naphthoquinonediazido-5-sulfonyl) -aniline, 2 '-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone, 1,2- Naphthoquinonediazide-5-sulfone-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride Condensate of 2 mol and 1 mol of 4,4'-diaminobenzophenone, 1,2-naphthoquinonediazide-
A condensate of 2 mol of 5-sulfonic acid chloride and 1 mol of 4,4'-dihydroxy-1,1'-diphenylsulfone,
Condensate of 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride with 1 mol of purprogalin, 1,2-
Examples thereof include 1,2-quinonediazide compounds such as naphthoquinonediazide-5- (N-dihydroabiethyl) -sulfonamide. In addition, Japanese Patent Publication No. 37-195
No. 3, No. 37-3627, No. 37-13109, No. 40-26126, No. 40-3801, No. 45-5
No. 604, No. 45-27345, No. 51-13013
JP-A-48-96575 and JP-A-48-63802.
And 1,2-quinonediazide compounds described in JP-A-48-63803 and the like.

Of the above o-quinonediazide compounds,
An o-quinonediazide ester compound obtained by reacting 1,2-benzoquinonediazidosulfonyl chloride or 1,2-naphthoquinonediazidosulfonylchloride with a pyrogallol-acetone condensed resin or 2,3,4-trihydroxybenzophenone is particularly preferred. As the o-quinonediazide compound used in the present invention, the above compounds may be used alone or in combination of two or more.

The ratio of the o-quinonediazide compound in the photosensitive composition is preferably from 6 to 60% by weight, particularly preferably from 10 to 50% by weight.

(Clathrate compound) The photosensitive composition of the present invention may contain a clathrate compound. The clathrate compound is not particularly limited as long as it is a compound that can take in (clathrate) a chemical species, but an organic compound soluble in a solvent used for preparing the composition is preferable. Examples of such organic compounds include, for example, “host guest chemistry”
(Michio Hiraoka et al., Kodansha, 1984, Tokyo) and other books and "Tetrahedron Report" (No. 226 (198
7) P5725A. Collet et al.), "Chemical Industry April Issue" ((1991) P278 Shinkai et al.), And "Chemical Industry April Issue ((1991) P288 Hiraoka et al.)".

Examples of the inclusion compounds which can be preferably used in the present invention include, for example, cyclic D-glucans, cyclophanes, neutral polyligands, cyclic polyanions, cyclic polycations, cyclic peptides, SPHERANDS, Cavitand (CAVITA
NDS) and their acyclic analogs. Among these, cyclic D-glucans and their non-cyclic analogs, cyclophanes, and neutral polyligands are more preferred.

The cyclic D-glucans and non-cyclic analogs thereof include, for example, compounds in which α-D-glucopyranose is linked by a glycooxide bond.

Examples of the compound include carbohydrates composed of D-glucopyranose groups such as starch, amylose and amylopecton, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and polymerization of D-glucopyranose groups. A cyclodextrin having a degree of 9 or more, such as cyclodextrin, and SO ₃ C ₆ H ₄ CH ₂ C ₆ H ₄ S
O ₃ group, NHCH ₂ CH ₂ NH group, NHCH ₂ CH ₂ NHC
H ₂ CH ₂ NH group, SC ₆ H ₅ group, N ₃ group, NH ₂ group, NEt
₂ groups, SC (NH ₂ ⁺ ) NH ₂ group, SH group, SCH ₂ CH ₂ N
Modified D-glucans into which substituents such as an H ₂ group, an imidazole group, and an ethylenediamine group have been introduced.
Further, a cyclodextrin derivative, a branched cyclodextrin, a cyclodextrin polymer, and the like are also included.

The branched cyclodextrin is a known cyclodextrin in which a water-soluble substance such as monosaccharide or disaccharide such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine is branched or added. Preferably, maltosyl cyclodextrin in which maltose is bonded to cyclodextrin (the number of bonded molecules of maltose may be one, two or three), or glucosylcyclodextrin (glucose in which glucose is bonded to cyclodextrin) May be any one molecule, two molecules, three molecules, etc.).

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

The neutral polyligand includes crown compounds, cryptands, cyclic polyamines and their non-cyclic analogs. The compound is known to effectively incorporate metal ions, but can also effectively incorporate cationic organic molecules.

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

These clathrates may be added as a simple substance, but they improve the solubility of the clathrate itself or the clathrate containing the molecules therein in a solvent and the compatibility with other additives. For this purpose, a polymer in which a substituent having an inclusion function is suspended as a pendant substituent on the polymer may be added together.

Among the above inclusion compounds, cyclic and acyclic D-
Glucans, cyclophanes, and acyclic cyclophane analogs are preferred. More specifically, cyclodextrin, calixarene, resorcinol-aldehyde cyclic oligomer, and para-substituted phenols acyclic oligomer are preferred. Most preferred are cyclodextrin and its derivatives, and among them, β-cyclodextrin and its derivatives are more preferred. The ratio of these clathrates to the photosensitive composition is 0.01%.
-10% by weight is preferred, and 0.1-5% by weight is more preferred.

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

The novolak resin used in the present invention includes, for example, phenol-formaldehyde resin, cresol-formaldehyde resin, and JP-A-55-5784.
No. 1 phenol-cresol-formaldehyde copolymer resin disclosed in JP-A-55-12
And a copolymer resin of p-substituted phenol and phenol or cresol and formaldehyde as described in No. 7553.

The molecular weight (polystyrene standard) of the novolak resin is preferably such that the number average molecular weight Mn is 3.00 ×.
10 ^{2 to} 7.50 × 10 ³ , weight average molecular weight Mw of 1.0
0 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn is 5.00 × 10 ^{2 to} 4.00 × 10 ³ and Mw is 3.00 ×
10 ^{3 to} 2.00 × 10 ⁴ .

The above novolak resins may be used alone or in combination of two or more. The proportion of the novolak resin in the photosensitive composition is preferably from 5 to 95% by weight (acrylic polymer).

The acrylic polymer that can be used in the present invention is a polymer obtained by polymerizing acrylic acid and its derivative, and a monomer other than acrylic acid and its derivative is copolymerized with the polymer. Also included.

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

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

The monomers other than acrylic acid and its derivatives used as acrylic acid and its derivatives and copolymerization components may be bonded to the above-mentioned polymer compound in either a block or random state.

The above polymers may be used alone or in combination of two or more. It can also be used in combination with other polymer compounds and the like.

