JP2775534B2 - Method for producing a lithographic printing plate support - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a support for aluminum or an alloy thereof for a lithographic printing plate, and more particularly to a anodic oxide film which is hardly stained, scratched, and consumed in a non-image area. The present invention relates to a lithographic printing plate support excellent in hardness and printing durability and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, there is a photosensitive lithographic printing plate (PS plate) in which a photosensitive composition is applied in a thin layer on an aluminum plate, and the above-mentioned aluminum plate is usually manufactured by a machine such as a brush grain method or a ball grain method. Is subjected to a roughening treatment such as a conventional method or an electrochemical method such as an electrolytic grain method or a method combining the two, and after the surface is made matte, is etched by an aqueous solution of an acid or an alkali, and further, After obtaining an anodizing treatment, if necessary, a hydrophilic treatment is performed, and a photosensitive layer is provided on the support to form a PS.
Edition. This PS plate usually has image exposure, development, correction,
A lithographic printing plate is formed by performing a gumming process, and the lithographic printing plate is attached to a printing machine for printing.

However, a positive-working PS in which a photosensitive layer having a positive effect is provided on a conventionally known lithographic printing plate support has been proposed.
The substances contained in the photosensitive layer are irreversibly adsorbed on the non-image areas of the lithographic printing plate obtained by imagewise exposing and developing the plate, and contaminate the non-image areas. There is a problem that it is difficult to identify the image portion, a correction mark is clearly left, and a non-uniform plate surface is formed.

Further, Japanese Patent Publication No. 46-35885 proposes treating an anodized aluminum plate with polyvinylphosphonic acid. It could not be sufficiently prevented. In addition, the conventional lithographic printing plate has a problem in that the ink attached to the non-image area is not quickly removed, thereby causing stains. And when the thickness of the anodic oxide film is increased to improve the scratch resistance of the non-image part of the conventional lithographic printing plate, the non-image part becomes more and more contaminated, and this contamination cannot be sufficiently prevented by the above method. There was also a disadvantage.

As a method of preventing non-image areas from being contaminated by an electrochemical treatment, a barrier type anodic oxidation treatment described in JP-A-53-2103 and formation of a porous anodic oxide film on the surface of an aluminum support, A method of performing anodizing treatment is known. In addition, after the porous anodic oxidation treatment, 100 V is applied in the presence of oxo acid ions such as boric acid.
The method of re-anodizing is described below in Japanese Patent Laid-Open No. 58-1536.
No. 99 is disclosed.

However, in these methods, the voltage of the barrier type anodic oxidation treatment or the re-anodization treatment is 100 V or less.
A sufficient voltage was not applied to seal the porous anodic oxide film, and thus the effect of preventing contamination of the non-image area was insufficient. When the porous anodic oxide film is relatively thin, the pores can be sealed by these methods. However, when the film is thin, the mechanical strength is weak and the non-image area is easily damaged. Further, when barrier type anodic oxidation treatment is performed on the grained surface, there is a disadvantage that the printing durability is reduced. In order to use a thick film (1 g / m ² or more) with sufficient sealing, a very high voltage is required. However, when the sealing treatment is performed at a high voltage, there is a disadvantage that the film causes dielectric breakdown, and a method of treating a thick film instead of this method has been desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a non-image part which is hardly contaminated, a non-image part is hardly damaged, hardly abraded and hardly stained, and water and ink are easily balanced. It is an object of the present invention to provide a lithographic printing plate support having high performance and high printing durability, and a method for producing the same.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, have accomplished the present invention. An aluminum support for a lithographic printing plate comprising inorganic particles having a hydroxyl group. Hereinafter, the present invention will be described step by step.

<Aluminum Plate> The aluminum plate used in the present invention is a plate-like body made of pure aluminum or an aluminum alloy containing aluminum as a main component and containing a trace amount of foreign atoms. Such heteroatoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of these foreign atoms is generally at most 10% by weight. Aluminum which is suitable for the support of the present invention is pure aluminum. However, since pure aluminum is difficult to produce due to the smelting technique, it is preferable that aluminum contains as little foreign atoms as possible. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly available materials can be appropriately used. The thickness of the aluminum plate used in the present invention is suitably about 0.1 to 0.5 mm.

<Roughening treatment> Prior to the method of anodizing an aluminum plate, a degreasing treatment with, for example, a surfactant or an alkaline aqueous solution and a graining treatment for removing rolling oil on the surface are performed as desired. . The graining method includes a method of mechanically roughening the surface and a method of electrochemically selectively dissolving the surface. As a method for mechanically roughening the surface, a known method called a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution. As disclosed in Japanese Patent Application Laid-Open (JP-A) No. 58-63902, a method in which both are combined can also be used.

