JP2001264990A - Photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative type photosensitive planographic printing plate free of the jumping of thin lines and a highlight even after printing in large quantities, excellent in printing durability and capable of accepting direct laser writing. SOLUTION: In the planographic printing plate obtained by disposing a photosensitive layer on an aluminum base with an anodic oxide coating formed after surface roughening, the amount of the anodic oxide coating on the base is 1.5-4.0 g/m2, the surface area of the base is 1-30 times the apparent surface area and the photosensitive layer contains a compound having an addition polymerizable ethylenic double bond, a photopolymerization initiator and an organic high molecular polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate, and more particularly to a lithographic printing plate which can be directly made with a laser.
The present invention relates to a negative photosensitive lithographic printing plate using a photopolymerizable composition having high sensitivity and good tone reproducibility.

[0002]

2. Description of the Related Art In recent years, with the development of image forming technology, a laser beam having a narrow beam is scanned on a plate surface, and a character document, an image document, and the like are formed directly on the plate surface without using a film document. Plate making can be performed directly. For example, JP-B-61-9621, JP-A-63-962
By using the photosensitive composition described in JP-A-178105, JP-A-2-244050 and the like, plate making can be directly performed without using a film original.

However, in the case of a high-sensitivity photopolymerizable printing plate, the adhesion between the photosensitive layer and the support is not always strong. There is a problem that the light part flies. In particular, when delicate highlight reproducibility and print stability are required, the problem that the fine lines and highlight portions gradually fly as the number of prints increases becomes more serious. This is thought to be because the dampening solution penetrates the photosensitive layer and spreads at the interface between the photosensitive layer and the support, thereby lowering the adhesion at the interface. As a countermeasure, by changing the binder in the photosensitive layer to suppress dampening water permeability, or to provide a layer containing a silicone compound having an addition-reactive functional group, in order to increase the interface adhesion, Further, it has been studied to provide a silicate layer on the anodic oxide film, but it has not been possible to obtain a sufficient effect.

[0004] In particular, recent market trends include strong demands for shortening the exposure time to improve productivity and for using the laser at a low output for the long life of the laser.
There has been a strong demand for higher sensitivity and higher printing durability of photosensitive lithographic printing plates that can be directly made by laser light.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a direct laser writable negative photosensitive lithographic printing plate which is excellent in printing durability and does not cause thin lines or highlights even when a large amount of printing is performed. The purpose is to:

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, as shown below, an aluminum support having a roughened surface and an anodic oxide film formed thereon has been
The amount of the anodic oxide film is 1.5 to 4.0 g / m ² , the surface area of the support is 1 to 30 times the apparent surface area, and the addition-polymerizable ethylene is provided on the support. This has been achieved by having a photopolymerizable photosensitive layer containing a compound having an acidic double bond, a photopolymerizable initiator, and an organic polymer. This means that the surface area of the support is usually 40 to 10 with respect to the apparent surface area by the anodic oxide film used as the support for a lithographic printing plate.
By contrast, when the photopolymerizable photosensitive layer is a photopolymerizable photosensitive layer, the dampening solution that has penetrated the photosensitive layer during printing can be prevented from diffusing at the interface, thereby preventing the damping solution from diffusing at the interface. It was possible to suppress the deterioration of adhesion.

Conventionally, as a method of treating a support for a positive or negative type photosensitive lithographic printing plate of the type of exposing using a film, a pressurized steam is used as a method of reducing the surface area of the support for the purpose of preventing stains such as residual color remaining films. Some sealing and hot water treatments have been considered. In the present invention, the printing durability of the highlight portion caused by the fountain solution penetrating the photosensitive layer, which is not a problem in the conventional lithographic printing plate, is caused by the large surface area of the support. The inventors have found that the problem can be solved by suppressing the surface area of the support to 1 to 30 times the apparent surface area as a support for the photopolymerizable photosensitive layer that can be directly drawn by a laser.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (Aluminum support) The aluminum support used in the photosensitive lithographic printing plate of the present invention is a dimensionally stable metal containing aluminum as a main component, and is made of aluminum or an aluminum alloy. In addition to a pure aluminum plate, it is selected from an alloy plate containing aluminum as a main component and containing a trace amount of a different element, or a plastic film or paper on which aluminum (alloy) is laminated or evaporated. Further, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-B-48-18327 may be used. In the following description, the above-mentioned substrates made of aluminum or an aluminum alloy are collectively used as aluminum substrates. The different elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium,
There are chromium, zinc, bismuth, nickel, titanium and the like, and the content of the foreign element in the alloy is 10% by weight or less.
In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to produce due to refining technology.
It may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and is conventionally known and used, for example, JIS A 1050, JIS A 1100, JIS
SA 3103, JIS A 3005, and the like can be appropriately used. The thickness of the aluminum substrate used in the present invention is about 0.1 mm to 0.6 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, and the user's request.

(Roughening treatment) The aluminum plate is subjected to a roughening treatment to a more preferable shape. The surface roughening method includes mechanical surface roughening, chemical etching, electrolytic grain, and the like as disclosed in JP-A-56-28893. Further, an electrochemical surface roughening method of electrochemically roughening in an electrolytic solution of hydrochloric acid or nitric acid, a wire brush graining method for scratching the aluminum surface with a metal wire, and a roughening of the aluminum surface with a polishing ball and an abrasive. A mechanical graining method such as a ball graining method, a brush graining method for roughening the surface with a nylon brush and an abrasive can be used, and the above roughening methods can be used alone or in combination. Among them, a method of forming a grain surface usefully used in the present invention is an electrochemical method of chemically roughening in a hydrochloric acid or nitric acid electrolyte, and a suitable current density is 50 C / dm. It is in the range of ^{2 to} 400 C / dm ² . More specifically, in an electrolytic solution containing 0.1 to 50% hydrochloric acid or nitric acid, the temperature is 20 to 100 ° C, and the time is 1 second to 1 hour.
30 minutes, is performed using a DC or AC at a current density of ^{100C / dm 2 ~400C / dm 2} . Electrochemical roughening is unavoidable in improving the adhesion between the photosensitive layer and the substrate because it is easy to provide fine irregularities on the surface.

By this roughening, the average diameter is about 0.5 to 2
Craters or honeycomb-shaped pits of 0 μm can be formed on the aluminum surface at an area ratio of 30 to 100%. The pits provided here have the effect of making the non-image portion of the printing plate less liable to stain and improving the printing durability. In the electrochemical treatment, the quantity of electricity necessary to provide sufficient pits on the surface, that is, the product of the current and the time during which the current is passed is an important condition in electrochemical surface roughening. It is desirable from the viewpoint of energy saving that sufficient pits can be formed with a smaller amount of electricity. The surface roughness after the roughening treatment is Ra = 0.
2 to 0.7 μm is preferred.