Further, as the acrylic polymer, an acrylic polymer having a phenolic hydroxyl group is preferable.

(Vinyl copolymer having a phenolic hydroxyl group) In the acrylic polymer having a phenolic hydroxyl group, the phenolic hydroxyl group is represented by the following general formula (I):
It is preferably contained as a structural unit represented by [VI].

[0127]

Embedded image

In the general formulas [I] to [VI], R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an optionally substituted alkylene group connecting a nitrogen atom or an oxygen atom to an aromatic carbon atom, m represents an integer of 0 to 10, and B represents a substituent. Represents a phenylene group or a naphthylene group which may have a substituent.

In the present invention, among these, a copolymer containing at least one structural unit represented by the general formula [II] is preferable.

Examples of the copolymerizable component of the acrylic polymer having the structural units represented by the general formulas [I] to [VI] include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. Styrene, α-methylstyrene, p-methylstyrene, styrenes such as p-chlorostyrene, acrylic acids such as acrylic acid and methacrylsan, for example, itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride,
For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, Α such as ethyl ethacrylate
Esters of methylene aliphatic monocarboxylic acids, for example, nitriles such as acrylonitrile and methacrylonitrile, for example, amides such as acrylamide and methacrylamide, for example, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxy Anilides such as acrylic anilide, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl esters such as vinyl benzoate, for example, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, Vinylidene chloride, vinylidene cyanide such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-
Ethylene derivatives such as dimethoxycarbonyl ethylene and 1-methyl-1-nitroethylene, for example, N-vinyl based compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene, N-vinyl pyrrolidone Monomers.

Among the above-mentioned monomers, acrylic acid, methacrylic acid, aliphatic monocarboxylic acid and the like may be used as the copolymerization component of the acrylic polymer having the structural units represented by the general formulas [I] to [VI]. Acid esters and nitriles exhibit excellent overall performance and are preferred. More preferably, methacrylic acids, methyl methacrylate, acrylonitrile,
Ethyl acrylate and the like.

Formulas (I) to (A) in an acrylic resin
The content of the structural unit represented by each of (VI) is 5 to
70 mol% is preferable, and especially 10 to 40 mol% is preferable.

The proportion of the acrylic polymer in the photosensitive composition is preferably from 5 to 95% by weight.

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

Examples of such compounds include Diaresin Brilliant, Yellow 6G, Dialesin Yellow 3G, Dialesin Yellow F, Dialesin Red Z, Dialesin Yellow H2G, manufactured by Mitsubishi Kasei Corporation.
Dialegin Yellow HG, Dialegin Yellow HC, Dialegin Yellow HL, Dialegin Orange HS, Dialegin Orange G, Dialegin Red GG, Dialegin Yellow GR, Dialegin Red S, Dialegin Red HS, Dialegin Red A, Diaresin Red H, Diacid Ride Yellow 2G, Nippon Kayaku Kaya Set
Yellow K-RL, Kayaset Yellow K-CL, Kayaset Yellow EG, Kayaset Yellow E-
AR, Kayaset Yellow AG, Kayaset Yellow GN, Kayaset Yellow 2G, Kayaset Yellow SF-G, Kayaset Orange K-RL, Kayaset Orange G, Kayaset Orange A-N, Kayaset Orange SF- R, Kayaset Flavin F
N, Kayaset Flavin FG, Kayaset Red K
-BL, Kayacryl Golden Yellow
yellow or orange dyes such as wGL-ED.

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

(Organic acid / inorganic acid / acid anhydride) The photosensitive composition of the present invention may contain an organic acid / inorganic acid / acid anhydride. Examples of the acid used in the present invention include an organic acid described in JP-A-60-88942 and JP-A-2-137850, and a new edition of Chemical Handbook, edited by The Chemical Society of Japan (Maruzen Publishing), pp. 92-158. And the inorganic acids described in (1). Examples of organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzylsulfonic acid, m
Sulfonic acids such as benzenedisulfonic acid, sulfinic acids such as p-toluenesulfinic acid, benzylsulfinic acid and methanesulfinic acid, phosphonic acids such as phenylphosphonic acid, methylphosphonic acid and chloromethylphosphonic acid, formic acid, acetic acid, propionic acid and butyric acid , Isobutyric acid, pentanoic acid, hexanoic acid, aliphatic monocarboxylic acids such as heptanoic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, o-, m-, p-hydroxybenzoic acid,
o-, m-, p-methoxybenzoic acid, o-, m-, p-
Aromatic monocarboxylic acids such as methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysin carboxylic acid, gallic acid, and 3,5-dimethylbenzoic acid. Also,
Saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, itaconic acid, malic acid, and tetrahydro Phthalic 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 mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and m-benzenedisulfonic acid; cis-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, benzoic anhydride, etc., 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 of the present invention may contain a surfactant. As the surfactant, an amphoteric surfactant, an anionic surfactant, a cationic surfactant,
Nonionic surfactants, fluorinated surfactants and the like can be mentioned.

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

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

(Compound that Generates Acid or Free Radical by Exposure) As the compound that generates an acid or free radical upon exposure, for example, a halomethyloxadiazole compound, a halomethyl-s-triazine compound and the like are 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.
JP-B-1-28369, JP-A-60-13853
No. 9, No. 60-177340, No. 60-24
No. 1049, for example.

The halomethyl-s-triazine compound is a compound having one or more halomethyl groups, preferably a trichloromethyl group, in the s-triazine ring.

The amount of the compound capable of forming 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.

(Dye) 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,
Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based dyes represented by 4-p-diethylaminophenyliminaphthoquinone, cyano-p-diethylaminophenylacetanilide, etc. are colored to colorless Alternatively, it is mentioned as an example of a color changing agent that changes to a different color tone.

On the other hand, examples of the color changing agent that 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, 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 0.01 to 10% by weight, more preferably 0.02 to 5% by weight.

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

(Oil Sensitizing Agent) An oil sensitizing agent for improving the oil sensitivity of the image area (for example, a half-esterified product of a styrene-maleic anhydride copolymer with an alcohol described in JP-A-55-527). , Pt-butylphenol-
Novolak resins such as formaldehyde resins, or partially esterified products thereof with o-quinonediazide compounds, fluorine surfactants, p-hydroxystyrene
0% fatty acid ester) is preferably used. The amount of these additives varies depending on the object and purpose of use, but is generally 0.01 to 30% by weight based on the total solid content.