<Porous anodic oxide film> As the electrolyte used for the porous anodic oxidation treatment of the aluminum plate, any electrolyte capable of forming a porous oxide film can be used. Generally, sulfuric acid and phosphoric acid Oxalic acid, chromic acid, or a mixed acid thereof, sodium hydroxide, potassium hydroxide, a mixed solution thereof, an ammonium fluoride addition bath, or the like is used, and the concentration is appropriately determined depending on the type of the electrolyte. Since the processing conditions for porous anodic oxidation vary depending on the electrolyte used, it cannot be specified unconditionally,
Generally, the concentration of the electrolyte is 1-80% by weight, and the liquid temperature is 5-
80 ° C., current density 1-80 A / dm ² , voltage 1-15
0V and the electrolysis time are suitably in the range of 5 seconds to 20 minutes. The amount of the porous anodized film is suitably 0.1-10 g / m ^2, but more preferably in the range of 1-6g / m ^2.

A particularly preferred anodic oxide film in the present invention is one formed by direct current using sulfuric acid as an electrolyte. The sulfuric acid electrolyte used for this anodic oxidation has a sulfuric acid concentration of 50 to 300.
g / liter and ^{3 to 1} as Al ³⁻ ions.
Preferably, it contains 5 g / l. In addition, 20-7
The anodic oxidation is preferably performed at a temperature of 0 ° C., the current density is preferably 3 to 20 A / dm ² , and the electrolysis time is preferably 5 to 300 seconds to obtain an oxide film having a desired thickness.

<Filling treatment> The pores of the anodic oxide film of the aluminum plate thus prepared are filled with inorganic particles having hydroxyl groups. The filling rate is suitably 10% or more,
25% or more is preferable. The inorganic particles having a hydroxyl group used in the present invention are preferably synthesized using a sol-gel method, and this method will be described in detail below.

In the sol-gel method, a metal raw material such as a metal alkoxide is dissolved in water and an organic solvent, and a catalyst such as an acid or an alkali or an additive (a polydentate ligand) is added thereto to carry out hydrolysis and polymerization. This is a reaction in which a sol of the metal compound is formed by causing a condensation reaction, and this is heat-treated to form a gel.The sol of the metal compound obtained in the middle of the sol-gel reaction is used in the present invention. It is preferable as an inorganic particle having a hydroxyl group. The particle diameter of the metal compound sol may be smaller than the pore diameter of the anodic oxide film. It is generally less than 1000 angstroms, preferably 10-500 angstroms, particularly preferably 20-200 angstroms.

The simplest method for adjusting the particle size is to control the reaction temperature and reaction time during the hydrolysis and polycondensation reactions. Generally, the reaction temperature is selected from the range of 10 ° C. to 80 ° C., and the time is selected from the range of 10 minutes to 5 hours. The lower the reaction temperature and the shorter the reaction time, the smaller the particle size. As the metal raw material used here, for example, metal alkoxide, metal acetylacetonate, metal acetate, metal oxalate, metal nitrate, metal sulfate, metal carbonate, oxychloride, chloride can be used.

Examples of metal alkoxides include LiOCH ₃ ,
NaOCH ₃ , B (OCH ₃ ) ₃ , Al (OC ₃ H ₇ ⁱ ) ₃ , Al (OCH ₃ ) ₃ , Al (OC ₂ H ₅ )
₃ , Al (OC ₄ H ₉ ) ₃ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ⁱ ) ₄ , S
i (OC ₄ H ₉ ^t ) ₄ , Ca (OCH ₃ ) ₂ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC _{3
^{H 7 i) 4, Ti (}} OC 4 H 9) 4, V (OC 2 H 5) 3, Cu (OCH 3) 2, Sr (OC
_{2 H 5) 2, Ba (} OC 2 H 5) 2, Zn (OC 2 H 5) 2, Ga (OC 2 H 5) 3, Y (OC
₄ H ₉ ) ₃ , Ge (OC ₂ H ₅ ) ₄ , Pb (OC ₄ H ₉ ) ₄ , Sb (OC ₂ H ₅ ) ₅ , Ta (OC ₃ H
_{7) 5, W (OC 2} H 5) 6, La (OC 3 H 7) 3, Nd (OC 2 H 5) 3, P (OCH 3) 3,
Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ , La [A
l (OC ₃ H ₇ ⁱ ) ₄ ] ₃ , Mg [Al (OC ₃ H ₇ ) ₄ ] ₂ , Mg [Al (OC
₄ H ₉ ^sec ) ₄ ] ₂ , Ni [Al (OC ₃ H ₇ ) ₄ ] ₂ , (C ₃ H ₇ O) ₂ Zr [Al (OC ₃ H ₇ ) ₄ ]
₂ , Ba [Zr ₂ (OC ₂ H ₅ ) ₉ ] _{2 and the} like.