The aluminum substrate thus roughened is chemically etched with an acid or an alkali. When an acid is used as an etching agent, it takes time to destroy a fine structure, which is disadvantageous in industrially applying the present invention. However, it can be improved by using an alkali as an etching agent. Alkali agents suitably used in the present invention include caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide, and the like. The preferred ranges of concentration and temperature are 1 to 50, respectively. %, 20 to 100 ° C., and a condition in which the amount of Al dissolved is 0.1 to 5 g / m ² is preferable. After etching, pickling is performed to remove dirt (smut) remaining on the surface. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. In particular, as a method for removing the smut after the electrochemical surface-roughening treatment, it is preferable to use a method described in JP-A-53-12739.
A method of contacting with sulfuric acid of 15 to 65% by weight at a temperature of 0 to 90 ° C. and a method of alkali etching described in JP-B-48-28123 are exemplified.

(Anodic Oxidation Treatment) The aluminum substrate treated as described above is further subjected to an anodic oxidation treatment. The anodizing treatment can be performed by a method conventionally performed in this field. Specifically, when a direct current or an alternating current is applied to aluminum in an aqueous solution or a non-aqueous solution by using sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid or the like alone or in combination of two or more thereof, aluminum is supported. An anodized film can be formed on the body surface. At this time, at least A
Components normally contained in 1 alloy plates, electrodes, tap water, groundwater and the like may of course be included. Furthermore, the second and third components may be added. Here, the second and third components include, for example, Na, K, Mg, Li, Ca, Ti, and A.
1, cations such as ions of metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Zn and ammonium ions;
Nitrate, carbonate, chloride, phosphate,
Examples include anions such as fluorine ions, sulfite ions, titanate ions, silicate ions, and borate ions, and the concentration may be about 0 to 10000 ppm. The conditions of the anodizing treatment vary depending on the electrolytic solution used and cannot be unconditionally determined. However, in general, the concentration of the electrolytic solution is 1 to 80%, the liquid temperature is -5 to 70 ° C, and the current density is 0. 5
~60A / dm ^2, voltage 1 to 100 V, electrolysis time 10
A range of 200 seconds is appropriate. Among these anodizing treatments, the method of anodizing at a high current density in a sulfuric acid electrolytic solution described in British Patent No. 1,412,768 is particularly preferable. In the present invention, the anodic oxide film preferably has a thickness of 1.5 to 4 g / m ² ,
/ And m is less than ² plate to easily enter the wound, significant power production exceeds 4g / m ² is necessary, which is economically disadvantageous. Preferably, it is 2-3 g / m ² .

(Process for Adjusting Surface Area) After the anodizing process, a process for reducing the surface area of the support to 1 to 30 times the apparent surface area is performed. The most common method for setting the surface area to a desired value is a sealing treatment of an anodized film with pressurized steam or hot water described in JP-A-4-176690 and JP-A-11-301135. In addition, silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment, electrodeposition sealing treatment, triethanolamine treatment, barium carbonate treatment, hot water treatment containing a trace amount of phosphate, etc. It can also be performed using a known method. The sealing film is formed, for example, from the bottom of the pore when the electrodeposition sealing process is performed, and is formed from the top of the pore when the steam sealing process is performed. Although the method of forming the pore-treated film is different, the sealing treatment is performed so that a support that satisfies a desired surface area range is obtained in any of the sealing treatments.

The method is not particularly limited as long as the surface area can be kept within the range. Examples thereof include immersion treatment with a solution, spray treatment, coating treatment, vapor deposition treatment, sputtering, ion plating, thermal spraying, and plating. Although it is mentioned, it is not particularly limited. As a specific treatment method, for example, at least one selected from the group consisting of an amino group, a carboxyl group and a salt thereof, and a sulfo group and a salt thereof disclosed in JP-A-60-149491. A layer comprising a compound having at least one group selected from the group consisting of a compound having at least one amino group and at least one hydroxyl group and a salt thereof disclosed in JP-A-60-232998. Layer containing a phosphate compound disclosed in JP-A-62-19494, and layer containing a phosphate disclosed in JP-A-62-19494.
No. 1,651, discloses a method in which a layer made of a polymer compound containing at least one kind of a monomer unit having a sulfo group as a repeating unit in a molecule is provided by coating.

Also, phosphonic acids having an amino group, such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, and glycerophosphonic acid which may have a substituent. Acids, organic phosphonic acids such as methylene diphosphonic acid and ethylene diphosphonic acid, organic phosphoric acid esters such as phenylphosphoric acid, naphthyl phosphoric acid, alkyl phosphoric acid and glycerophosphoric acid, which may have a substituent, having a substituent Organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid,
There is also a method of providing a compound layer selected from amino acids such as glycine and β-alanine, and a hydrochloride of an amine having a hydroxyl group such as a hydrochloride of triethanolamine.

The silane coupling agent having an unsaturated group may be coated, for example, N-3- (acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (3-acrylic). Roxypropyl)
Dimethylmethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxysilane, 3- (N-allylamino)
Propyltrimethoxysilane, allyldimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, 3-butenyltriethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, methacrylamidopropyltriethoxysilane, N- (3- (Methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxydimethyl) dimethylethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethyl Methoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyltriet Shishiran methacryloxypropyl methyltrimethoxysilane, methacryloxypropyltris (methoxyethoxy) silane, methoxy dimethylvinylsilane, 1-methoxy-3- (trimethylsiloxy) butadiene, styrylethyltrimethoxysilane,
3- (N-styrylmethyl-2-aminoethylamino)
-Propyltrimethoxysilane hydrochloride, vinyldimethylethoxysilane, vinyldiphenylethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, O- (vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, vinyltriethoxysilane, Vinyl trimethoxy silane, vinyl tri-t-butoxy silane, vinyl triisopropoxy silane, vinyl triphenoxy silane, vinyl tris (2-methoxy ethoxy) silane, diallyl amino propyl methoxy silane and the like can be mentioned. Of these, a coupling agent containing a methacryloyl group or an acryloyl group, which has a high reactivity of the unsaturated group, is preferable. However, if the unsaturated group is bifunctional, a vinyl group or an allyl group may be used.

In addition, a sol-gel coating treatment disclosed in JP-A-5-50779 and JP-A-5-24617
No. 1, JP-A-6-234284, JP-A-6-191173, and JP-A-6-230563, a method for treating a backcoat material by coating. Treatment of phosphonic acids described in JP-A-6-262873;
The coating treatment described in JP-A-6-297875, the method of anodizing by the method described in JP-A-10-109480, the specifications of Japanese Patent Application Nos. 10-252078 and 10-253411 are disclosed. Any method such as the immersion treatment method described above may be used.

[Image-forming layer] The following photosensitive layer (hereinafter also referred to as an image-forming layer) is formed on the support of the present invention prepared as described above, if necessary. In a photosensitive lithographic printing plate having a photopolymer type negative photopolymerizable image forming layer, for example, JP-A-8-320551, JP-A-10-237118, and JP-A-10-1613
No. 17, JP-A-10-282679, JP-A-11-65096, JP-A-11-115338, Japanese Patent Application No. 11-68247, Japanese Patent Application No. 11-26911, JP-A-10-282682 Gazette, JP 10
JP-A-282679, JP-A-10-161317, and the like.