These components are dissolved in the following solvents,
The photosensitive lithographic printing plate of the present invention can be produced by providing a photosensitive layer by coating and drying the surface of the support. There is no particular limitation on the usage of the solvent.

(Solvent) Solvents usable for dissolving the photosensitive composition of the present invention include fatty acids such as methanol, ethanol, n-propanol, i-propanol, n-butanol, n-pentanol and hexanol. Aliphatic alcohols, 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, methylhexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone,
γ-butyrolactone, 3-hydroxy-2-butanone,
4-hydroxy-2-butanone, 4-hydroxy-2-
Pentanone, 5-hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol Propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, ethylene glycol alkyl ethers and their acetates (MC, EC, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether,
Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, MC acetate, EC acetate), diethylene glycol monoalkyl ethers and their acetates (diethylene glycol monomethyl ether, monoethyl ether, mono i-propyl ether, monobutyl ether, diethylene glycol monomethyl ether acetate, etc.), Diethylene glycol dialkyl ethers (DMDG, DEDG, DBD
G, MEDG), triethylene glycol alkyl ethers (monomethyl ether, monoethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, etc.), propylene glycol alkyl ethers and their acetates (monomethyl ether, monoethyl ether, n-propyl ether) , Monobutyl ether, dimethyl ether, diethyl ether, monomethyl ether acetate, monoethyl ether acetate, etc.), dipropylene glycol alkyl ethers (monomethyl ether, monoethyl ether, n-propyl ether, monobutyl ether, dimethyl ether, diethyl ether), ethyl formate , Propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, Methyl propionate, carboxylic acid esters such as ethyl propionate, methyl butyrate, ethyl butyrate, etc., dimethylformamide, dimethyl sulfoxide,
Dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, methyl benzoate, ethyl benzoate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more.

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

(Coating) As a method for coating the photosensitive substance according to the present invention, conventionally known methods, for example, die coater coating, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating And methods such as electrostatic air spray coating, roll coating, blade coating, and curtain coating.

[0165] While the photosensitive layer thickness is not particularly limited, is preferably in the range of 5 to 30 mg / dm ² in total thickness, more preferably 20 mg / dm ² or less in total thickness as shown in claim 5, It is more preferably in the range of 5 to ²⁰ mg / dm ² , and particularly preferably in the range of 8 to 16 mg / dm ² .

(Coating Layer) In the photosensitive lithographic printing plate according to the present invention, a coating layer composed of a water-insoluble organic solvent-soluble polymer compound having a film-forming ability can be formed on the photosensitive layer.

As a method for applying the coating layer, a conventionally known coating method is used in the same manner as the application of the photosensitive composition layer.

(Matting Agent) It is preferable to further provide a mat layer on the surface of the photosensitive layer provided as described above. The mat layer shortens the time of evacuation during contact exposure using a vacuum printing frame, and prevents crushing of fine halftone dots at the time of exposure due to poor adhesion and blurring. Specifically, JP-A-50-125805, JP-B-57-6582,
Examples thereof include a method of providing a mat layer as described in JP-A-61-28986 and a method of thermally fusing a solid powder as described in JP-B-62-62337.

The purpose of the mat layer is to improve the vacuum adhesion between the image film and the photosensitive lithographic printing plate in the contact exposure, thereby shortening the evacuation time and further reducing the collapse of minute dots during exposure due to poor adhesion. It is to prevent. As a method for applying the mat layer, a method of thermally fusing powdered solid powder described in JP-A-55-12974, and a method of spraying polymer-containing water described in JP-A-58-182636, are used. There is a method of drying the mat layer, and any method may be used. However, it is preferable that the mat layer itself is dissolved in the alkali developer or can be removed by this.

The method for applying the mat layer is the same as the method for applying the photosensitive composition layer by a conventionally known method.

(Exposure) When the photosensitive lithographic printing plate thus obtained is used, a conventionally used method can be applied. For example, a transparent original having a line image, a halftone dot 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. As a light source suitable for exposure, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp and the like are used.

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

Preferred developers and replenishers are [SiO
₂ ] / [M] (where [SiO ₂ ] represents the molar concentration of SiO ₂ and [M] represents the molar concentration of the alkali metal) is from 0.15 to 1.0, and the SiO ₂ concentration is It is an aqueous solution of an alkali metal silicate that is 0.5 to 5.0% by weight based on the total weight. Particularly preferably, [SiO 2
₂ ] / [M] is 0.25 to 0.75, the SiO ₂ concentration is 1.0 to 4.0% by weight, and [SiO ₂ ] /
[M] is 0.15 to 0.5, and the SiO ₂ concentration is 1.
0 to 3.0% by weight.

The above-mentioned developing solutions and developing replenishing solutions can contain water-soluble or alkali-soluble organic and inorganic reducing agents.

Examples of the organic reducing agent include phenol compounds such as hydroquinone, methol, and methoxyquinone, and amine compounds such as phenylenediamine and phenylhydrazine. Examples of the inorganic reducing agent include:
For example, sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, sulfites such as potassium bisulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite,
Examples thereof include phosphites such as sodium dihydrogen phosphite and potassium dihydrogen phosphite, hydrazine, sodium thiosulfate, and sodium dithionite.

These water-soluble or alkali-soluble reducing agents are preferably contained in the developing solution and the developing replenisher at 0.05 to 10% by weight. The developing solution and the developing replenisher may contain an organic acid carboxylic acid. These organic carboxylic acids include aliphatic carboxylic acids having 6 to 20 carbon atoms and aromatic carboxylic acids in which a benzene ring or a naphthalene ring is substituted with a carboxyl group.

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

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

The aromatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt. The content of the aliphatic carboxylic acid or aromatic carboxylic acid can be at least 0.1 to 30% by weight.

Further, the developer and the developing replenisher can contain various anionic, nonionic and cationic surfactants and organic solvents.

Further, known additives can be added to the developing solution and the developing replenisher.

[0182]

EXAMPLES The present invention will be described below with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Support> An aluminum plate (material: 1050, tempered H16) having a thickness of 0.3 mm was degreased in a 5% aqueous sodium hydroxide solution maintained at 65 ° C. for 1 minute. After
It was washed with water, immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 1 minute, neutralized, and further washed with water.

This aluminum plate was placed in a 1.0 wt% aqueous hydrochloric acid solution at a temperature of 25 ° C., a current density of 100 A / dm ² ,
Electrolytic surface roughening was performed with an alternating current under the conditions of a processing time of 60 seconds.