Examples of metal acetylacetonates include:
Ir (CH ₃ COCH (OCH ₃ ), Mn (CH ₃ COCHCH ₃ ) ₂ Zn (CH ₃ COCHCOCH ₃ ) ₂ ,
Al (CH ₃ COCHCOCH ₃ ) ₃ , Cu (CH ₃ COCHCOCH ₃ ) ₂ , Cr (CH ₃ COCHCOCH
₃ ) ₃ , Ce (CH ₃ COCHCOCH ₃ ) ₃ and the like. Examples of metal acetate _{salt, Zn (CH 3 COO) 2} · 2H 2 O, Cd (CH 3 COO) 2 · 2H 2 O, CH 3 COO
K, Ca (CH ₃ COO) ₂・ H ₂ O, CH ₃ COOAg, Cr (CH ₃ COO) ₃ , Co (CH
₃ COO) _{2 ・} 4H ₂ O, Sr (CH ₃ COO) ₂ , Y ₂ H ₂ O ・, CH ₃ COOCs, Ce (CH
₃ COO) _{3 ・} H ₂ O, Cu (CH ₃ COO) ₂ , Cu (CH ₃ COO) ₂・ H ₂ O, CH ₃ COON
a, CH ₃ COONa ・ 3H ₂ O, Mg (CH ₃ COO) ₂・ 4H ₂ O, Mn (CH ₃ COO) ₂・ 4
H ₂ O, Mn (CH ₃ COO) ₃・ 2H ₂ O, CH ₃ COOLi, CH ₃ COOLi ・ 2H ₂ O
and so on.

Examples of metal oxalates include KOCOCOOK
H ₂ O, SnC ₂ O ₄ , K ₂ TiO (C ₂ O ₄ ) ₂・ 2H ₂ O, FeC ₂ O ₄・ 2H ₂ O, BaC ₂ O
Such as ₄ · H ₂ O. Examples of the metal _{nitrate, Zn (NO 3) 2 ·} 6H 2
_{O, Al (NO 3) 3} · 9H 2 O, Y (NO 3) 3 · 6H 2 O, Ca (NO 3) 2 · 4H 2 O, Cr
_{(NO 3) 3 · 9H 2} O, Co (NO 3) 2 · 6H 2 O, ZrO (NO 3) 2 · 2H 2 O, Fe (NO
_{3) 3 · 9H 2 O,} Ni (NO 3) 2 · 6H 2 O, Nd (NO 3) 3 · 6H 2 O, Ba (NO 3)
_{2, Mg (NO 3) 2} · 6H 2 O, Mn (NO 3) 2 · 6H 2 O, La (NO 3) 3 · 6H 2 O, Li
NO ₃ and others.

Al ₂ (SO ₄ ) ₃ , (NH ₄ ) Al
(SO ₄ ) ₂ , KAl (SO ₄ ) ₂ , CsAl (SO ₄ ) ₂ , TlAl (SO ₄ ) ₂ , NaAl (S
O ₄ ) ₂ , Sb ₂ (SO ₄ ) ₃ , Y ₂ (SO ₄ ) ₃ , K ₃ Y (SO ₄ ) ₃ , In ₂ (SO ₄ )
_{3, CaSO 4, Na 2 Ca} (SO 4) 2, CrSO 4, CoSO 4, KHSO 4, NaHSO
₄ , Ba (HSO ₄ ) ₂ , Mg (HSO ₄ ) ₂ , LiHSO ₄ , FeSO ₄ , (NH ₄ ) ₂ Fe (S
O ₄ ) ₂ , Cu ₂ SO ₄ , CuSO ₄ , NiSO ₄ , VSO ₄ , BaSO ₄ , MgS
O ₄ , MnSO ₄ , La ₂ (SO ₄ ) ₃ , Li ₂ SO ₄ and the like.

Examples of metal carbonates include ZnCO ₃ , Y ₂ (CO ₃ ) ₃ ,
In ₂ (CO ₃ ) ₃ , CaCO ₃ , CrCO ₃ , CoCO ₃ , Co ₂ (CO ₃ ) ₃ , Ca (HC
O ₃ ) ₂ , KCoH (CO ₃ ) ₂ , Ni (HCO ₃ ) ₂ , Mg (HCO ₃ ) ₂ , LiHCO ₃ , Sr
CO ₃ , FeCO ₃ , Cu ₂ CO ₃ , NiCO ₃ , BaCO ₃ , BaCO ₃ , MgCO ₃ ,
_{(NH 4) 2 CO 3 ·} MgCO 3, CaCO 3 · MgCO 3, MnCO 3, La 2 (C
O ₃ ) ₃ and Li ₂ CO ₃ . Sb as an example of an oxychloride
OCl, CrO ₂ Cl ₂ , Si ₂ OCl ₆ , ZrOCl ₂ , WOCl ₄ , FeOCl, CuCl _{2 ・}
2CuO ・ 4H ₂ O, CuCl _{2 ・} Cu (OH) ₂ NbOCl ₃ , VOCl, BiOCl, M
oCl, POCl ₃ and the like.