(Adhesive layer) Before the photosensitive layer is formed on the aluminum substrate which has been subjected to the above-mentioned surface area adjustment treatment, in order to improve the adhesiveness between the photosensitive layer and the substrate,
An adhesive layer may be further provided on the surface of the substrate. The adhesive layer is not particularly limited, and examples thereof include an adhesive layer including a silicone compound having a functional group capable of causing an addition reaction by a radical (hereinafter, referred to as an addition-reactive functional group). The application of the adhesive layer containing a silicone compound having an addition-reactive functional group is preferably performed by a method using an organic silicone compound as a raw material. In particular,
When the addition reactive functional group is represented by R ¹ , the following formula (1):

R ¹ Si (OR ² ) ₃ (1)

(Wherein, R ¹ represents a functional group capable of causing an addition reaction by a radical such as an alkenyl group or an alkynyl group. OR ² represents a hydrolyzable alkoxy group or —OC.
Represents an OCH ₃ group. By treating an aluminum substrate with the organosilicone compound (1) represented by the formula (1), a metal, metal oxide, hydroxide, -OH
A covalent bond with the substrate surface by reacting with a group or a silanol group formed by a chemical conversion treatment of the substrate;

(R ³ O) ₂ (R ¹ ) Si—
(2)

(Wherein R ³ represents a bond to an alkyl group or a hydrogen atom of the same or different type as R ² , or a bond to another adjacent Si atom). ). In the above, the following formula (1a) or (1b) in which two or more addition-reactive functional groups (R ¹ ) are bonded to a central Si atom:

(R ¹ ) ₂ Si (OR ² ) ₂ (1a) (R ¹ ) ₃ SiOR ² (1b)

The organosilicone compound represented by the formula (1)
a) (1b) can also be used. When the addition-reactive functional group (R ¹ ) is a functional group bonded to the central Si atom via —O—,

(R ¹ ) ₄ Si (1c)

The organosilicone compound (1)
c) can also be used. The organic silicone compound (1) is applied to the aluminum substrate when at least one of the four R ¹ bonded to the central Si atom remains without being hydrolyzed. When the organic silicone compound (1) is applied on an aluminum substrate, it may be used alone or may be used after being diluted with a suitable solvent. Water and / or a catalyst can be added to bind the organosilicone compound (1) more firmly on the aluminum substrate. As the solvent, methanol,
Alcohols such as ethanol, propanol, isopropanol, ethylene glycol and hexylene glycol are preferred. As the catalyst, acids such as hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid and the like, or bases such as ammonia and tetramethylammonium hydroxide can be used.

The amount of addition-reactive functional groups on the aluminum substrate varies depending on the type of addition-reactive functional group to be bonded, ² per generally 0.01 to 1000 pieces 10 nm, 0.05-200 or if preferred, Preferably 0.1 to
It is appropriate to use 50. Sufficient light adhesive strength and addition-reactive functional group content is less than ² per 0.01 pieces 10nm difficult to obtain. By applying the organic silicone compound (1) thickly, the amount of the addition-reactive functional group per 10 nm ² can be substantially increased. Is 10 nm ²
Since there are at most 10 pieces, even if it is applied too thickly, it is useless. In order that the amount of the addition-reactive functional group is excessive and the hydrophilicity of the non-image area when used as a PS plate is not insufficient, 10n
It is preferable that the amount of the addition-reactive functional group per m ^{2 be} 1000 or less.

Therefore, when the addition-reactive functional group is bonded (planted) to the aluminum substrate surface using the organic silicone compound, the type and amount of the solvent for diluting the organic silicone compound and the hydrolysis for the hydrolysis on the substrate surface are required. The amount of water to be added (if added), the type and amount of catalyst to promote hydrolysis on the substrate surface (if added), the method of applying the organic silicone compound solution on the substrate, and after applying to the substrate It is necessary to change various process parameters such as drying atmosphere, drying temperature, drying time, etc., and control the amount of the addition-reactive functional group retained on the substrate surface so as to be within the above range. The amount of the addition-reactive functional group retained on the aluminum substrate surface is determined by measuring the surface of the substrate after the treatment by an appropriate method, for example, a fluorescent X-ray analysis method or an infrared absorption method. It can be determined by performing quantification, quantification of the amount of carbon-carbon multiple bonds, and the like.

As described above, a silicate film is formed on an aluminum substrate, and an addition-reactive functional group is bonded to the surface of the silicate film to complete the support of the present invention. However, when a PS plate is formed using this support (addition reactive support),
Simply treating the aluminum substrate using only the organic silicone compound of the formula (1) may cause printing stains. That is, a photopolymerizable photosensitive composition is coated on a support having an addition-reactive functional group attached thereon to form a photosensitive layer, and imagewise exposure is performed on this to cause image-wise interfacial light adhesion, By removing the unexposed portion with the developing solution, a photopolymerized adhesion film remains on the support according to the light pattern. Then, when ink and water are applied to the ink, the ink adheres to the imagewise exposed portion that has been photopolymerized and adhered to the unexposed portion to form a printing plate, but when the organic silicone compound is used alone, In some cases, excess organic functional groups may be present in unexposed areas where water should adhere, and ink may adhere to water and stains may be observed on printed matter.

Therefore, in order to prevent this printing stain, it is preferable to fix a large number of OH groups in addition to the addition-reactive functional group (R ¹ ) on the surface of the aluminum substrate to enhance the hydrophilicity. Preferably, in the bonding of the addition-reactive functional group to the aluminum substrate surface, the formula (1): R ¹ Si (OR ² ) ₃
In addition to the organosilicone compound (1) represented by the following formula (3): Si (OR ⁴ ) ₄ (wherein —OR ⁴ is a hydrolyzable alkoxy group, alkoxyalkoxy group, aryloxy group or —OCOCH ₃ And R ⁴ may be the same as or different from R ² ), and an organic silicone compound (3) represented by the formula (2)
At the same time as binding the reaction site represented by the formula (4):

(R ³ O) ₂ (OH) Si— (4)

It is preferable to bind a hydrophilic site represented by Here, in the formula, R ³ represents an alkyl group, a hydrogen atom, or a bond to another adjacent Si atom.
Most preferably, ³ is a hydrogen atom from the viewpoint of hydrophilicity. When R ³ is other than a hydrogen atom, hydrophilicity can be enhanced by washing the surface with an alkaline solution, if necessary.

