JPH1078656A - Photosensitive resin composition for planographic printing and photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior adhesion, satisfactory printing resistance and chemical resistance by incorporating a specified compd. as a component of a resin binder. SOLUTION: In this photosensitive resin compsn., one or more kinds of compds. represented by the formula are contained as components of a resin binder. In the formula, each of R1 and R2. is H, halogen, alkyl, alkoxy or aryl, (n) is 0-50 and the mean value (n) is 0-20, preferably 0-10. The average mol.wt. of the resin binder is 220-4,000, preferably 240-2,000 and the resin binder may be obtd. by allowing phenol to react with dicyclopentadiene. A sensitizer used is preferably an o-naphthoquinonediazido compd. such as an ester compd. of o-naphthoquinonediazidosulfonic acid and a low molecular compd., oligomer or polymer having phenolic hydroxyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition used for lithographic printing. For more information,
The present invention relates to a photosensitive resin composition for lithographic printing having excellent properties such as chemical resistance and adhesion.

[0002]

2. Description of the Related Art Conventionally, phenol novolak resins, poly-parahydroxystyrene resins, polyester resins soluble in aqueous alkali solutions, polyamide resins, polyacrylamide resins, and the like are generally used as binder resins for photosensitive resin compositions used for lithographic printing. Has been used. However, when only these known resins are used, the adhesion to the printing plate is poor, the abrasion resistance is insufficient, and the printing durability is deteriorated due to the occurrence of background stain during printing, or the cleaning liquid At present, it is strongly desired to solve these problems because there is a problem in erosion of the image area, that is, a problem in chemical resistance.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition for lithographic printing which has excellent adhesion and good printing durability and chemical resistance.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on a photosensitive resin composition for lithographic printing which has excellent adhesion and good printing durability and chemical resistance. Was completed. That is, the present invention provides a photosensitive resin composition containing a photosensitive agent and a binder resin, wherein at least one compound represented by the general formula (1) (formula 2) is contained as a component of the binder resin. Characteristic photosensitive resin composition for lithographic printing, the photosensitive resin composition for lithographic printing using an o-naphthoquinonediazide compound as a photosensitive agent, and a flat plate having the photosensitive resin composition on a support It relates to a printing plate.

[0005]

Embedded image (In the formula, R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and n represents 0 to 50.)

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The photosensitive resin composition for lithographic printing of the present invention comprises at least one compound represented by the general formula (1) as a binder resin component in a photosensitive resin composition containing a photosensitive agent and a binder resin. It is made. In the compound represented by the general formula (1), R ₁ ,
R ₂ is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkoxy group or an aryl group, preferably a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), and an alkyl group having 1 to 8 carbon atoms (eg,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n
-Pentyl group, isopentyl group, neopentyl group, tert
-Pentyl group, n-hexyl group, cyclohexyl group, n
-Heptyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, etc.),
An alkoxy group having 1 to 8 carbon atoms (e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-
Butoxy group, isobutoxy group, sec-butoxy group, n-
A pentyloxy group, a neopentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, or the like; or an aryl group having 6 to 10 carbon atoms (for example, Phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-tert-butylphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 3-fluorophenyl group, 1-naphthyl group, 2-naphthyl group, etc.), and more preferably a hydrogen atom, a chlorine atom, and a carbon number of 1 to 1.
An alkyl group having 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, particularly preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or It is an aryl group having 6 to 10 carbon atoms.

The resin of the general formula (1) used in the present invention can be easily obtained by reacting phenols with dicyclopentadiene, and n is distributed between 0 and 50. Is from 0 to 20, preferably from 0 to 10. The average molecular weight is 220-4000, preferably 240-2000. In the photosensitive resin composition for lithographic printing of the present invention, the compound represented by the general formula (1) is contained as an essential component of the binder resin, but other binder resins may be used in combination. Examples of other binder resins used in the present invention include phenol aralkyl resins, phenol novolak resins, poly-parahydroxystyrene resins, polyester resins soluble in aqueous alkali solutions, polyamide resins, polyacrylamide resins, and the like. When another binder resin is used in combination, the proportion of the compound represented by the general formula (1) is 1 to 50%, preferably 5 to 30% of the total binder resin.