Examples of chlorides include ZnCl ₂ , AlCl ₃ , SbCl
₃ , CaCl ₂ , CrCl ₂ , SiCl ₄ , CoCl ₂ , ZrCl ₂ , SrCl ₂ , WC
l ₄ , TaCl ₅ , TiCl ₄ , FeCl ₂ , Cu ₂ Cl ₂ , CuCl ₂ , NbCl
_{5, BaCl, BiCl, MgCl 2} , MnCl 2, MoCl 2, LaCl 3, Li
Cl and others. On the other hand, any general acid or alkali can be used as the catalyst. Preferred are sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, potassium hydroxide and the like.

The additives include ethylene glycol, propylene glycol, butanediol, hexylene glycol, acetylacetone / ethanolamine, diethanolamine / triethanolamine, oxalic acid, tartaric acid, citric acid, tripolyphosphoric acid, pyrophosphoric acid, tetrametaphosphoric acid, and phosphorous acid. Any substance having a polydentate ligand such as acid, hypophosphoric acid, and metaphosphorous acid may be used, and has an action of preventing precipitation of a metal hydroxide formed during hydrolysis and polycondensation reaction. Have.

The solvent is used for dissolving the metal raw material and is not particularly limited as long as it functions as a solvent, and any solvent may be used. Specific examples include lower alcohols such as methanol and ethanol, and ketones such as acetone, methyl ethyl ketone and diethyl ketone. The method for filling the inorganic particles having a hydroxyl group obtained as described above into the pores of the anodic oxide film is as follows.
There is something .

(1) By immersing an anodized aluminum plate in a solution containing inorganic particles having hydroxyl groups whose particle size is sufficiently controlled, inorganic particles having hydroxyl groups in the pores of the anodic oxide film are obtained. To fill. As immersion conditions, immersion time was 10 seconds-2 hours, immersion temperature was 10 ° C.-90.
° C. Preferably, the immersion time is 30 seconds to 30 minutes, and the immersion temperature is 20.
-60 ° C.

Alternatively, inorganic particles having a hydroxyl group on the anodic oxide film are applied on the anodic oxide film to fill the pores of the anodic oxide film. As a coating method, a method such as bar coating, wheeler coating, and curtain coating can be used. When the organometallic compound is used, the unhydrolyzed alkyl group in the organometallic compound, the acid used as the catalyst, the alkali, the solvent, and the like remain in the formed inorganic particles having a hydroxyl group. It exists in a state where it has been done. If this residue is present in a large amount, it is not preferable because it leads to staining during printing. 10 remaining alkyl groups
% Is important. In addition, immersion treatment of an anodized aluminum plate in a solution containing inorganic particles having hydroxyl groups, or application treatment only on an aluminum plate anodized with a solution containing inorganic particles having hydroxyl groups, requires only an anodized film. Cannot be firmly filled in the holes. Therefore, after the filling treatment of the pores of the anodized film, the residue in the inorganic particles containing a hydroxyl group (alkyl group, catalyst, solvent) to improve the stain during printing.
Heat treatment is performed to remove the impurities and to firmly fill the pores of the anodic oxide film. The heat treatment is performed at a temperature of 10 ° C. to 500 ° C. for 10 seconds in the air or under a reduced pressure atmosphere.
2 hours, desirably at a temperature of 10 ° C.-300 ° C. for 10 seconds-3
0 minutes is appropriate.

Thereafter, after the immersion treatment or the coating treatment, the film formed from the inorganic particles having a hydroxyl group adheres not only in the pores of the anodic oxide film but also outside the pores (surface) of the anodic oxide film. This film has insufficient hardness and WBL (Weak Baundary Layer) between the photosensitive layer and the anodic oxide film
If necessary, the film formed from inorganic particles having hydroxyl groups outside the pores (surface) of the anodized film is subjected to chemical treatment by immersion in acid, alkali, etc.
After the removal, a water washing process is performed. Acid used for dissolution / removal
Any alkali can be used as long as it can dissolve a film formed from inorganic particles having a hydroxyl group. For example, sulfuric acid,
Nitric acid, potassium hydroxide, sodium hydroxide, potassium carbonate, potassium bicarbonate and the like are used. The concentration is 1-80
% By weight, the liquid temperature is preferably 1-80 ° C., and the immersion time is preferably 10 seconds-1 hour. Under these conditions, the inorganic particles having hydroxyl groups filled in the pores of the anodic oxide film are hardly removed.
Further, the formation of the inorganic particles having a hydroxyl group can be carried out in the pores of the anodic oxide film.

