JPS62216796A - Manufacture of supporter for planograph plate - Google Patents

Abstract

PURPOSE:To provide a long run type planograph plate at low cost by applying sandblast graining and sulfuric acid anodic oxidation onto an aluminum substrate then immersing said substrate into a metallic salt aqueous solution. CONSTITUTION:An aluminum substrate is sandblasted and subjected to sulfuric acid anodic oxidation, then immersed into an aqueous solution containing 0.01-20wt% of salt of more than one kind of metals selected from calcium, barium, magnesium, strontium or manganese and an organic or inorganic acid. Preferably, the temperature of the aqueous solution is 40-120 deg.C and the immersing time is 5sec-10min. A supporting member for planograph plate manufactured in such a manner has a surface of high hydrophilicity, a high adhesive property with a photosensitive resin compound and an excellent adhesive property with an optically crosslinked macromolecular photosensitive resin having inferior adhesive property.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a support for lithographic printing plates, and in particular a method for producing a support with improved adhesion to photosensitive resin compositions. It is related to.

(Prior Art) Currently, supports for lithographic printing plates are generally subjected to anodizing treatment for the purpose of improving printing durability and water retention.

The anodic oxidation treatment is carried out by using an aluminum substrate as an anode and energizing the aluminum substrate through an electrolytic solution by direct current, alternating current, AC/DC superposition, or the like. As the electrolyte in this case, sulfuric acid or phosphoric acid is generally used. Among these, sulfuric acid anodizing is the most common industrial anodizing method because it allows low-voltage treatment and produces an oxide film that is wear-resistant. It is widely used in the production of supports such as quinone diazide positive type 28 plates. However, this sulfuric acid anodic treatment has the major drawback of poor adhesion to many polymeric photosensitive resins, and a printing plate with high resistance to φ11 force has not been obtained.

On the other hand, the oxidized film of the phosphoric acid anode has good adhesion to the polymer photosensitive resin, but the oxidized film of the phosphoric acid anode requires extremely high voltage due to the low conductivity of phosphoric acid. The process is expensive, phosphoric acid is relatively expensive, and it is difficult to control the properties of the electrolyte because it is easily affected by aluminum ions that accumulate during the process. is a disadvantageous method.

[Problem that the invention seeks to solve]

The problem to be solved by the present invention is to completely improve the adhesion to a photosensitive resin of an aluminum substrate for a printing plate which has been subjected to a sulfuric acid anodization treatment after a graining treatment.

[Failure to solve the problem]

As a means to solve the above-mentioned problems, the present invention provides that an aluminum substrate is subjected to (at) graining treatment, (bl) sulfuric acid anodization treatment, and (c) calcium, barium, magnesium, strontium, and manganese. Provided is a method for producing a support for a lithographic printing plate, characterized in that it is treated with an aqueous solution containing a salt of one or more selected metals and an organic acid or an inorganic acid (hereinafter referred to as metal salt aqueous solution).

The metal salt used in the present invention is a calcium, barium, magnesium, strontium or hamanganate salt of an organic or inorganic acid, and examples of the organic salt include formic acid,
Aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, lauric acid, valmitic acid, and stearic acid; unsaturated aliphatic monocarboxylic acids such as oleic acid and linoleic acid; citric acid, succinic acid, adipic acid, Aliphatic dicarboxylic acids such as maleic acid; oxycarboxylic acids such as lactic acid, gluconic acid, malic acid, tartaric acid, and citric acid; aromatic carboxylic acids such as sulfuric acid, mandelic acid, salicylic acid, and phthalic acid. Inorganic acids include sulfuric acid; nitric acid; hydrochloric acid, hydrogen bromide, halogenated acids such as hydrogen iodide; I get kicked. Among these, organic acid salts of calcium or barium are preferred, and among them, aliphatic monocarboxylic acid salts are preferred! R
Salts are particularly preferred. In the present invention, two or more of these metal salts may be used in combination.

The concentration of the metal salt as described above in the aqueous metal salt solution used in the present invention is preferably o, oi to 20% by weight, and 0.1 to 1.
01 (amount % is more preferable.

The treatment method using a metal salt aqueous solution (hereinafter referred to as metal salt treatment) in the present invention includes, for example, immersing an aluminum substrate that has been grained by various conventionally known methods and subjected to sulfuric acid anodization treatment in a metal salt aqueous solution. The temperature of the immersion bath at that time is preferably 40 to 120°C, and the immersion time is preferably 5 seconds to 10 minutes.

As the aluminum substrate used in the present invention, any conventionally known aluminum substrate for lithographic printing plates can be used. Examples include aluminum alloy plates containing aluminum (steel, magnesium, chromium, zinc, nickel, titanium, etc.).