Next, a desmut treatment is performed in a 5% aqueous sodium hydroxide solution at 60 ° C. for 10 seconds.
0% sulfuric acid solution, temperature 20 ° C, current density 3A / d
Anodizing was performed under the conditions of m ² and a processing time of 1 minute.
Then, it was immersed in a 1% aqueous solution of sodium nitrite kept at 80 ° C. for 30 seconds, washed with water and dried at 80 ° C. for 3 minutes.
After immersion for 30 seconds in an aqueous solution of carboxymethyl cellulose (concentration: 0.1 wt%) kept at 85 ° C.,
For 5 minutes to produce a support.

<Preparation of Photosensitive Solution (A) for Upper Layer> (filler weight: 18.7%) Novolak resin a solution (molar ratio of phenol: m-cresol: p-cresol: 10:54:36, weight average molecular weight) 6.7 g Pyrogallol acetone resin (weight average molecular weight 3000) and o-naphthoquinone diazide-5-sulfonyl chloride condensate (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH ( Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g FC-430 (Sumitomo 3M) 0.03 g cis-1, 2-cyclohexanedicarboxylic acid 0.2 g cyclohexanone: methyl ethyl ketone = 70: 30 10 0 ml High molecular compound (Chemical formula 1) 0.2 g TiO ₂ dispersion (prepared using Dynomill with the following composition ratio) TiO ₂ (Surface treatment with AlO ₂ and SiO ₂ , 8% by weight of Al to TiO ₂ , to TiO ₂ 2 wt% content) average long axis length: 250 nm average minor axis length: 25n m acicular ratio: 10, Mohs hardness: 6 to 6.5 1.4 g novolak resin (same composition as the solution a) 0 6.6 g cyclohexanone / methyl ethyl ketone = 70: 30 20 ml <Preparation of photosensitive solution (B) for lower layer> (filler weight: 7.0%) Novolak resin (same composition as solution a) 6.7 g pyrogallol acetone resin (weight average molecular weight) 3000) and o-naphthoquinone di azido-5-sulfonyl chloride condensate (esterification ratio 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Ctoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g FC-430 (Sumitomo 3M Co., Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g cyclohexanone: methyl ethyl ketone = 70: 30 100 ml polymer compound 0.2 g TiO ₂ dispersion (prepared using Dynomill with the following composition ratio) TiO ₂ (AlO ₂ , surface treatment with SiO ₂ , containing 8% by weight of Al with respect to TiO ₂ and ₂ % by weight of Si with respect to TiO ₂ ) Average major axis length: 400 nm Average minor axis length: 40 nm Needle ratio: 10, Mohs hardness : 6 to 6.5 0.5 g Novolak resin (same composition as the above liquid a) 0.21 g cyclohexanone: methyl ethyl ketone = 70: 3 07ml polymer compound

[0187]

Embedded image

J: k: 1: m: n = 30: 20: 30:
15: 5 The polymer compound was prepared by converting benzyl methacrylate: 4-hydroxyphenyl methacrylamide: acrylonitrile: methyl methacrylate: methacrylic acid to 30: 2
It is a polymer compound polymerized at a molar ratio of 0: 30: 15: 5. The synthesis method can be obtained by a conventionally known synthesis method.

<Preparation of photosensitive lithographic printing plate sample> On the above-mentioned support, the above-mentioned photosensitive solution for lower layer (B) and photosensitive solution for upper layer (A)
Was coated with a wet-on-wet method while the lower layer was in a wet state using a two-slit die coater, and dried at 80 ° C. to prepare a photosensitive lithographic printing plate sample. The dry thickness of the photosensitive layer was 10 mg / dm ^{2 for the} lower layer,
The upper layer was 4 mg / dm ² .

Example 2 In the photosensitive solutions (A) and (B) of Example 1, TiO ₂
A lithographic printing plate was prepared in the same manner as in Example 1 except that the following titanium oxide dispersion was used instead of the dispersion.

<Photosensitive solution A for upper layer> (filler weight: 18.7%) Titanium oxide (TTO-55 spherical, average particle size 35 nm: manufactured by Ishihara Sangyo Co., Ltd.) Surface treatment with Al ₂ O ₃ and SiO ₂ ( Moisture hardness: 6 to 6.5 1.4 g Novolak resin (same composition as liquid a) 0.6 g Cyclohexanone: methyl ethyl ketone = 70:30 20 ml <Lower layer photosensitive liquid B> (filler weight: 7.0%) (lower layer photosensitive liquid B) Filler weight: 7.0% Titanium oxide (TTO-55 spherical, average particle diameter 35 nm: Ishihara Sangyo ( Co., Ltd.) Surface treatment with Al ₂ O ₃ and SiO ₂ (Al 8% by weight with respect to titanium oxide, Si 2% by weight with respect to titanium) Mohs hardness: 6 to 6.5 0.5 g Novolak resin (the above 0.21 g cyclohexanone: methyl ethyl ketone = 70: 30 7 ml Example 3 The same procedure as in Example 2 was performed except that the following filler dispersion was used in place of the TiO ₂ dispersion in the upper layer photosensitive solution A. A lithographic printing plate was prepared in the same manner as in Example 1.

(Filler weight: upper layer = filler 1, 8.1% + filler 2, 8.1% = 16.2% lower layer = 7.0%) (filler dispersion 1) α-alumina dispersion (the following composition) Α-alumina (spherical: average particle size 400 nm, specific surface area (BET) 3 m ² / g) Surface treatment with SiO ₂ (containing 8% by weight of Si based on alumina) Mohs hardness: 90 0.6 g novolak resin (same composition as liquid a) 0.26 g cyclohexanone: methyl ethyl ketone = 70:30 8.57 ml (filler dispersion liquid 2) titanium oxide dispersion liquid (prepared using Dynomill with the following composition) titanium oxide (TTO- 55, spherical, average particle size 35 nm: manufactured by Ishihara Sangyo Co., Ltd. (containing 8% by weight of Al based on titanium oxide and 2% by weight of Si based on titanium) Mohs hardness: 6-6.5 0.6 g Novolak resin (same composition as solution a) 0.26 g cyclohexanone: methyl ethyl ketone = 70: 30 8.57 ml Example 4 In Example 1, the TiO ₂ dispersion in the upper layer photosensitive solution (A) Example 1 was repeated except that the following barium ferrite dispersion A was used in place of TiO ₂ dispersion in the lower layer photosensitive solution (B).
A lithographic printing plate was prepared in the same manner as described above.