(2) An aluminum plate anodically oxidized in a solution containing inorganic particles having a hydroxyl group is used as one electrode to perform filling by electrolysis. In this case, an inorganic salt such as chromic acid, phosphoric acid, sulfuric acid or nitric acid, an organic acid such as acetic acid or maleic acid, or a surfactant is added to the treatment liquid to improve the stability of the inorganic particles in the solution. Can be.
Electrolysis conditions vary depending on the type of inorganic particles used,
The current density is 0.5-100 A / dm ² , and the processing temperature is 5-
90 ° C., treatment time is 1 second-1 hour. After filling by electrolysis, if necessary, heat treatment may be performed in the same manner as in (1) to perform immersion treatment in acid or alkali. <Hydrophilic layer> The surface of aluminum filled with such a hydrophilic compound in the pores of the anodic oxide film is described in JP-A-60-149949, JP-A-60-232998, and JP-A-62-1.
A hydrophilic layer as described in JP-A-9494 can be provided.

Before or after providing the hydrophilic layer,
As described in U.S. Pat. No. 3,181,461
To alkali metal silicates (sodium silicate, potassium silicate
)).Also polyvinyl
It can also be treated with phosphonic acid.  <Photosensitive layer> On the lithographic printing plate support thus obtained,
By providing a more known photosensitive layer, a photosensitive lithographic printing plate
Obtainable. A lithographic printing plate obtained by making a plate
Has excellent performance. Hereinafter, representative of the photosensitive composition
What is typical?

(1) A photosensitive composition comprising an o-quinonediazide compound. Examples of the positive-acting photosensitive diazo compound include JP-B-43-2
No. 8403, benzoquinone-1,2
- ester or naphthoquinone-1,2-diazide sulfonic acid chloride with diazide sulfonic acid chloride with a polyhydroxy phenyl and Pirigaroru - esters of acetone resin is most preferable. Other suitable o-quinonediazide compounds include U.S. Pat. No. 3,046,120.
Benzoquinone-1,2-diazidesulfonic acid chloride or naphthoquinone-1,2-diazidesulfonic acid chloride and an ester of a phenol formaldehyde resin described in the specifications of US Pat. is there.

Although the o-quinonediazide compound alone forms the photosensitive layer, a resin soluble in alkaline water may be used in combination as a binder. Novolak resins are examples of resins soluble in alkaline water, such as phenol formaldehyde resin, cresol formaldehyde resin, pt-butyl formaldehyde resin, phenol-modified xylene resin, and phenol-modified mesitylene resin. Other useful alkali water-soluble resins include polyhydroxystyrene, copolymers of polyhalogenated acrylic acid and other vinyl compounds. Further details of the photosensitive layer comprising an o-quinonediazide compound and its developer are described in U.S. Pat. No. 4,259,434.

(2) Photosensitive Composition Containing Diazo Resin and Binder A negative working photosensitive diazo compound is disclosed in US Pat. No. 2,062.
Diphenylamine-p which is a reaction product of a diazonium salt disclosed in the specifications of U.S. Pat. Nos. 3,631 and 2,667,415 with an organic condensing agent having a reactive carbonyl group such as aldol or acetal; -Condensation product of diazonium salt and formaldehyde (photosensitive diazo resin)
Is preferably used. Other useful condensed diazo compounds are described in U.S. Pat. No. 3,679,419, JP-A-60-8091.
JP-A-59-78340, JP-A-56-1210
No. 31, JP-A-61-91654, JP-A-59-78
No. 340, JP-A-62-59948, British Patent No. 1,3.
No. 12,925 and No. 1,312,926. These types of photosensitive diazo compounds are usually obtained in the form of water-soluble inorganic salts and can therefore be applied from aqueous solutions. Further, these water-soluble diazo compounds can be combined with an aromatic or aliphatic compound having one or more phenolic hydroxyl groups, sulfonic acid groups or both by a method disclosed in British Patent No. 1,280,885. It is also possible to use a substantially water-insoluble photosensitive diazo resin which is a reaction product of the reaction.