The mixing ratio between the organosilicone compound (1) of the formula (1) and the organosilicone compound (3) of the formula (3) is as follows:
Since the efficiency of bonding (planting) each of them to the surface of the support varies depending on the properties of the support, a suitable range cannot be determined in a straightforward manner. However, specifically, the support is treated by changing the ratio of the two, and the photo-adhesion based on the addition-reactive functional group R ¹ and the hydrophilicity derived from the partial structure represented by the formula (4) are obtained. Are determined experimentally and used. In any case, the density of the addition-reactive functional group should be within the above range. Specifically, the mixing molar ratio of the organic silicone compound (3) to the organic silicone compound (1) is 0.05 to 500.
Is suitable, but preferably 0.2 to 200, and more preferably 1 to 100. Also, within this range, equation (3)
As the amount of the hydrophilic group derived from the organic silicone compound (3) increases, the hydrophilicity of the non-image portion increases. However, even when the density of the hydrophilic group is low, the density of the hydrophilic group can be improved by hydrophilizing the addition reactive functional group.

The bonding of the addition-reactive functional group to the surface of the aluminum substrate can be roughly classified into the above-mentioned method (hereinafter referred to as the SC method) using an organic silicone compound as it is, and an organic silicone compound. A method comprising using an organic-inorganic composite in which an addition-reactive functional group is fixed to an inorganic polymer containing a -Si-O-Si- bond obtained by hydrolysis and polycondensation (hereinafter referred to as SG). Called the law). When this organic-inorganic composite is applied to an aluminum substrate and dried, the inorganic polymer portion adheres to the substrate, and the addition-reactive functional group remains on the substrate surface as it is.

In the case of the SC method, the bonding position of the addition-reactive functional group on the aluminum substrate surface is likely to be a position having a specific property on the substrate surface, and it may be difficult to uniformly distribute the functional group on the substrate surface. is there. That is, a covalent bond with the Si atom is formed only at a specific acid point or base point, and the distribution of the addition-reactive functional group is likely to be controlled by the distribution of acid points or base points on the aluminum substrate surface. Therefore, unevenness may occur in the optical adhesive strength and the non-image area hydrophilicity. In such situations, it is advantageous to follow the SG method.

In detail, besides the SC method and the SG method, in addition to intermediate methods, for example, a part or all of OR ² in the organosilicon compound (1) of the formula (1): R ¹ Si (OR ² ) ₃ It is also possible to use an organic silicone compound having two or three molecules bonded by hydrolysis as a starting material. According to the addition method of the addition reactive functional group by the SG method, the organosilicone compound (1) of the formula (1) is optionally mixed with the organosilicone compound (3) of the formula (3) at a desired mixing ratio, in a liquid, in the presence of a catalyst if necessary, -OR ² and -O without causing the at addition-reactive functional groups R ¹ reaction
Causes hydrolyzed with R ⁴ to carry out the polycondensation reaction, as a liquid composition comprising inorganic polymer Si atoms in the center is connected by -Si-O-Si- bonds, which was applied to an aluminum substrate surface, Optionally drying attaches the addition reactive functional groups on the substrate. When the SG method is used, the distribution of the addition-reactive functional group bonded and fixed on the aluminum substrate surface is hardly influenced by the distribution of chemical properties such as acid sites and base sites on the substrate surface. When an organic silicone compound (3) is used in combination with the organic silicone compound (1) as a starting material, an addition-reactive functional group site represented by the above formula (2) and a hydrophilic group represented by the above formula (4) are used. Since the relative ratio to the site is substantially determined by the charging ratio of the organosilicone compound (1) and the compound (3), there is an advantage that the prescription determination path for obtaining an optimum surface is more orderly than the SC method.

Specific examples of the organic silicone compound (1) represented by the above formula (1) used in the present invention include the following.

CH ₂ ＣＨCH—Si (OCOCH ₃ ) ₃ , C
_{H 2 = CH-Si (OC} 2 H 5) 3, CH 2 = CH-Si
(OCH ₃ ) ₃ , CH ₂ ＣＨCHCH ₂ —Si (OC
_{2 H 5) 3, CH 2} = CHCH 2 NH (CH 2) 3 -Si (O
_{CH 3) 3, CH 2 =} CHCOO- (CH 2) 3 -Si (O
_{CH 3) 3, CH 2 =} CHCOO- (CH 2) 3 -Si (O
_{C 2 H 5) 3, CH} 2 = C (CH 3) COO- (CH 2) 3 -
_{Si (OCH 3) 3, CH} 2 = C (CH 3) COO- (CH
_{2) 3 -Si (OC 2 H} 5) 3, CH 2 = C (CH 3) COO
— (CH ₂ ) ₄ —Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ )
_{COO- (CH 2) 5 -Si (} OCH 3) 3, CH 2 = CH
COO— (CH ₂ ) ₄ —Si (OCH ₃ ) ₃ , (CH ₂ ＣC
_{(CH 3) COO- (CH 2} ) 3) 2 -Si (OCH 3) 2,
_{CH 2 = C (CH = CH} 2) -Si (OCH 3) 3, CH 2
ＣＨCH—SO ₂ MH— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ ,
_{CH 2 = CH-ph-O} -Si (OCH 3) 3, CH 2 = C
_{H-ph-CONH- (CH 2} ) 3 -Si (OCH 3) 3,
_{CH 2 = CH-ph-CH} 2 NH- (CH 2) 3 -Si (O
_{CH 3) 3, ph: HC≡C} -Si (OC 2 H 5 showing a benzene _{ring) 3, CH 3 C≡C-Si} (O
C ₂ H ₅ ) ₃ ,

[0040]

Embedded image

CH ₂ ＣＨCHCH ₂ O—Si (OCH ₃ ) ₃ ,
(CH ₂ ＣＨCHCH ₂ O) ₄ Si, HO—CH ₂ —C≡C—
_{Si (OC 2 H 5) 3} , CH 3 CH 2 = CO-C≡C-Si
(OC ₂ H ₅ ) ₃ , CH ₂ ＣＨCHS— (CH ₂ ) ₃ —Si (O
CH ₃ ) ₃ , CH ₂ ＣＨCHCH ₂ O— (CH ₂ ) ₂ —SCH _{2
-Si (OCH 3) 3, CH} 2 = CHCH 2 S- (CH 2) 3
—S—Si (OCH ₃ ) ₃ , (CH ₃ ) ₃ CCO—C≡C—
_{Si (OC 2 H 5) 3} , (CH 2 = CH) 2 N- (CH 2) 2
—SCH ₂ —Si (OCH ₃ ) ₃ , CH ₃ COCH = C (C
_{H 3) -O-Si (OCH} 3) 3.

Specific examples of the organosilicone compound (3) represented by the formula (3) include tetramethoxysilane,
Tetraethoxysilane, tetraisopropoxysilane,
Tetra (n-propoxy) silane, tetra (n-butoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane,
Examples thereof include tetrakis (2-methoxyethoxy) silane, tetraphenoxysilane, and tetraacetoxysilane, and among them, tetraethoxysilane is preferable.