(Filler weight: upper layer = barium ferrite A, 17.9% + barium ferrite B, 9.0% = 26.9% lower layer = 7.0%) Barium ferrite dispersion A (Dynomill with the following composition ratio) Barium ferrite (average particle diameter 50 nm, plate ratio 6, specific surface area (BET) 60 m ² / g, Al 7% by weight with respect to barium ferrite, Si 2% by weight with respect to barium ferrite Mohs hardness: 5.5 1.4 g Novolak resin (same composition as liquid a) 0.6 g cyclohexanone: methyl ethyl ketone = 70: 30 20 ml barium ferrite dispersion B (prepared using a Dynomill with the following composition ratio) barium ferrite (average particle size 50 nm, plate ratio 6, the specific surface area ^{(BET) 60 m 2 / g} , barium Al ferrite Mois hardness: 5.5 0.7 g Novolak resin (same composition as liquid a) 0.3 g Cyclohexanone: methyl ethyl ketone = 70:30 10 ml Example 5 In Example 1, the following photosensitive solution (A) for the upper layer was replaced with the TiO ₂ dispersion solution and the following SnO ₂ dispersion solution A was used, and the photosensitive solution for the lower layer (B) was replaced with the TiO ₂ dispersion solution and the following SnO ₂ dispersion solution was used. _{2 A} lithographic printing plate was prepared in the same manner as in Example 1 except that Dispersion B was used.

(Filler weight: upper layer: 18.7% lower layer: 7.0%) SnO ₂ dispersion liquid A (prepared using a Dyno mill with the following composition ratio) SnO ₂ (surface treatment with AlO ₂ , SiO ₂ : Al) 8% by weight of the SnO _2, the Si to SnO ₂ 2 wt% content) 1.4 g average major axis length: 400 nm average minor axis length: 40 nm acicular ratio: 10 pH = 5. 5 Mohs hardness: 6.5 novolak resin (same composition as the solution a) 0.6 g Cyclohexanone: methyl ethyl ketone = 70: 30 20ml SnO ₂ dispersion B (prepared using a Dyno mill with the following composition ratio) SnO ₂ (AlO _2, SiO ₂ surface treatment: Al 8 wt% relative to SnO ₂ and the Si to SnO ₂ 2 wt% content) 0.5 g average major axis length: 600 nm average minor axis length: 50 nm acicular ratio: 12 pH = 5 . 5 Mohs hardness: 6.5 Novolak resin (same composition as liquid a) 0.21 g cyclohexanone: methyl ethyl ketone = 70: 30 7 ml Example 6 In Example 1, the photosensitive solution (A) for the upper layer was changed to a TiO ₂ dispersion liquid. , TiO ₂ dispersion a below, with B, lithographic printing performed in the same manner except for using the TiO ₂ dispersion C below in place of TiO ₂ dispersion from example 1 in the lower layer for photosensitive solution (B) A plate was prepared.

(Filler weight: Upper layer: 16.2% Lower layer: 7.0%) TiO ₂ dispersion liquid A (prepared using a Dyno mill with the following composition ratio) TiO ₂ (Surface treatment with AlO ₂ , SiO ₂ : Al) 8 wt% relative to TiO _2, the Si to TiO ₂ 2 wt% content) 0.7 g average major axis length: 250 nm average minor axis length: 25 nm acicular ratio: 10 novolak resin (same composition as the solution a) 0 0.3 g cyclohexanone: methyl ethyl ketone = 70: 30 10 ml TiO ₂ dispersion B (prepared using Dynomill with the following composition ratio) TiO ₂ (surface treatment with AlO ₂ and SiO ₂ : Al is 8% by weight with respect to TiO ₂ , Si is to TiO ₂ 2 wt% content) 0.5 g average major axis length: 150 nm average minor axis length: 12.5 nm acicular ratio: 12 pH = 5.5 Mohs hardness: 6-6.5 novolak resin (Same composition as liquid a above) 0.21 g Cyclohexanone: methyl ethyl ketone = 70: 30 7 ml TiO ₂ dispersion C (prepared using Dynomill with the following composition ratio) TiO ₂ (Surface treatment with AlO ₂ , SiO ₂ : Al to TiO ₂ to 8 wt%, the Si to TiO ₂ 2 wt% content) 0.5 g average major axis length: 400 nm average minor axis length: 40 nm acicular ratio: 10 pH = 5. 5 Mohs hardness: 6 to 6.5 Novolak resin (same composition as liquid a) 0.21 g cyclohexanone: methyl ethyl ketone = 70/30 7 ml Example 7 The upper photosensitive solution (A) of Example 1 was changed to a TiO ₂ dispersion liquid. A lithographic printing plate was prepared in the same manner as in Example 1 except that the following TiO2 dispersion A and barium ferrite dispersion B were used.

(Filler weight: upper layer = TiO ₂ , 9.3% + barium ferrite, 9.3% = 18.6% lower layer = 7.0%) TiO ₂ dispersion A (using a Dyno mill with the following composition ratio) _{Preparation) TiO 2 (AlO 2, SiO} 2 with a surface treatment: Al a relative TiO ₂ 8 wt%, the Si to TiO ₂ 2 wt% content) 0.7 g average major axis length: 250 nm average minor axis length: 25 nm Needle ratio: 10 pH = 5. 5 Mohs hardness: 6 to 6.5 Novolak resin (same composition as liquid a) 0.3 g cyclohexanone: methyl ethyl ketone = 70:30 10 ml barium ferrite dispersion B (prepared using a Dyno mill with the following composition ratio) Barium ferrite (average) Particle size 50 nm, plate ratio 6, specific surface area (BET) 60 m ² / g, Al 7% by weight based on barium ferrite, Si 2% by weight based on barium ferrite) Mohs hardness: 5.5 0.7 g novolak resin (same composition as solution a) 0.3 g cyclohexanone: methyl ethyl ketone = 70: 30 10 ml Example 8 In Example 1, the following TiO ₂ dispersion liquid is used in the upper photosensitive solution (A) and the lower photosensitive solution B. A lithographic printing plate was prepared in the same manner as in Example 1 except that A and B were used.