Further, as described in JP-A-56-121031, it can be used as a reaction product with hexafluoroborate. In addition, diazo resins described in British Patent No. 1,312,925 are also preferable. Such a diazo resin is used together with a binder. Preferred binders have an acid value of 10-20.
0 is an organic high molecular polymer, and as a specific example,
It contains acrylic acid, methacrylic acid, crotonic acid or maleic acid as an essential polymerization component.
2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate as described in US Pat. No. 23,276, or ternary with methacrylonitrile, acrylic acid or methacrylic acid and optionally further copolymerizable monomers Or a quaternary copolymer, JP-A-53-1
No. 20903, acrylic acid or methacrylic acid having a hydroxy group at the end and esterified with a group containing a dicarboxylic acid ester residue, and optionally other copolymerizable monomers A monomer having an aromatic hydroxyl group at the end thereof (for example, N- (4-hydroxyphenyl) methacrylamide, etc.) as described in JP-A-54-98614, acrylic acid or Copolymers of methacrylic acid and, if necessary, at least one other copolymerizable monomer, alkyl acrylate or methacrylate, acrylonitrile or methacryloyl as described in JP-A-56-4144. Copolymers of nitriles and unsaturated carboxylic acids are included. Further, acidic polymer vinyl alcohol derivatives and acidic cellulose derivatives are also useful. Furthermore, Japanese Patent Application Laid-Open No. Sho 60-18243
Nos. 7 and 61-281236, and a polyvinyl butyral resin having a carboxyl group and a polyurethane having a carboxyl group as described in British Patent No. 2,185,120. Resin is also a preferred example.

(3) -CH = C is added to the main chain or side chain of the polymer.
Composition comprising polymer compound containing HC = O group -CH = CH as photosensitive group on main chain or side chain of polymer
Those mainly containing a photosensitive polymer such as polyesters, polyamides and polycarbonates containing -C = O group (for example, U.S. Pat. Nos. 3,030,208 and 3,707,
Nos. 373 and 3,453,237), 2-propenylidenemalonic acid compounds such as cinnamylidenemalonic acid, and photosensitive polyesters. (Eg, US Pat. No. 2,952)
No. 6,878 and No. 3,173,787), a hydroxy group-containing polymer such as polyvinyl alcohol, starch, cellulose and the like. Acid esters (eg, US Pat.
No. 690,966, No. 2,752,372, No. 2,732,
No. 301 etc.) and the like. These compositions may further contain sensitizers, stabilizers, plasticizers, pigments, dyes, and the like.

(4) Copolymer composition which causes a polymerization reaction upon irradiation with actinic rays, for example, US Pat. Nos. 2,760,863 and 3,060,0
No. 23 describes a composition comprising an addition polymerizable unsaturated compound having two or more terminal ethylene groups and a photopolymerization initiator. The compound capable of being dimerized by irradiation with actinic rays and the compound capable of undergoing a polymerization reaction may further contain a resin, a sensitizer, a thermal polymerization inhibitor, a dye, a plasticizer, and the like as a binder.

(5) Electrophotographic photosensitive layer The electrophotographic photosensitive layer is mainly composed of a photoconductive compound and a binder. However, for the purpose of improving sensitivity, obtaining a desired photosensitive wavelength range, etc., a known electrophotographic photosensitive layer may be used. The pigment, dye, chemical sensitizer, and other additives can be used. The photosensitive layer can be composed of a single layer or a plurality of layers having separate functions of charge generation and charge transport. A lithographic printing plate can be obtained by forming a toner image on the photosensitive layer by a known electrophotographic process, using this as a resist layer, and decoating the non-image portion. For example, Shoko 3
Nos. 7-17162 and 38-6961, JP-A-56-196.
No. 107246, No. 60-254142, Japanese Patent Publication No. 59
Nos. 36259 and 59-25217, and JP-A-56-
No. 146145, No. 62-194257, No. 57-1
No. 47656, No. 58-100862, No. 57-16
It has been described in numerous publications, including 1863, any of which can be used.

The above photosensitive composition is usually composed of water, an organic solvent,
Alternatively, a solution of these mixtures is applied to the support according to the present invention and dried to prepare a photosensitive lithographic printing plate. The coating amount of the photosensitive composition is generally about 0.1 to about 5.0.
g / m ² is suitable, and about 0.5 to about 3.0 g / m ² is more preferred. The photosensitive lithographic printing plate thus obtained is subjected to image exposure with a light source containing an active ray such as a carbon arc lamp, a xenon lamp, a mercury lamp, a tungsten lamp, a metal halide lamp and the like, and then developed to obtain a lithographic printing plate.

[0037]

The lithographic printing plate obtained by exposing and developing the photosensitive lithographic printing plate using the support of the present invention has no contamination of the non-image area in both the negative type and the positive type, and the correction step Thus, the image portion can be easily identified. In addition, no correction marks are generated, so that the printed marks are not stained by the correction marks, and the non-image portion is excellent in scratch resistance, abrasion resistance and stain resistance. Moreover, the printing durability is high. Further, since the photosensitive layer does not remain after the development, it has a feature that the balance between water and ink can be easily obtained.