Since the surface of the aluminum plate is contaminated with oil, rust, dust, etc., it is subjected to degreasing treatment such as solvent degreasing or alkaline degreasing, as necessary, and then graining treatment.

In general, the graining treatment carried out in the present invention may be performed by any of the conventionally known graining methods for lithographic printing plate substrates, such as ball polishing method, brush polishing method, plastic polishing method, Mechanical surface roughening methods such as puff polishing and liquid honing methods; electrochemical surface roughening methods that roughen the surface by immersing it in a softening bath such as ring number, nitric acid, or a mixture thereof. .

Furthermore, after this graining treatment, sodium hydroxide, potassium hydroxide,
Etching treatment (followed by desmutting treatment) with an aqueous alkali solution such as IJum (tertiary phosphoric acid) may also be performed. Although this etching process is not necessarily performed, it is advantageous to perform this process when it is desired to improve the hydrophilicity of the non-image area.

Furthermore, this aluminum substrate is subsequently subjected to sulfuric acid anodic oxidation treatment. 4JfL anodic oxidation treatment can be carried out by a conventionally known method. For example, an aluminum substrate is used as an anode, carbon or lead is used as a cathode, and sulfur is placed in an electrolytic solution, and an electric current is passed through it. In particular, it is possible to form an anodized layer M on the surface of the aluminum substrate. In this case, the sulfuric acid electrolyte may contain a small amount of chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, phosphoric acid, etc. The anodizing treatment conditions are an electrolyte concentration of 1
~80% by weight, liquid temperature 5~70°C, current density [L5~5D
A/dm", voltage 1~100■, electrolysis time 30 seconds~3
A range of 0 minutes is preferable, and the weight of the anodic oxide film is as follows:
A range of 01 to 10 fI/m'' is preferred.

The object of the present invention is achieved by subsequently subjecting the obtained aluminum substrate to the metal salt treatment as described above.

The support treated with metal salt according to the present invention has a good hydrophilic surface and high adhesion to the photosensitive resin composition, and can be used as it is as a support for lithographic printing-J1 plate. can not use.

As a suitable hydrophilic treatment agent, conventionally known ones can be used, for example, silicon is an alkali metal silicate such as soda; zirconium positive potassium fluoride; phosphate glass:
Potassium dichromium powder: hydrophilic polymers such as gelatin, polyvinylpyrrolidone, sodium polyacrylate, sodium salt of carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, and sodium polyvinylbenzenesulfonate.

The hydrophilic treatment agent is generally prepared as an aqueous solution at room temperature or at 1
Processed at temperatures below 00°C. The concentration of the hydrophilic treatment agent water bath solution is preferably cL001 to 20% by weight, and the treatment time is preferably 5 seconds to 10 minutes. Thereafter, the substrate is washed with water and dried to obtain a lithographic printing plate substrate.

Furthermore, when the hydrophilic treatment agent is a hydrophilic polymer, it is also possible to form an undercoat υ layer without washing with water after the treatment, apart from the above-mentioned hydrophilic treatment method. In this case, the coating amount is 5
~150m9/m! is preferred.

The support for a lithographic printing plate produced in this way is a photo-crosslinkable polymeric photosensitive resin that has poor adhesion in conventional supports treated with sulfuric acid anodization, such as cinnamic acid residues. Photosensitive tree 'Jr1 (% Kaisho 5
0-6404, JP-A-52-86488, etc.), photosensitive resins having phenine/diacrylic acid residues in the polymer structure (JP-A-52-112681, JP-A-58-1988) No.-185198, JP-A-60-1385
No. 42, JP-A-60-165646, JP-A-60-1
91244, etc.); photosensitive resins having a photosensitive unsaturated double bond adjacent to an aromatic nucleus; photosensitive resins having a photosensitive azide group in the polymer structure;
No. 8-52210, Special Publication No. 44-31837, Special Publication No. 4
It also has excellent adhesion to photosensitive resins such as those described in No. 3-21067.

As the photosensitive resin used in the photosensitive layer provided on the support of the present invention, any photosensitive resin used in the photosensitive layer of the conventionally known lithographic printing plate 11 can be used.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to the following Examples without exceeding the gist thereof.

〔Example〕

(An aluminum plate with a thickness of 124 mm and JIS 1050 was grained with abrasive sand and a nylon brush until the surface roughness and center average roughness) reached 05 μm. Subsequently, 1
It was etched in a 0% aqueous sodium hydroxide solution at 40°C for 20 seconds, washed with water, desmutted by immersing it in a 30% nitric acid aqueous solution for 30 seconds, and washed with water.

Next, in a 20% aqueous sulfuric acid solution at 6.0°C and a current density of 2
Anodic oxidation treatment was carried out using direct current at λ/drn'' to obtain an anodic oxidation film with a film weight of 5 l/-.Subsequently, it was washed with water.