(Filler weight: Upper layer: 9.7% Lower layer: 5.0%) TiO ₂ dispersion A (prepared using a Dyno mill with the following composition ratio) TiO ₂ (Surface treatment with AlO ₂ , SiO ₂ : Al) 8 wt% relative to TiO _2, the Si to TiO ₂ 2 wt% content) 0.7 g average major axis length: 250 nm average minor axis length: 25 nm acicular ratio: 10 pH = 5. 5 Mohs hardness: 6-6.5 novolak resin (same composition as the solution a) 0.3 g Cyclohexanone: methyl ethyl ketone = 70: 30 10ml TiO ₂ dispersion B (prepared using a Dyno mill with the following composition ratio) TiO ₂ (AlO _2, SiO ₂ with a surface treatment: Al a relative TiO ₂ 8 wt%, the Si to TiO ₂ 2 wt% content) 0.35 g average major axis length: 400 nm average minor axis length: 40 nm acicular ratio: 10 pH = 5. 5 Mohs hardness: 6 to 6.5 Novolak resin (same composition as liquid a) 0.15 g cyclohexanone: methyl ethyl ketone = 70:30 5 ml Example 9 Photosensitive solution for upper layer (A) and photosensitive solution B for lower layer in Example 1 A lithographic printing plate was prepared in the same manner as in Example 1 except that the following TiO ₂ dispersions A and B were used.

(Filler weight: upper layer = TiO ₂ A, 18.3% + TiO ₂ B, 4.6% = 22.9%) TiO ₂ dispersion liquid A (prepared using a Dyno mill with the following composition ratio) TiO ₂ ( AlO _2, SiO ₂ with a surface treatment: Al a relative TiO ₂ 8 wt%, 2 wt% content relative to TiO ₂ and Si) 1.4 g subsequently, the surface treated with 0.14g acrylic resin (the polymer compound) Average major axis length: 250 nm Average minor axis length: 25 nm Needle ratio: 10 pH = 5. 5 Mohs hardness: 6 to 6.5 Novolak resin (same composition as liquid a) 0.46 g cyclohexanone: methyl ethyl ketone = 70:30 10 ml TiO ₂ dispersion B (prepared using Dyno mill with the following composition ratio) TiO ₂ (AlO _2, SiO ₂ with a surface treatment: Al a relative TiO ₂ 8 wt%, the Si to TiO ₂ 2 wt% content) 0.35 g average major axis length: 400 nm average minor axis length: 40 nm acicular ratio: 10 pH = 5. 5 Mohs hardness: 6 to 6.5 Novolak resin (same composition as solution a) 0.15 g cyclohexanone: methyl ethyl ketone = 70:30 5 ml Comparative Example 1 The photosensitive solution A for the upper layer in Example 1 was used with a one-slit die coater. To form a photosensitive lithographic printing plate. The dry thickness of the photosensitive layer is 14 m.
g / dm ² .

Comparative Example 2 The photosensitive solution A for the upper layer in Example 2 was applied in a single layer using a one-slit die coater and dried at 80 ° C. to prepare a photosensitive lithographic printing plate. The dry thickness of the photosensitive layer is 14 m.
g / dm ² .

Comparative Example 3 Barium Ferrite Dispersion A for the Upper Layer in Example 4
Is applied in a single layer using a one-slit die coater,
C. to dry a photosensitive lithographic printing plate. The dry thickness of the photosensitive layer was 14 mg / dm ² .

Comparative Example 4 The upper layer SnO ₂ dispersion A in Example 5 was applied in a single layer using a one-slit die coater and dried at 80 ° C. to prepare a photosensitive lithographic printing plate. The dry thickness of the photosensitive layer was 14 mg / dm ² .

Comparative Example 5 The TiO ₂ dispersion A and the barium ferrite dispersion B for the upper layer in Example 7 were mixed, coated in a single layer using a one-slit die coater, dried at 80 ° C., A lithographic printing plate was prepared. The dry thickness of the photosensitive layer was 14 mg.
/ Dm ² .

<Evaluation Method> (Sensitivity) A sensitivity measurement step tablet (No. 2 manufactured by Eastman Kodak Co., concentration difference 0.15) was applied to the obtained sample.
21 kW gray scale), 4 kW
Metal halide lamp (vi made by Dainippon Screen Co., Ltd.)
o Quick) as a light source from a distance of 90 cm. Next, this sample was subjected to SDR-1 (manufactured by Konica Corporation).
The developer was developed at 27 ° C. for 20 seconds with a developer diluted 6-fold with water.

The sensitivity was defined as the exposure time at which 3.0 steps of the step tablet were completely cleared.

(Printing durability) The obtained sample was developed in the same manner as in the sensitivity measurement described above, and the obtained lithographic printing plate was applied to a printing machine GTO manufactured by Heidelberg Co., Ltd. to obtain a coated paper, a printing ink (Toyo Ink) Printing was carried out using SEU-3, 2.5% (manufactured by Konica Corporation) and New Bright Red (manufactured by Co., Ltd.) and dampening failure appeared on the solid portion of the printed image. Printing was continued until the ink was deposited on the non-image area, and the number of prints at that time was counted.

(Remaining Ballpoint Pen) Drawing is performed using a pilot oil-made ballpoint pen while applying a load of 50 g to the sample. Thereafter, exposure was performed from a distance of 90 cm using a 4 kW metal halide lamp (bio Quick manufactured by Dainippon Screen Co., Ltd.) as a light source. Next, this sample was developed at 27 ° C. for 20 seconds with a developer obtained by diluting the SDR-1 developer 6 times with water. The remaining state of the ballpoint pen ink of the obtained sample was visually evaluated in the following three stages.

：: Ballpoint pen ink does not remain at all Δ: Ballpoint pen ink remains at some places ×: Ballpoint pen ink remains completely (ballpoint pen is damaged) Apply a load of 50 g to the sample and use a pilot oil-made ballpoint pen. draw. Next, this sample was washed with a developer obtained by diluting the SDR-1 developer 6 times with water.
Development was performed at 7 ° C. for 20 seconds. The damage of the photosensitive layer in the drawing area of the ballpoint pen ink was visually evaluated in the following three stages.

：: No damage to the photosensitive layer Δ: Part of the photosensitive layer disappeared and grain was exposed ×: The photosensitive layer was completely eliminated and grain was exposed (chemical resistance) The obtained photosensitive lithographic printing plate was used as a light source. As 4
Using a kW metal halide lamp, 50% flat-screen originals were brought into close contact with each other and exposed to light at 8 mW / cm ² for 60 seconds. This exposed lithographic printing plate
-1 Developer was diluted 6 times with water, and developed at a developing temperature of 27 ° C. for a developing time of 20 seconds. The obtained lithographic printing plate was immersed in an ultraplate cleaner (manufactured by ABC Chemical Co., Ltd.), and the chemical resistance was determined at the time when the image area began to be damaged. The results obtained are shown below.