[0038]

The present invention will be specifically described below with reference to examples. In the examples, (%) indicates (% by weight) unless otherwise specified. Example 1 The surface of a JIS1050 aluminum sheet was grained with a rotary nylon brush using a Pumice-water suspension as an abrasive. At this time, the surface roughness (center line average roughness) was 0.5 μm. After washing with water, the substrate was immersed in a 10% aqueous solution of sodium hydroxide at 70 ° C. to perform etching so that the amount of aluminum dissolved was 6 g / m ² . After washing with water, it was immersed in a 30% nitric acid aqueous solution for 1 minute to neutralize, and sufficiently washed with water. After that, 0.
Electrolytic surface roughening was performed for 20 seconds in a 7% nitric acid aqueous solution using a rectangular alternating waveform having a voltage of 6 volts at the time of anode (power supply waveform described in Example of Japanese Patent Publication No. 58-5795).
After immersing in a 50% solution of 0% sulfuric acid to wash the surface,
Washed with water.

Further, a porous anodic oxidation treatment was performed in a 5% phosphoric acid aqueous solution using a direct current to prepare a substrate 1. At this time, the weight of the anodic oxide film was 4 g / m ² . Next, the following inorganic particles A having a hydroxyl group were synthesized. In A, aluminum triisopropoxide: toluene: acetylacetone was adjusted to a weight ratio of 2: 39: 1, and reacted by stirring with a stirrer at room temperature for 1 hour to control the particle diameter of the inorganic particles having a hydroxyl group to about 50 angstroms or less. did. This solution was applied to the surface of the anodic oxide film on the substrate 1 by a spin coating method, and the pores were filled with inorganic particles. After that, the temperature is 100 ° C
For 10 minutes to fix the inorganic particles in the pores.
Then, it is immersed in a 1 mol% aqueous solution of potassium hydrogencarbonate at 40 ° C. for 3 minutes to remove extra inorganic particles on the anodic oxide film.
The substrate 2 was prepared by removing the film formed from and washing with water.
A photosensitive solution having the following composition was applied to the substrates 1 and 2 so that the coating weight after drying was 2.0 g / m ² to form a photosensitive layer.

Composition Ester compound of naphthoquinone-1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) 0.75 g Cresol novolak resin 2.00 g Oil Blue # 603 0.04 g Ethylene dichloride 16 g 2-Methoxyethyl acetate 12 g The photosensitive lithographic printing plate thus prepared was placed in a vacuum printing frame at a distance of 1 m from a distance of 1 m through a transparent positive film to a 3 kW metal halide. After exposure with a lamp for 50 seconds, the molar ratio of SiO ₂ / Na ₂ O was 1.74.
5.26% aqueous solution of sodium silicate (pH = 12.
Developed in 7). After development, Heidelberg printing machine S
When printing at 0R-KZ, both printing plates gave 100,000 good prints. However, a plate containing no inorganic particles in the pores of the anodic oxide film is highly contaminated in the non-image area and has an absorbance at 600 nm of 0.08,
It was difficult to maintain the balance between water and ink, and poor printability. On the other hand, no contamination of non-image areas occurred on the plate containing the inorganic particles having hydroxyl groups in the pores of the anodic oxide film. Example 2 The surface of a JIS1050 aluminum sheet was grained with a rotating nylon brush using a Pumice-water suspension as an abrasive. The surface roughness (center line average roughness) at this time was 0.5 μm.
Met. After washing with water, the substrate was immersed in a 10% aqueous solution of sodium hydroxide at 70 ° C. to perform etching so that the amount of aluminum dissolved was 6 g / m ² . After washing with water, it was immersed in a 30% nitric acid aqueous solution for 1 minute to neutralize, and sufficiently washed with water. Then,
Electrolytic surface roughening was performed for 20 seconds in a 0.7% nitric acid aqueous solution using a rectangular wave alternating waveform with a voltage of 6 volts at the time of anode (power supply waveform described in Example of JP-A-58-5795). The surface was washed by immersing it in a 50% solution of 20% sulfuric acid, and then washed with water. Further, a porous anodic oxidation treatment was performed in a 20% sulfuric acid aqueous solution using a direct current to prepare a substrate 3. At this time, the weight of the anodic oxide film was 4 g / m ² . In the same manner as in Example 1, the following inorganic particles B having a hydroxyl group
Was synthesized. B is ethyl silicate: ethanol: water:
It is formed by adjusting the weight ratio of nitric acid to 10: 73: 2: 0.1, stirring and reacting at room temperature for 4 hours with a stirrer, and controlling the particle diameter of the inorganic particles to about 30 angstroms or less. This solution was applied on the surface of the anodic oxide film by a spin coating method on the substrate 3, and the pores were filled with inorganic particles. Inorganic particles by heat treatment at 100 ° C for 10 minutes
After fixing the probe in the hole , the gel film on the anodic oxide film was dissolved by immersion in a 1 mol% aqueous solution of potassium hydrogencarbonate at 40 ° C. for 60 minutes and washed with water to prepare a substrate 4. In this way, the photosensitive layer having the following composition was applied so that the coating weight after drying was 2.0 g / m ² with and without the inorganic particles in the pores to form a photosensitive layer.