In the photosensitive resin composition for lithographic printing of the present invention, any photosensitive agent can be used as the photosensitive agent. Preferred photosensitizers include o-naphthoquinonediazide compounds. Examples of the o-naphthoquinonediazide compound used in the present invention include an ester compound of o-naphthoquinonediazidesulfonic acid and a low-molecular compound having a phenolic hydroxyl group, an oligomer or a polymer. Specifically, Japanese Patent Publication No. 38-12083, Japanese Patent Publication No. 52-28401, Japanese Patent Publication No. 50-50
No. 83, JP-A-63-198046, JP-A-1-101544, JP-A-4-110946, German Published Patent No. 4106356, U.S. Pat.
The following formulas (2) to-disclosed in 162190 and the like.
(9) Compounds represented by (Chemical Formula 3) can be exemplified.

[0009]

Embedded image [In the above formula, Q represents a group represented by the following formula (10) (Formula 4), and m and n represent arbitrary integers. ]

[0010]

Embedded image

In the photosensitive resin composition for lithographic printing of the present invention, the content of the photosensitive agent is 5 to 5% with respect to the binder resin.
It is 50%, preferably 10 to 30%. The photosensitive resin composition for lithographic printing of the present invention, in addition to the components listed above,
If necessary, a dye, a pigment, a sensitizer, a plasticizer, a surfactant and the like can be further added. The photosensitive lithographic printing plate of the present invention has the photosensitive resin composition of the present invention on a support. As a method of applying the photosensitive resin composition for lithographic printing of the present invention to the surface of a support, after preparing a coating solution by dissolving the photosensitive resin composition in a solvent, conventionally known methods, for example, spin coating, Coating methods such as wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used. The coating amount in this case varies depending on the purpose, usually, 0.5 to 5.0 g / m ² as solids, preferably, adjusted to be 1.0 to 3.0 g / m ^2.

Solvents that can be used to dissolve each component of the photosensitive resin composition for lithographic printing of the present invention include ethyl lactate, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate,
Examples include dimethylformamide, dimethylsulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents can be used alone or in combination of two or more.

Examples of the support usable in the present invention include metal plates such as aluminum, zinc and copper, metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum and iron, paper, plastic films and glass. Examples thereof include a board or resin-coated paper, aluminum metal foil-coated paper, and a hydrophilized plastic film. Particularly preferred is an aluminum plate, and it is most preferable to use an aluminum plate that has been subjected to graining treatment, anodic oxidation treatment, and if necessary, sealing treatment.

The photosensitive lithographic printing plate using the photosensitive resin composition for lithographic printing of the present invention can be subjected to a developing treatment by a usual method. As a positive development processing method, for example, there is a method of exposing through a transparent positive film from a light source such as an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, and a tungsten lamp, and then developing with an alkali developing solution. On the other hand, as a negative development processing method, for example, through a transparent negative film, after exposing from a light source such as an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, and then heated at 110 ° C. to 150 ° C. for several minutes, A method of exposing the entire surface and finally developing with an alkali developing solution can be used.

Examples of the alkali developer used above include aqueous solutions of alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, potassium metasilicate, and sodium diphosphate. The concentration of the alkali metal salt is preferably 0.5 to 5% by weight. Further, a surfactant, alcohol, or the like may be added to the developer as needed.

[0016]

The present invention will be described in more detail with reference to the following examples, which, of course, are not intended to limit the scope of the present invention. Example 1 2.0 g of a naphthoquinonediazide compound represented by the formula (2), 1.5 g of a phenol resin compound represented by the formula (11) (formula 5) (average molecular weight Mw = 890), a phenol aralkyl resin [Mitsui Toatsu Millex XL-225, manufactured by Chemical Co., Ltd .; average molecular weight Mw = 6500] 5.1
g, blue dye UV-Blue-784 [manufactured by Mitsui Toatsu Chemicals, Inc.] 0.05 g, 1,2-naphthoquinone-2-
A coating solution of a photosensitive resin composition comprising 0.06 g of diazido-4-sulfonyl chloride and 100 g of ethyl lactate was applied on an aluminum support using a spin coater so as to give a solid content of 2.0 g / m ^2. Apply, 9
After drying at 0 ° C. for 5 minutes, a positive photosensitive lithographic printing plate was obtained.