(Pressure resistance) The surface of the photosensitive layer was rubbed with a felt bar, and the surface condition was observed.

5: Normal 4: Gloss on the surface has changed 3: Began to be whitened 2: Half or more whitened 1: Completely white (Evaluation of small spot reproducibility) Step tablet for sensitivity measurement (No. 2, manufactured by Eastman Kodak Co., Ltd.
15 steps each of 21 gray scales) and UGRA plate control wedge
8mW / cm ² using kW metal halide lamp
Exposure was performed by irradiating. The exposed photosensitive lithographic printing plate was developed with a developer obtained by diluting a commercially available developer (manufactured by SDR-1 Konica Co., Ltd.) 6-fold, and the developing time was 20 seconds.
Development was performed at a development temperature of 27 ° C. Also, the screen ruling 150
The area on the plate of 50% halftone dots per line / inch was measured and the dot reproducibility was evaluated. The area was measured with a Macbeth densitometer. The small dot reproducibility indicates that the closer the halftone dot area ratio on the plate is to 50%, the better.

[0211]

[Table 1]

As is clear from the table, the sample of the present invention was high in sensitivity and excellent in printing durability and chemical resistance. Furthermore, the sample of the present invention was superior to the comparative sample in that there was no remaining ballpoint pen ink, and there was no damage to the drawing area due to the ballpoint pen ink.

Example 10 Example 1 was repeated except that the TiO ₂ dispersion was used in the upper layer photosensitive solution (A) and the lower layer photosensitive solution (B).
A lithographic printing plate was prepared in the same manner as described above.

(Photosensitive solution A for upper layer) Filler weight: 1.1% TiO ₂ dispersion (prepared using a Dynomill with the following composition ratio) TiO ₂ (needle-shaped, average major axis length 3 μm, average minor axis length: 0) .3Myuemu, acicular _{ratio: 10 pH = 5.5 AlO 2,} SiO 2 with a surface treatment: 2% by weight of 8 wt% Si with respect to TiO ₂ to TiO ₂ to Al) 0.1 g Mohs hardness: 6 to 6 0.5 novolak resin (same composition as above) 0.04 g cyclohexanone: methyl ethyl ketone = 70: 30 1.4 ml (photosensitive solution B for lower layer) Filler weight: 0.5% TiO ₂ dispersion (prepared using a Dynomill with the following composition ratio) ) TiO ₂ (AlO _2, SiO ₂ with a surface treatment: Al of TiO ₂ to 8 wt%, 2 wt% with respect to TiO ₂ and Si) 0.05 g average long axis length: 4 [mu] m, an average minor axis length: 0. 4 μm, needle ratio: 1 , PH = 5.5 novolak resin (the same composition) 0.02 g cyclohexanone: methyl ethyl ketone = 70: 30 photosensitive solution of 0.7ml Example 11 Example 1 (A), in place of the TiO ₂ dispersion in (B) Except for using the following titanium oxide dispersion,
A lithographic printing plate was prepared in the same manner as in Example 1.

(Photosensitive solution A for upper layer) Filler weight: 1.1% TiO ₂ dispersion (prepared using Dynomill with the following composition ratio) Titanium oxide (FTL300: manufactured by Ishihara Sangyo Co., Ltd.) 0.1 g Novolak resin ( 0.04 g cyclohexanone: methyl ethyl ketone = 70: 30 1.4 ml (lower layer photosensitive solution B) Filler weight: 0.5% TiO ₂ dispersion B (prepared using a Dynomill with the following composition ratio) Titanium oxide ( FTL300: manufactured by Ishihara Sangyo Co., Ltd.) 0.05 g Novolak resin (same composition as above) 0.02 g Cyclohexanone: methyl ethyl ketone = 70: 30 0.7 ml Comparative Example 6 In the photosensitive solutions (A) and (B) of Example 1, TiO was used. _{2 A} lithographic printing plate was prepared in the same manner as in Example 10 except that no dispersion was added.

Example 12 A lithographic printing plate was prepared in the same manner as in Example 10, except that the following dispersion was added instead of the titanium oxide dispersion.

(Photosensitive solution A for upper layer) Filler weight: 1.1% Dispersion of fine particle A (prepared using Dynomill with the following composition ratio) Fine particle A: mica surface-treated with SnO ₂ and Sb ₂ O ₅ (Otsuka Chemical 0.1 g of novolak resin (same composition as above) 0.04 g Cyclohexanone: methyl ethyl ketone = 70: 30 1.4 ml (Photosensitive solution B for lower layer) Filler weight: 0.5% Dispersion of fine particle A Fine particles A: mica TiO ₂ dispersion B surface-treated with SnO ₂ and Sb ₂ O ₅ (prepared using a Dynomill with the following composition ratio) (WK941 manufactured by Otsuka Chemical Co., Ltd.) ) 0.05 g Novolak resin (same composition as above) 0.02 g Cyclohexanone: methyl ethyl ketone = 70: 30 0.7 ml Example 13 Except for adding a dispersion of the following in place of the titanium oxide dispersion liquid in 施例 10 was prepared lithographic printing plates were performed in the same manner as in Example 11.

(Photosensitive solution A for upper layer) Filler weight: 1.1% Fine particle C dispersion (prepared using Dynomill with the following composition ratio) Fine particle C: 0.1 g of mica surface-treated with a silane coupling agent (synthesis method) Is shown below.) Methyl methoxysilane is used as a coupling agent, dissolved in distilled water, and then sprayed onto mica powder that is stirred under high pressure in a mixing vessel. Thereafter, the mica fine powder surface-treated with silane is obtained by performing a drying treatment.

Novolak resin (same composition as above) 0.04 g cyclohexanone: methyl ethyl ketone = 70: 30 1.4 ml (lower layer photosensitive solution B) Filler weight: 0.5% Fine particle C dispersion (using a Dynomill with the following composition ratio) Preparation) Fine particles C: mica surface-treated with silane coupling agent 0.05 g novolak resin (same composition as above) 0.02 g cyclohexanone: methyl ethyl ketone = 70:30 0.7 ml Comparative Example 7 Replaced with titanium oxide dispersion in Example 10 A lithographic printing plate was prepared in the same manner as in Example 11 except that the following dispersion was added.