Although the SC method and the SG method are used to bond the addition-reactive functional group to the surface of the aluminum substrate, the type of solvent, the method of applying the substrate, and the method of drying are the same. In the case of the method, it is necessary to prepare an inorganic polymer composition having an addition-reactive functional group in advance. Preferred examples are shown below. Solvents that can be used to polycondensate the organosilicone compounds (1) and (3) represented by the formulas (1) and (3) together with hydrolysis to obtain a composition suitable for the SG method include methanol, ethanol, and propanol. And alcohols such as isopropanol, ethylene glycol and hexylene glycol. The amount of the solvent to be used is generally 0.2 to 0.2 based on the total weight of the organosilicone compounds (1) and (3) used.
It is 500 times, preferably 0.5 to 100 times, more preferably 1 to 20 times. If the used amount is less than 0.2 times, the reaction solution is apt to gel over time and becomes unstable, which is not preferable. If it is more than 500 times, the reaction takes several days, which is not preferable. The amount of water added to hydrolyze the organic silicone compound is generally 0.1 to 1000 mol, preferably 0.1 to 1000 mol per mol of the organic silicone compound.
The amount is from 5 to 200 mol, more preferably from 1.5 to 100 mol. The amount of water is 0.1 mol / mol of the organic silicone compound.
When the amount is less than 1 mol, the progress of the hydrolysis and the subsequent polycondensation reaction becomes very slow, and it takes several days until stable surface treatment becomes possible, which is not preferable. On the other hand, when the amount of water is more than 1000 mol per 1 mol of the organic silicone compound, when the resulting composition is applied to a metal surface, poor adhesion occurs, and the composition has poor stability over time and gels immediately. In many cases, it becomes difficult to perform the coating operation stably.

The reaction temperature for preparing a composition suitable for the SG method is usually from room temperature to about 100 ° C., but depending on the type of catalyst described below, a temperature below room temperature or above 100 ° C. may be used. it can. It is also possible to carry out the reaction at a temperature higher than the boiling point of the solvent, and if necessary, a reflux condenser may be provided in the reactor. Examples of the catalyst used as necessary include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, malic acid, and oxalic acid, and bases such as ammonia, tetramethylammonium hydroxide, potassium hydroxide, and sodium hydroxide. Can be used. The catalyst is added in an amount of 0.001 to 0.001 mol per mol of the organic silicone compound based on the total amount of the organic silicone compound (1) and the organic silicone compound (3) optionally added.
1 mol, preferably 0.002 to 0.7 mol, more preferably 0.003 to 0.4 mol. Add 1 catalyst
More than a mole does not have a particular economic benefit compared to its additive effect.

When a weak acid such as acetic acid or malic acid is used as a catalyst, the reaction temperature is advantageously in the range of 400 ° C. to 1000 ° C. However, when a strong acid such as sulfuric acid or nitric acid is used as a catalyst, The range of 10 ° C to 60 ° C is good. When phosphoric acid is used as a catalyst, the reaction can be performed at 10 ° C to 90 ° C. In the process of preparing the composition used in the SG method, and in the process of applying and drying the composition on an aluminum substrate, heat is often applied. However, when a volatile acid is used as a catalyst, the volatile acid volatilizes in peripheral devices. It may adhere and corrode it. When the present method is used in a step mainly using iron as a raw material, it is preferable to use nonvolatile sulfuric acid and / or phosphoric acid as a catalyst.

As described above, the composition comprising the organosilicone compound represented by the formulas (1) and (3), the organic solvent, water and, if necessary, the catalyst is treated at an appropriate reaction temperature,
When the reaction time and, if appropriate, the appropriate stirring conditions are selected for the reaction, a polycondensation reaction occurs together with the hydrolysis, and Si—O
-A polymer or a colloidal polymer containing a Si bond is generated, and the viscosity of the liquid composition is increased to form a sol. Equation (1)
When preparing a sol solution using both the organosilicone compounds represented by (3) and (3), both organosilicone compounds may be loaded into the reaction vessel from the beginning of the reaction, or hydrolysis and polymerization may be performed by only one of them. After the condensation reaction has proceeded to some extent, the other organosilicone compound may be added to terminate the reaction. When the sol liquid used in the SG method is left at room temperature, the polycondensation reaction may continue to proceed and gel. Therefore, the sol liquid once prepared by the above method is diluted in advance with a solvent to be used for dilution at the time of application to an aluminum substrate, thereby preventing or delaying the gelation of the sol liquid. .

In both the SC method and the SG method, in order to bond a desired amount of an organosilicone compound or an addition-reactive functional group to a support, the organic silicone compound or an addition-reactive functional group on the support is required. In order to eliminate the distribution unevenness, it is preferable to adjust the concentration by adding a solvent before applying these treatment liquids to the support. Alcohols, especially methanol, are preferred as solvents for this purpose, but other solvents, organic compounds,
Inorganic additives, surfactants and the like can also be added. Examples of other solvents include methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-
Methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, acetylacetone, ethylene glycol and the like can be mentioned. Examples of organic compounds that can be added include epoxy resins, acrylic resins, butyral resins, urethane resins, novolak resins, pyrogallol-acetone resins, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polypropylene glycol, and the like. Examples of the inorganic additive include colloidal silica and colloidal alumina. ethylene glycol,
High-boiling solvents such as ethylene glycol monomethyl ether increase the stability of the solution diluted to the concentration applied to the support and ensure the reproducibility of the addition-reactive functional groups bound to the support. . Organic compounds such as a novolak resin and a pyrogallol-acetone resin have the same effect, but have a side effect of reducing the hydrophilicity of the surface of the obtained support, and it is necessary to finely adjust the addition amount.

When a sol solution or a liquid composition suitable for the SG method is applied to an aluminum substrate surface and then air-dried or heated and dried, the inorganic polymer composed of Si—O—Si bonds is gelled, and at the same time, the surface of the aluminum substrate is gelled. Covalently bond. The drying is performed to volatilize the solvent, residual water and optionally the catalyst, but the step can be omitted depending on the purpose of use of the treated substrate. Also in the SC method, this drying step has the meaning of ensuring the close contact between the organosilicone compound and the aluminum substrate in addition to the volatilization of the solvent, residual water and the like. Therefore, depending on the purpose, after the drying is completed, the temperature may be further increased and the heating may be continued. The maximum temperature during drying and, optionally, subsequent heating is preferably in such a range that the addition-reactive functionality R ¹ does not decompose. Therefore, the drying temperature conditions that can be used are from room temperature to
The temperature is 200 ° C, preferably room temperature to 150 ° C, and more preferably room temperature to 120 ° C. The drying time is generally 1 second to 30 minutes, preferably 5 seconds to 10 minutes, more preferably 10 seconds to 3 minutes. Liquid composition (organic silicone compound or its solution or sol) used in the present invention
Construction methods include brush coating, dip coating, atomizing,
Various types such as spin coating and doctor blade coating can also be used, and are determined in consideration of the shape of the surface of the aluminum substrate, the required film thickness to be processed, and the like.

On the aluminum substrate as described above, (1)
A photopolymerizable layer described later is formed on a support having a surface roughening treatment, (2) anodizing treatment, (3) surface area adjustment treatment of the present invention, and, if necessary, (4) an adhesive layer. The photosensitive lithographic printing plate of the present invention is formed by forming a photosensitive layer composed of the composition.