Composition Ester compound of naphthoquinone-1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) 0.75 g Cresol novolak resin 2.00 g Oil Blue # 603 0.04 g Ethylene dichloride 16 g 2-Methoxyethyl acetate 12 g The photosensitive lithographic printing plate thus prepared was placed in a vacuum printing frame at a distance of 1 m from a distance of 1 m through a transparent positive film to a 3 kW metal halide. After exposure with a lamp for 50 seconds, the molar ratio of SiO ₂ / Na ₂ O was 1.74.
5.26% aqueous solution of sodium silicate (pH = 12.7)
Developed. After development, Heidelberg printing machine SOR
When printing with -KZ, both printing plates are 1
0,000 good prints were given. However, a plate containing no inorganic particles in the pores of the anodic oxide film is highly contaminated in the non-image area, has an absorbance of 0.08 at 600 nm, and has poor printability, poor balance between water and ink, and poor printability. I was On the other hand, the plate containing the inorganic particles in the pores of the anodized film did not cause any contamination of the non-image area. Example 3 The surface of a JIS1050 aluminum sheet was grained with a rotating nylon brush using a Pumice-water suspension as an abrasive. The surface roughness (center line average roughness) at this time was 0.5 μm.
Met. After washing with water, the substrate was immersed in a 10% aqueous solution of sodium hydroxide at 70 ° C. to perform etching so that the amount of aluminum dissolved was 6 g / m ² . After washing with water, it was immersed in a 3% aqueous solution of nitric acid for 1 minute to neutralize, and sufficiently washed with water. Then,
Electrolytic surface roughening was performed for 20 seconds in a 0.7% nitric acid aqueous solution using a rectangular wave alternating waveform with a voltage of 6 volts at the anode (power supply waveform described in Example of Japanese Patent Application Laid-Open No. 58-5795). The surface was washed by immersion in 20% sulfuric acid at 20 ° C. and then washed with water. Further, a porous anodic oxidation treatment was performed in a 20% sulfuric acid aqueous solution using a direct current to prepare a substrate 5. At this time, the weight of the anodic oxide film was 2.5 g / m ² . Thereafter, the substrate 5 was subjected to No. 3 sodium silicate 2.5 wt%, 70 ° C.,
After dipping for 4 seconds, the substrate was washed with water to obtain a substrate 6. In the same manner as in Example 2, the following inorganic particles B having a hydroxyl group were synthesized. B
Is ethyl silicate: ethanol: water: nitric acid at a weight ratio of 1
It is formed by adjusting the ratio to 0: 73: 2: 0.1 and reacting at room temperature for 4 hours, and controlling the particle diameter of the inorganic particles to about 30 angstroms. This solution was applied to the surface of the anodic oxide film by a spin coating method on the substrate 5, and the pores were filled with inorganic particles. 100 ° C., after fixing the inorganic particles into the pores by heat treatment for 10 minutes, the 40 ° C. 1Mo
The substrate 7 was immersed in a 1% aqueous solution of potassium hydrogen carbonate for 60 minutes to dissolve the film formed from the inorganic particles on the anodized film, and washed with water to prepare a substrate 7. In this way, the photosensitive layer having the following composition was applied so that the coating weight after drying was 2.0 g / m ² with and without the inorganic particles in the pores to form a photosensitive layer.

Negative photosensitive layer formulation Lipophilic polymer compound (2-hydroxyethyl methacrylate copolymer) 5.0 g diazo resin (condensate of p-diazodiphenylamine and p-formaldehyde 0.5 g) Victoria Pure Blue BOH 0.15 g dipicolinic acid 0.15 g phosphorous acid 0.1 g water 5.0 g 1-methoxy-2-propanol 45.0 g methyl ethyl ketone 50.0 g Plates that do not contain inorganic particles in the pores of the anodized film In addition, the non-image area was extremely stained, and it was difficult to print because it was difficult to maintain the balance between water and ink. However, the plate containing the inorganic particles in the pores of the anodic oxide film did not cause any contamination of the non-image area.

Continuation of front page (58) Fields surveyed (Int.Cl. ⁶ , DB name) B41N 3/03 G03F 7/00 503

Claims (2)

(57) [Claims] 1. Production of an aluminum support for a lithographic printing plate containing inorganic particles having hydroxyl groups in pores of an anodized film.
The method according to claim 1 , wherein the inorganic particles having a hydroxyl group on the anodized film.
Apply inorganic particles or contain inorganic particles having hydroxyl groups
Immerse the anodized aluminum plate in the solution
A manufacturing method characterized in that: Wherein the inorganic particles is obtained by hydrolysis and polycondensation of organic or inorganic metal compounds in a liquid The process of claim 1 wherein.