The aluminum substrate thus grained and anodized is then subjected to metal salt treatment. The metal salt treatment method was carried out by immersing the aluminum substrate in the Kincho salt aqueous solution listed in Table 1 under the conditions listed in Table 3. Subsequently, it was washed with water and dried to prepare a support for a lithographic printing plate.

For Examples 6 to 11, this support was further provided with a sixth
It was subjected to hydrophilic treatment under the conditions listed in the table, washed with water, dried, and used.

On the support prepared in [1] above, one of the photosensitive resin compositions (listed in Table 3) adjusted in the composition ratio listed in Table 1 below was coated with a foam 2-. was dried to obtain a photosensitive lithographic printing plate having a photosensitive layer with a film thickness of t2 μm.

[3] Evaluation of adhesion and hydrophilicity of the support for planographic printing plate 11 with the photosensitive layer A negative film of the test pattern was brought into close contact with the photosensitive planographic printing plate prepared in [2] above, and a position 11 rL away from the photosensitive planographic printing plate was placed. Using a W metal halide lamp (Idol Fin 1000J at Iwasaki Electric Company Exhibition) for output 1 installed in
Optimal exposure time for each photosensitive resin composition (listed in Table 3)
Exposure is performed to form an image, and then the following second step is performed.
A developer was selected according to the photosensitive resin from among the developer solutions shown in Table 3) and developed using this developer to produce a printing plate. The printing plate produced in this way was installed in an FC four-color lithographic printing machine, and printed using standard ink for lithographic printing 11 under the same conditions as the lithographic printing 111J near the dormitory.
100,000th sheet] At the time of i11, adhesiveness and hydrophilicity were evaluated. Adhesion is evaluated by whether a print faithful to the original image can be obtained without plate skipping, etc., and hydrophilicity is evaluated by:
Evaluation was made based on whether or not a clear image without background stains could be obtained on the printed matter.

Table 2 *1) Perex NBLJ: Sodium tert-butylnaphthalene sulfone anionic surfactant manufactured by Kao Atlas ■.

*2) "Niracol NP-100j...Nonionic surfactant manufactured by Hatamitsu Chemicals (Co., Ltd.).

For comparison, the following comparative example was conducted.

Comparative Example 1: A photosensitive lithographic printing plate was prepared and plate-made in the same manner as in Example 1 except that the metal salt treatment was not performed, and the printing plate was evaluated.

Comparative Example 2: A photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that it was immersed in hot water on a metal salt-treated plate, plate-made, and the first plate was evaluated. .

Comparative Example 3...Example 6 except that metal salt treatment was not performed
A photosensitive lithographic printing plate was prepared and plate-made in the same manner as above, and the printing plate was evaluated.

The contents and results of each side above are summarized in Table 6.

〔Effect of the invention〕

The method for producing the support of the present invention includes calcium, barium,
By treating the aluminum substrate with an aqueous solution containing a salt of one or more metals selected from the group consisting of magnesium, strontium, and manganese and an organic or inorganic acid, the adhesion between the photosensitive layer and the support can be improved. This method of improvement has made it possible to provide a long-run type lithographic printing plate at a low cost even in the conventional adhesive type lithographic printing plate.

Agent Patent attorney Katsutoshi Takahashi Procedural amendment (spontaneous) February 2, 1988 Director General of the Patent Office Kuro 1) Mr. Akira, Indication of the case 1986 Patent Application No. 61099 2, Title of the invention Manufacturing method for lithographic printing plate support 3, relationship with the case of the person making the amendment Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (2)
88) Inu Nippon Ink Chemical Industry Co., Ltd. Representative Kawamura
Kuni Shigeru 4, Agent: Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Phone number: Tokyo (03) 272-4511 (main representative) (8
876) Patent Attorney Katsutoshi Takahashi 5, Subject of amendment 6, Contents of amendment (1) Akira, 74fl, page 9, line 12, “
Sodium polyvinylbenzenesulfonate, etc."

Corrected to "polyacrylic acid, polyvinylphosphonic acid, etc."

that's all

Claims (1)

[Claims] 1. An aluminum substrate (a) grained, (b) sulfuric acid anodized, (c) one or more members selected from the group consisting of calcium, barium, magnesium, strontium, and manganese. 1. A method for producing a lithographic printing plate support, which comprises treating with an aqueous solution containing a salt of a metal and an organic or inorganic acid. 2. The method according to claim 1, wherein the aqueous solution (c) is a hot aqueous solution at a temperature of 40 to 120°C. 3. (c) The concentration of salt contained in the aqueous solution is 0.01 to 20
3. The method according to claim 1 or 2, wherein the amount is % by weight.