[0017]

Embedded image The aluminum support used above was produced as follows. That is, a 0.25 mm-thick aluminum plate [material 1050, tempered H16] was degreased in a 5% by weight aqueous sodium hydroxide solution at 60 ° C. for 1 minute, and then in a 0.5 molar aqueous hydrochloric acid solution at room temperature. , An electrolytic etching treatment was performed for 30 seconds at a current density of 60 A / dm ² . Then, after desmutting for 10 seconds in a 5% by weight aqueous sodium hydroxide solution at 60 ° C.,
Anodizing treatment was performed in a 20% by weight aqueous sulfuric acid solution at 3 A / dm ² for 1 minute. Finally, a sealing treatment was performed with water at 30 ° C. for 20 seconds.

A positive original film is adhered to the photosensitive lithographic printing plate obtained as described above, and a 2 kW metal halide lamp manufactured by Iwasaki Electric Co., Ltd., idle fin 2000 is used.
Was exposed for 70 seconds under the condition of 8.0 mW / cm ² from a light source of No. 1, and developed at 27 ° C. for 20 seconds with a 6-fold water diluent of a developing solution SDR-1 manufactured by Konica Corporation. I got The lithographic printing plate was evaluated for chemical resistance, printing durability, and adhesion. The chemical resistance is determined by a cleaning solution used to remove background stains generated in the non-image area during printing (here, an ultra plate cleaner UP manufactured by ABC Chemical Co., Ltd.).
C]. That is, the lithographic printing plate on which an image was formed by development was immersed in UPC at room temperature for 30 minutes and 60 minutes, washed with water, and compared with the image portion before immersion. Printing durability is from Toyo Ink Co., Ltd.
Heidel GTO using Mark Five Red Ink
And a printing test was carried out, and the plate surface was determined to be wiped with the above-mentioned ultraplate cleaner every 1000 prints. The adhesion was evaluated by applying cellophane tape to the image area and then repeating the peeling three times to confirm whether or not the image area was peeled off. The results are shown in Table 1 (Table 1).

Example 2 2.0 g of a naphthoquinonediazide compound represented by the above formula (2), 2.1 g of a phenol resin compound represented by the formula (12) (formula 6) (average molecular weight Mw = 680), a phenol aralkyl resin [ Manufactured by Mitsui Toatsu Chemicals, Inc., Millex XL-225; average molecular weight Mw = 6500] 5.3
g, blue dye UV-Blue-784 [manufactured by Mitsui Toatsu Chemicals, Inc.] 0.05 g, 1,2-naphthoquinone-2-
A coating solution of a photosensitive resin composition comprising 0.06 g of diazido-4-sulfonyl chloride and 100 g of ethyl lactate was applied to an aluminum support by a spin coater so as to give a solid content of 2.0 g / m ^2. And dried at 90 ° C. for 5 minutes to obtain a positive photosensitive lithographic printing plate. Hereinafter, operation and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

[0020]

Embedded image

Example 3 2.0 g of a naphthoquinonediazide compound represented by the above formula (2), 1.6 g of a phenol resin compound represented by the formula (13) (formula 7) (average molecular weight Mw = 1530), a phenol aralkyl resin [ 4. Millex XL-225, manufactured by Mitsui Toatsu Chemicals, Inc .; average molecular weight Mw = 6500]
1 g, blue dye UV-Blue-784 [manufactured by Mitsui Toatsu Chemicals, Inc.] 0.05 g, 1,2-naphthoquinone-2-
A coating solution of a photosensitive resin composition comprising 0.06 g of diazido-4-sulfonyl chloride and 100 g of ethyl lactate was applied to an aluminum support by a spin coater so as to give a solid content of 2.0 g / m ^2. And dried at 90 ° C. for 5 minutes to obtain a positive photosensitive lithographic printing plate. Hereinafter, operation and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

[0022]