(Photopolymerizable Photosensitive Layer) The main components of the photopolymerizable photosensitive layer used in the present invention are a compound containing an addition-polymerizable ethylenic double bond, a photopolymerization initiator, an organic polymer binder and the like. Various compounds such as a coloring agent, a plasticizer, and a thermal polymerization inhibitor are added as necessary. The compound containing an addition-polymerizable double bond can be arbitrarily selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated bonds. For example, those having chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated esters. Examples include amides of a carboxylic acid and an aliphatic polyamine compound.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carbosic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate rate, Ruby penta acrylate,
Sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hydride Kishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy)
Phenyl] dimethylmethane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. Crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethyl glycol glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, and 1,6-hexamethylene. Screw-
Examples include methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide. Other examples include
A hydroxyl group-containing vinyl monomer represented by the following general formula (A) was added to a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule is exemplified.

CH ₂ ＣC (R ⁵ ) COOCH ₂ CH (R ⁶ ) OH (A)

(Where R ⁵ and R ⁶ are H or CH
_{Shows 3} . Urethane acrylates described in JP-A-51-37193;
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. Further, the Journal of the Adhesion Society of Japan vol. 20, no. 7,300-
308-page (1984) as photocurable monomers and oligomers can also be used. In addition, these usage amounts are 5 to all components.
70% by weight (hereinafter abbreviated as%), preferably 10 to
50%.

As the photopolymerization initiator, various photoinitiators known in patents and literatures can be used depending on the wavelength of the light source used.
Alternatively, a combination system (photoinitiating system) of two or more photoinitiators can be appropriately selected and used. For example, when light near 400 nm is used as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, and the like are widely used. Visible light of 400 nm or more, Ar laser, second harmonic of semiconductor laser, SH
Even when a G-YAG laser is used as a light source, various photoinitiating systems have been proposed. For example, US Pat.
No. 0,445, a certain photosensitive dye, a complex initiation system of a dye and an amine (Japanese Patent Publication No. 44-20189),
A combination system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. 45-37377), and a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Application Laid-Open No. 54-1979).
155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), and a system of a cyclic triazine and a merocyanine dye (JP-A-54-15102).
No. 4), a system of 3-ketocoumarin and an activator (Japanese Unexamined Patent Publication No.
112681, JP-A-58-15503), a system of biimidazole, a styrene derivative and a thiol (JP-A-5959 / 1983).
-140203), a system of an organic peroxide and a dye (JP-A-59-140203, JP-A-59-189340).
), A system of a dye having a rhodanine skeleton and a radical generator (JP-A-2-244050), a system of a titanocene and a 3-ketocoumarin dye (JP-A-63-221110), a titanocene and a xanthene dye, an amino group or a urethane group. (Japanese Unexamined Patent Publication (Kokai) Nos. 4-221958 and 4-2)
19756) and a system of titanocene and a specific merocyanine dye (Japanese Patent Application Laid-Open No. 6-295061). The use amount of these photopolymerization initiators is 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.2 to 50 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound. Can be used.

The photopolymerizable composition usually contains an organic polymer as a binder, and such an organic polymer has compatibility with a photopolymerizable ethylenically unsaturated compound. As long as the organic polymer is
It doesn't matter which one you use. Preferably, an organic high molecular polymer which is soluble or swellable in water or weakly alkaline water which enables water development or weakly alkaline water development is selected. The organic high-molecular polymer is selected and used depending on the application as a water, weakly alkaline water or organic solvent developer as well as a film-forming agent of the composition. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such organic high-molecular polymers include addition polymers having a carboxylic acid group in a side chain, for example, JP-A-59-44615,
JP-B-54-34327, JP-B-58-12577
No., JP-B-54-25957, JP-A-54-9272.
No. 3, JP-A-59-53836, JP-A-59-710
No. 48, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer,
There are croton copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in a side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate (meth) acrylic acid / optionally Other Addition-Polymerizable Vinyl Monomer Copolymers] are preferred. In addition, polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamides and polyethers of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
These organic high-molecular polymers can be mixed in an arbitrary amount in the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably it is 30 to 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the organic high molecular weight polymer is preferably in the range of 1/9 to 9/1. A more preferred range is 2/8 to 8/2, and still more preferably 3/8.
7 to 7/3. On the other hand, JP-A-10-23711
The use of the photopolymerizable composition described in 8 is also preferable from the viewpoints of high sensitivity and improvement in film strength.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization is prohibited in order to prevent unnecessary thermal polymerization of a polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add an agent. Suitable thermal polymerization inhibitors include haloid quinone, p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl −
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The addition amount of the thermal polymerization inhibitor is about 0.01 to the weight of the whole composition.
% To about 5% is preferred. Also, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition by oxygen, and is unevenly distributed on the surface of the photosensitive layer in a drying process after coating. Is also good. The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition. Further, a coloring agent may be added for the purpose of coloring the photosensitive layer. Examples of the coloring agent include phthalocyanine pigments, azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of dye and pigment added is about 0.5% of the total composition.
% To about 5% is preferred. In addition, additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film. The amount of these additives is preferably 10% or less of the total composition.

When the photopolymerizable composition of the present invention is applied on a support, it is used after being dissolved in various organic solvents.
As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxy Ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N N- dimethylformamide, dimethyl sulfoxide, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 1 to 50% by weight.

A surfactant can be added to the photopolymerizable composition of the present invention in order to improve the coated surface quality. The coating amount is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying. More preferably, 0.
It is 3 to 5 g / m ² . More preferably, 0.7 to 3 g /
m ² .

(Oxygen Shielding Protective Layer) In the photosensitive lithographic printing plate of the present invention, an oxygen shielding protective layer containing a water-soluble vinyl polymer may be appropriately provided on the photosensitive layer. Examples of the water-soluble vinyl polymer contained in the oxygen-barrier protective layer of the present invention include polyvinyl alcohol and its partial esters, ethers, and acetals, or a substantial amount of unsubstituted water to make them necessary water-soluble. Copolymers containing vinyl alcohol units are included. Examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100% and a polymerization degree of 300 to 2400. Specifically, Kuraray Co., Ltd. PVA-105, PVA-11
0, PVA-117, PVA-117H, PVA-12
0, PVA-124, PVA-124H, PVA-C
S, PVA-CST, PVA-HC, PVA-203,
PVA-204, PVA-205, PVA-210, P
VA-217, PVA-220, PVA-224, PV
A-217EE, PVA-220, PVA-224, P
VA-217EE, PVA-217E, PVA-220
E, PVA-224E, PVA-405, PVA-42
0, PVA-613, L-8 and the like.

As the above copolymer, 88 to 100%
Hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal and copolymers thereof are mentioned. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination. Known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of a film may be added to the oxygen-barrier protective layer of the present invention. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, and sorbitol. Also. A water-soluble (meth) acrylic polymer may be added.