(Photosensitive solution A for upper layer) Filler weight: 7.7% Dispersion of fine particle A (prepared using Dynomill with the following composition ratio) Fine particle A: mica surface-treated with SnO ₂ , Sb ₂ O ₅ (Otsuka Chemical 0.7 g Novolak resin (same composition as above) 0.3 g Cyclohexanone: methyl ethyl ketone = 70: 30 10 ml (Lower layer photosensitive liquid B) Filler weight: 5.5% Fine particle A dispersion (described below) Fine particle A: Pulverized product of mica (WK941 manufactured by Otsuka Chemical Co., Ltd.) surface-treated with SnO ₂ and Sb ₂ O ₅ 0.5 g Novolak resin (same composition as above) 0.21 g Cyclohexanone : Methyl ethyl ketone = 70:30 7.1 ml Comparative Example 8 The following dispersion was added in place of the titanium oxide dispersion in Example 10. Outside was prepared lithographic printing plates were performed in the same manner as in Example 11.

(Photosensitive solution A for upper layer) Filler weight: 1.1% Dispersion of fine particle B (prepared using Dynomill with the following composition ratio) Fine particle B: pulverization of hydrophobic synthetic mica (MK100 manufactured by Corp Chemical Co., Ltd.) 0.1 g Novolak resin (same composition as above) 0.04 g cyclohexanone: methyl ethyl ketone = 70: 30 1.4 ml (lower layer photosensitive solution B) Filler weight: 0.5% Fine particle B dispersion (using a Dynomill with the following composition ratio) Fine particles B: pulverized product of hydrophobic synthetic mica (MK100 manufactured by Corp Chemical Co., Ltd.) 0.05 g novolak resin (same composition as above) 0.02 g cyclohexanone: methyl ethyl ketone = 70:30 0.7 ml The dispersions A, B, and C were particles having the shapes shown in Table 2 below.

[0222]

[Table 2]

<Evaluation method> In addition to the above, the following was also evaluated.

(Applicability) ：: Good applicability ：: Slight foam generation ×: Many foam generation (dispersion stability) ：: No precipitate generated △: Slight precipitate generated ×: Table 3 shows the results obtained.

[0225]

[Table 3]

As is clear from Table 3, the sample of the present invention is superior to the comparative sample in terms of printing durability and chemical resistance, has high sensitivity with no remaining ballpoint pen ink, and has small dot reproducibility and pressure resistance. Also, a printing plate excellent in dispersion stability can be obtained.

[0227]

As demonstrated in the examples, according to the present invention, high sensitivity, which is excellent in printing durability and chemical resistance, has no ballpoint pen ink residue, and is excellent in small dot reproducibility, pressure resistance and dispersion stability. A printing plate was obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09C 3/10 C09C 3/10 C09D 5/00 C09D 5/00 C 7/12 7/12 Z 201/00 201/00 G03F 7/00 503 G03F 7/00 503 7/039 7/039 7/095 7/095

Claims (19)

[Claims] 1. A support comprising at least two layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or electron beam. A photosensitive resin composition comprising at least one layer containing a filler having a Mohs hardness of 5 to 10. 2. The photosensitive resin composition according to claim 1, wherein at least one of the photosensitive composition layers contains two or more fillers having different Mohs hardnesses. 3. The Mohs hardness of the filler contained in the uppermost photosensitive composition layer is different from the Mohs hardness of the filler contained in at least one layer other than the uppermost layer. 3. The photosensitive resin composition according to 2. 4. A support comprising two or more layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam. A photosensitive resin composition comprising at least one layer containing a needle filler having a needle ratio of 2 to 50. 5. A support comprising two or more layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam. A photosensitive resin composition comprising at least one layer containing a plate-like filler having a plate-like ratio of 3 to 500. 6. The method according to claim 1, wherein at least one of the photosensitive composition layers comprises
The photosensitive resin composition according to claim 4, comprising two or more fillers having different shapes. 7. A support comprising two or more layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam. In at least one layer, a spherical or plate-like filler having an average particle diameter of 0.01 to 20 µm, and a needle-like having an average major axis length of 0.03 to 20 µm. Photosensitive resin composition. 8. The method according to claim 1, wherein at least one of the photosensitive composition layers comprises
The photosensitive resin composition according to claim 7, comprising two or more fillers having different particle diameters. 9. A support comprising at least two layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam. % Of the filler to be contained in the binder resin contained in the uppermost layer is defined as (A)%, and
The layer does not contain a filler or, if so, the weight% of the filler relative to the binder resin contained in the layer
(B)%, (A) and (B) are different from each other. 10. A support comprising two or more layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam. The photosensitive resin composition according to claim 1, wherein the filler contained in at least one layer contains a filler surface-treated with an inorganic or organic oxide. 11. A support comprising two or more layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam. The photosensitive resin composition according to claim 1, wherein the filler contained in at least one layer is surface-treated with a vinyl polymer compound. 12. A support comprising two or more layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam. A photosensitive resin composition characterized in that at least one layer contains 0.1 to 5.0 parts by weight of a needle-like or plate-like filler based on 100 parts by weight of the solid content of the layer. 13. An acicular filler having an average major axis length of 0.03 to 20 μm, and a plate-like filler having a particle diameter of 0.01 to 20 μm.
The photosensitive resin composition as described in the above. 14. A support comprising two or more layers including a photosensitive composition layer containing a compound capable of generating an acid by light, actinic radiation or an electron beam. A photosensitive resin composition comprising at least one layer containing uniaxially oriented tabular fine particles. 15. The photosensitive resin according to claim 14, wherein the uniaxially oriented tabular fine particles are contained in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the solid content of the photosensitive composition layer. Composition. 16. The photosensitive resin composition according to claim 14, wherein the surface of the uniaxially oriented tabular fine particles is surface-treated with an inorganic oxide or an organic oxide having a Mohs hardness of 5 to 10. . 17. The photosensitive resin composition according to claim 14, wherein the average elastic modulus of the uniaxially oriented tabular fine particles is from 550 kg to 850 kg / mm ² . 18. The photosensitive resin composition layer has a dry film thickness of 1 to 10.
The amount is 18 mg / dm ^2.
8. The photosensitive resin composition according to any one of items 7 to 7. 19. The method according to claim 1, wherein the uppermost photosensitive layer or at least one photosensitive layer other than the uppermost layer is applied by a wet-on-wet method. Photosensitive resin composition.