Embedded image

Example 4 2.0 g of a naphthoquinonediazide compound represented by the formula (2), 1.8 g of a phenol resin compound represented by the formula (14) (formula 8) (average molecular weight Mw = 1080), a phenol aralkyl resin [ 3. Made by Mitsui Toatsu Chemicals, Inc., Millex XL-225; average molecular weight Mw = 6500]
9 g, blue dye UV-Blue-784 [manufactured by Mitsui Toatsu Chemicals, Inc.] 0.05 g, 1,2-naphthoquinone-2-
A coating solution of a photosensitive resin composition comprising 0.06 g of diazido-4-sulfonyl chloride and 100 g of ethyl lactate was applied on an aluminum support using a spin coater so as to have a solid content of 2.0 g / m ^2. Apply, 9
After drying at 0 ° C. for 5 minutes, a positive photosensitive lithographic printing plate was obtained. Hereinafter, operation and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

[0024]

Embedded image

Example 5 2.0 g of a naphthoquinonediazide compound represented by the formula (3), 2.2 g of a phenol resin compound represented by the formula (15) (formula 9) (average molecular weight Mw = 880), a phenol aralkyl resin [ Manufactured by Mitsui Toatsu Chemicals, Inc., Millex XL-225; average molecular weight Mw = 6500] 4.4
g, blue dye UV-Blue-784 [manufactured by Mitsui Toatsu Chemicals, Inc.] 0.05 g, 1,2-naphthoquinone-2-
A coating solution of a photosensitive resin composition comprising 0.06 g of diazido-4-sulfonyl chloride and 100 g of ethyl lactate was applied on an aluminum support using a spin coater so as to have a solid content of 2.0 g / m ^2. Apply, 9
After drying at 0 ° C. for 5 minutes, a positive photosensitive lithographic printing plate was obtained. Hereinafter, operation and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

[0026]

Embedded image

Example 6 2.0 g of a naphthoquinonediazide compound represented by the above formula (2), 3.3 g of a phenol resin compound represented by the above formula (11), 3.0 g of a cresol novolak binder resin (average molecular weight Mw = 5000) 3.0 g , Blue dye UV
-Blue-784 [manufactured by Mitsui Toatsu Chemicals, Inc.] 0.0
5 g, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 0.06 g and ethyl lactate 100 g
A photosensitive resin composition coating solution consisting of was coated on an aluminum support using a spin coater so as to have a solid content of 2.0 g / m ² , and dried at 90 ° C. for 5 minutes.
A positive photosensitive lithographic printing plate was obtained. Hereinafter, operation and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 2.0 g of a naphthoquinonediazide compound represented by the formula (2), 6.0 g of a cresol novolak binder resin compound (average molecular weight Mw = 5000), blue dye U
V-Blue-784 [manufactured by Mitsui Toatsu Chemicals, Inc.]
05 g, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 0.06 g and ethyl lactate 100
g of a photosensitive resin composition coating solution was applied to an aluminum support using a spin coater so as to have a solid content of 2.0 g / m ² and dried at 90 ° C. for 5 minutes. The resulting photosensitive lithographic printing plate was obtained. Hereinafter, Example 1
The same operation as described above was performed and evaluated. The results are shown in Table 1.

[0029]

[Table 1] As is clear from Table 1, it can be seen that the lithographic printing plate obtained by using the photosensitive resin composition of the present invention exhibits extremely excellent printing durability, chemical resistance and adhesion.

[0030]

According to the present invention, it has become possible to provide a photosensitive resin composition for lithographic printing having good printing durability, chemical resistance and adhesion.

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Rihoko Suzuki 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemicals Co., Ltd.

Claims (3)

[Claims] 1. A photosensitive resin composition containing a photosensitive agent and a binder resin, wherein at least one compound represented by the general formula (1) (formula 1) is contained as a component of the binder resin. A photosensitive resin composition for lithographic printing. Embedded image (In the formula, R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and n represents 0 to 50.) 2. The photosensitive resin composition for lithographic printing according to claim 1, which comprises an o-naphthoquinonediazide compound as a photosensitive agent. 3. A photosensitive lithographic printing plate comprising the photosensitive resin composition according to claim 1 on a support.