The photosensitive lithographic printing plate thus obtained was
r laser, the second harmonic of semiconductor laser (SHG-L
D, 350-600 nm), directly exposed by a YAG-SHG laser, and then developed. As a developing solution used for such a developing process, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tertiary sodium phosphate, potassium,
Same ammonium, dibasic sodium, same potassium,
Inorganic alkali agents such as ammonium, sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium Can be Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkali agents are used alone or in combination of two or more. Among the above-mentioned alkaline aqueous solutions, the developing solution in which the effect of the present invention is further exhibited is an aqueous solution containing an alkali metal silicate and having a pH of 12 or more. The aqueous solution of the alkali metal silicate depends on the ratio (generally represented by the molar ratio of [SiO ₂ ] / [M ₂ O]) of silicon oxide SiO ₂ and the alkali metal oxide M ₂ O, which are the components of the silicate, and the concentration. The developing property can be adjusted. For example, as disclosed in JP-A-54-62004,
When the molar ratio of iO ₂ / Na ₂ O is 1.0 to 1.5 (that is, [Si
O ₂ ] / [Na ₂ O] is 1.0 to 1.5, and SiO 2
₂ is an aqueous solution of sodium silicate having a content of 1 to 4% by weight, or [SiO ₂ ] / [M] is 0.5 to 0.75 (as described in JP-B-57-7427). That is, [SiO ₂ ] / [M ₂ O] is 1.0 to 1.5),
An alkali metal silicide having a SiO ₂ concentration of 1.4% by weight and said developer containing at least 20% potassium, based on gram atoms of total alkali metal present therein. Acid salts are preferably used.

Further, the photosensitive lithographic plate was prepared using an automatic developing machine.
When developing a printing plate, it has a higher alkali strength than the developing solution.
By adding a high aqueous solution (replenisher) to the developer,
Without replacing the developer in the development tank for a long time,
It is known that photosensitive lithographic printing plates can be processed
ing. This replenishment system is also preferably applied in the present invention.
Is done. For example, disclosed in Japanese Patent Application Laid-Open No. 54-62004.
[SiO 2_Two] / [Na_TwoO]
When the molar ratio is 1.0 to 1.5 (that is, [SiO 2_Two] / [Na
_TwoO] is 1.0 to 1.5), and SiO_TwoContent of
Using an aqueous solution of 1-4% by weight sodium silicate,
Continuous or interrupted depending on the throughput of the photosensitive lithographic printing plate.
Successively SiO_Two/ Na_TwoWhen the molar ratio of O is 0.5 to 1.5 (immediately
C [SiO _Two] / [Na_TwoO] is 0.5 to 1.5)
A method of adding an aqueous solution of sodium acid (replenisher) to the measurement of development,
Further, it is disclosed in Japanese Patent Publication No. 57-7427.
[SiO_Two] / [M] is 0.5 to 0.75 (that is,
[SiO_Two] / [M_TwoO] is 1.0 to 1.5),
SiO_TwoAlkali metal silicon having a concentration of 1 to 4% by weight
Alkali metal used as replenisher using acid salt developer
Silicate [SiO_Two] / [M] is 0.25 to 0.75
(Ie [SiO_Two] / [M_TwoO] is 0.5 to 1.5)
And both the developer and the replenisher are contained therein.
Based on gram atoms of all alkali metals present
Contains at least 20% potassium
A development method is preferably used. Development processing in this way
The photosensitive lithographic printing plate thus obtained is described in JP-A-54-8002.
Each public such as 55-115045 and 59-58431
As described in the report, washing water, surfactants, etc.
Rinsing solution, non-containing gum arabic, starch derivative, etc.
Post-treated with a sensitizing solution. The photosensitive lithographic printing plate of the present invention
Use various combinations of these processes for post-processing
Can be. Lithographic printing plate obtained by such processing
Is mounted on an offset press and used to print multiple sheets.
It is.

[0068]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. <Method for preparing support> A comprising the components shown in Table 1 below
After adjusting the molten metal, performing molten metal treatment and filtration,
An ingot with a width of 1200 mm and a width of 1200 mm was prepared by DC casting, and the surface was scraped off with an average 10 mm surface grinder, then kept at 550 ° C. for about 5 hours, and then hot-rolled when the temperature dropped to 400 ° C. A rolled plate having a thickness of 2.7 mm was obtained using a mill, and heat treatment was further performed at 500 ° C. using a continuous annealing machine, followed by cold rolling to finish to a thickness of 0.24 mm. After this aluminum plate was made 1030 mm in width, it was continuously treated.

[0069]

[Table 1]

(A) Using an existing mechanical roughening device,
While a suspension of an abrasive (pumice or quartz sand) having a specific gravity of 1.12 and water was supplied to the surface of the aluminum plate as a polishing slurry, mechanical roughening was performed with a rotating roller-shaped nylon brush. The average particle size of the abrasive is 40-4
5 μm and the maximum particle size was 200 μm. Nylon brush is made of 6/10 nylon, hair length 50mm,
The hair diameter was 0.3 mm. Nylon brush is φ3
A hole was made in a 00 mm stainless steel tube and planted so as to be dense. Three rotating brushes were used. The distance between the two support rollers (φ200mm) below the brush is 300m
m. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 KW plus with respect to the load before pressing the brush roller against the aluminum plate. The rotation direction of the brush was the same as the movement direction of the aluminum, and the rotation speed was 200 rpm.

(B) The aluminum plate was prepared by adding a caustic soda concentration of 2.6 wt%, an aluminum ion concentration of 6.5 wt%,
Etching treatment by spraying was performed at a temperature of 70 ° C., and 13 g / m ^{2 of the} aluminum plate was dissolved. Thereafter, washing with water was performed by spraying. (C) Desmut treatment was performed by spraying with a 1% by weight aqueous solution of nitric acid (containing 0.5% by weight of aluminum ions) at a temperature of 30 ° C., and then washing with water was performed by spraying. As the nitric acid aqueous solution used for the desmutting, a waste liquid from a step of performing electrochemical surface roughening using an alternating current in a nitric acid aqueous solution was used.

(D) Electrochemical surface roughening treatment was continuously performed using an AC voltage of 60 Hz. At this time, the electrolytic solution was a 1 wt% aqueous solution of nitric acid (aluminum ion 0.5 w
t%, containing ammonium ion 0.007 wt) at a temperature of 50 ° C. In the AC power supply, the time TP until the current value reaches a peak from zero is 2 msec, and the duty ratio is 1:
1. Using a trapezoidal rectangular wave alternating current, electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. Current density is 3 at peak current
0 A / dm ² , and the amount of electricity was 255 C / dm ² in total of the amount of electricity when the aluminum plate was an anode. 5% of the current flowing from the power supply was diverted to the auxiliary anode. Thereafter, water washing by spraying was performed. (E) The aluminum plate was subjected to an etching treatment at 70 ° C. by spraying at a concentration of 26% by weight of caustic soda and a concentration of 6.5% by weight of aluminum ions, and the aluminum plate was 1.3%.
g / m ² , and removal of a smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening is performed using alternating current at the preceding stage, and dissolution of an edge portion of the generated pit, Edges are smoothed. Then, it was washed with water by spraying.

(F) Desmut treatment was performed by spraying with a 25 wt% sulfuric acid aqueous solution (containing 0.5 wt% aluminum ions) at a temperature of 60 ° C., and then washing with water was performed by spraying. (G) Anodizing apparatus of the existing two-stage power supply electrolytic treatment method (first and second electrolytic unit lengths 6 m each, first power supply unit length 3 m, second power supply unit length 3 m, first and second power supply electrode lengths 2.4 m each) ), The concentration of sulfuric acid in the electrolytic part is 100 g / liter (containing 0.5 wt% of aluminum ions), the temperature is 50 ° C., and the specific gravity is 1.
1. Anodizing treatment was performed at a conductivity of 0.39 S / cm.
Thereafter, washing with water was performed by spraying.

At this time, in the anodic oxidation apparatus, the current from the power supply flows to the first power supply electrode provided in the first power supply unit, flows to the plate-shaped aluminum via the electrolytic solution, and is applied to the plate by the first electrolytic unit. An oxide film is formed on the surface of the aluminum plate, and returns to the power supply through the electrolytic electrode provided in the first power supply unit. On the other hand, the current from the power supply flows to the second power supply electrode provided in the second power supply unit, similarly flows to the plate aluminum through the electrolytic solution, and forms an oxide film on the surface of the plate aluminum in the second electrolytic unit. The amount of electricity supplied from the power supply to the first power supply unit and the amount of electricity supplied from the power supply to the second power supply unit are the same, and the power supply current density on the oxide film surface in the second power supply unit is approximately 25 (A / dm ² ). In the second feeder,
Power was supplied from the oxide film surface of 1.35 g / m ² . The final oxide film amount was 2.7 g / m ² . The substrate so far is referred to as [A]. In the substrate [A], the substrate manufactured except for the brush polishing step (a) is referred to as [B]. In the substrate [B], a substrate having a final oxide film amount of 0.4 g / m ² by changing the current density during anodic oxidation is referred to as a substrate [C], and a substrate having a final oxide film amount of 5 g / m ² is referred to as a substrate [D].

(Method of Forming Image of Image Forming Layer 1) Next, a liquid composition (sol solution) of the SG method was prepared by the following procedure. The following composition was weighed into a beaker and stirred at 25 ° C. for 20 minutes.

Si (OC ₂ H ₅ ) ₄ 38 g 3-methacryloxypropyltrimethoxysilane 13 g 85% phosphoric acid aqueous solution 12 g ion-exchanged water 15 g methanol 100 g

The solution was transferred to a three-necked flask, and the three-necked flask equipped with a reflux condenser was immersed in an oil bath at room temperature. The contents of the three-necked flask were heated to 50 ° C. in 30 minutes while stirring with a magnetic stirrer. While maintaining the bath temperature at 50 ° C., the reaction was further performed for 1 hour to obtain a liquid composition (sol solution). This sol solution was diluted with methanol / ethylene glycol = 20/1 (weight ratio) so as to be 0.5% by weight, applied with a wheeler to a substrate, and dried at 100 ° C. for 1 minute. The coating amount at that time was 4 mg / m ² .
The amount of the Si element was also determined by the fluorescent X-ray analysis method, and this amount was used as the amount of the Si coating.

On the aluminum plate thus treated, a high-sensitivity photopolymerizable composition having the following composition was applied so as to have a dry coating amount of 1.4 g / m ^2, and dried at 100 ° C. for 1 minute. A photosensitive layer was formed.

[Photopolymerizable composition] Pentaerythritol tetraacrylate 2.0 g Allyl methacrylate / methacrylic acid 2.0 g Copolymer (copolymer molar ratio 75/25) Compounds described in JP-A-10-237118 0.50 g No. I-19 Compound described in JP-A-10-237118 0.06 g B-2 Compound described in JP-A-10-237118 0.10 g No. C-2 methyl ethyl ketone 20 g propylene glycol monomethyl ether acetate 20 g

An aqueous solution of 3% by weight of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 500) was applied onto the photosensitive layer so that the dry coating weight was 2.5 g / m ² .
After drying at 120 ° C. for 3 minutes, a photosensitive lithographic printing plate was obtained.
These plates were converted to CSI's PLATE-JET4 (FD-
Using a YAG laser (10.8 mW, 532 nm), 1-99% was exposed in two portions at 1% intervals under various energy conditions of 4000 dpi at 175 lines / inch. Thereafter, the substrate was exposed to 120 ° C. for 20 seconds and subjected to post-heating treatment.

The development was carried out by immersion in the following developer at 25 ° C. for 30 seconds. (Developer) 1K potassium silicate 30g potassium hydroxide _{15g C 12 H 25 -C 6 H} 4 -O-C 6 H 4 -SO 3 Na 3g Water 1000g

Next, gum solution FP manufactured by Fuji Photo Film Co., Ltd.
-2W was diluted twice with water, and the plate was treated according to the usage. For printing durability measurement, a diamond IF manufactured by Mitsubishi Heavy Industries as a printing machine
-2, and Graph G (N) manufactured by Dainippon Ink and Chemicals, Inc. was used as the ink. 150,000 sheets were printed while sampling the printed matter every 5000th sheet from the start of printing. Table 2 shows the number of prints in which 2% halftone dots in the highlight portion could be reproduced by visual evaluation as highlight reproducibility.
Shown in

[0083]

[Table 2]

* Specific surface area: Actually measured surface area / apparent surface area The actual surface area was calculated on the basis of physical adsorption from the adsorbed amount of a mixed gas of helium and 0.1% krypton using Yuasa Ionics' cantasorb. . Specifically, the support was cut into a size of 3 cm × 6 cm, and the apparent surface area at this time was 18 cm ² . 6c
Make 15 samples cut to m × 2 mm. This is U
After being degassed at 180 ° C. for 1 hour while flowing N ₂ into a tube, the detector is fixed at the measurement position of the cantasorb, and the detector is stabilized while flowing a mixed gas of helium and 0.1% krypton. After the U-tube was immersed in liquid nitrogen and cooled sufficiently, the adsorbed gas released when returning to room temperature naturally was detected, and the surface area calculated from the detected value was defined as the actual surface area.

[0085]

As described above, according to the present invention,
The photosensitive layer and the support are firmly adhered to each other. Even if ink on the plate surface is removed with a high-sensitivity and acidic plate cleaner, and even if a large amount of printing is performed, highlights do not fly, and laser writing with printing durability is possible. A photosensitive lithographic printing plate can be provided.

Claims (1)

[Claims] 1. A planographic printing plate comprising a photosensitive layer provided on a roughened aluminum support having an anodized film formed thereon, wherein the amount of the anodized film on the support is 1.5 to 4.
0 g / m ² , the surface area of the support is 1 to 30 times the apparent surface area, and the photosensitive layer has a compound having an addition-polymerizable ethylenic double bond, a photopolymerization initiator, A photosensitive lithographic printing plate comprising an organic polymer.