JP2000338669A - Photosensitive composition and photosensitive planographic printing plate material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high sensitivity, to enable water development and to utilize such a light source as a high output semiconductor laser which emits near IR by incorporating a polymer having an oxazoline group in a side chain and an azido compound. SOLUTION: This photosensitive composition contains a polymer having an oxazoline group in a side chain and an azido compound. The polymer is preferably a polymer containing repeating units of the formula, wherein R1 is methyl, L is an arbitrary combining group which combines the principal chain of the polymer with an oxazoline group, the oxazoline group may directly bond to the principal chain and R2 and R3 are each H or an alkyl. When the polymer having repeating units of the formula is combined with the azido compound or a photo-acid generating agent, the oxazoline group causes crosslinking reaction in a part irradiated with light and a negative type photosensitive composition is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photosensitive composition, and more particularly to a photosensitive lithographic printing plate material utilizing the same. More specifically, the present invention relates to a photosensitive composition capable of forming an image using a laser and a photosensitive lithographic printing plate material. Further, the present invention relates to a water-soluble photosensitive composition suitable for forming a screen resist using a photosensitive water-soluble resin, a color filter, a phosphor pattern, and the like. The invention also relates to a negative photosensitive lithographic printing plate having sensitivity to light in the wavelength range of near infrared light.

[0002]

2. Description of the Related Art In recent years, semiconductor lasers have been increasing in output, longer life and lower cost, and have attracted attention as a preferable exposure light source. External semiconductor lasers having an output of 1 W or more have appeared on the market.

A so-called CTP for directly outputting digital data on a printing plate using the above-described semiconductor laser.
For use as a lithographic printing plate, see JP-A-7-20
No. 629, No. 271029, and No. 9-244226. Among these publications, a publication relating to a lithographic printing plate discloses a lithographic printing plate having a photosensitive layer basically containing a phenol resin, an infrared absorber, and an acid generator. Such a lithographic printing plate is exposed by, for example, a high-output semiconductor laser or the like, and utilizes the fact that the acid generated from a photoacid generator changes the solubility of a phenol resin in a developer due to crosslinking or the like.
In the negative type treatment, when using such a method, it is described in the above specification that the plate surface is subjected to heat treatment after exposure, and is required for promoting crosslinking of the phenol resin by a strong acid generated in the exposed part. In the process, the difference in solubility between the exposed and unexposed portions is not kept constant depending on the heating temperature. For example, if the heating is not performed sufficiently, the exposed portion may be dissolved to the exposed portion by a developer, or conversely, If the heating temperature is too high, there is a problem that the unexposed portion is partially insolubilized and the development is not sufficiently performed. Further, there is a problem in that the photosensitive layer naturally cures due to long-term storage property, particularly storage under high-temperature conditions, and that storage sensitivity decreases.

When a photosensitive composition basically containing an alkali-soluble resin, a photoacid generator, and an acid-catalyzed crosslinking agent (such as a resole resin or methylolmelamine) as described above is used, an alkaline aqueous solution is required for development. Water-developable photosensitive compositions and printing plates using the same, because of the problem of waste of alkaline developer and the problem of replenishment of the developer for maintaining the pH of the developer at an appropriate level. However, at present, no satisfactory system has been found.

For example, examples of a water-developable photosensitive composition include a system containing water-soluble diazide and polyvinylpyrrolidone (JP-A-48-90185) and a system containing polyvinylformamide (JP-A-10-301272). Gazette)
However, none of these was sufficient in terms of sensitivity. Furthermore, when trying to utilize such a photosensitive composition as a lithographic printing plate, there was a problem that a water-soluble polymer such as polyvinylpyrrolidone or polyvinylformamide had poor ink receptivity and could not be used as a printing plate. .

[0006]

SUMMARY OF THE INVENTION The present invention provides a photosensitive composition which has high sensitivity as a photosensitive material, can be developed with water, and can be used with a light source such as a semiconductor laser with near-infrared light and high output. That is the task. Another object of the present invention is to provide a lithographic printing plate material which can be developed with an aqueous developer having excellent image quality and printing durability.

[0007]

The object of the present invention is basically achieved by the following constitution. (1) A photosensitive composition comprising a polymer having an oxazoline group in a side chain and an azide compound. (2) A photosensitive composition comprising a polymer having an oxazoline group in a side chain and a photoacid generator. (3) A photosensitive composition comprising a polymer having a phenolic hydroxyl group, a compound having two or more oxazoline groups in a molecule, and a photoacid generator.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the photosensitive compositions shown in the above (1) and (2) will be described. Preferred examples of the polymer having an oxazoline group in the side chain include a polymer containing a repeating unit represented by the following general formula 1.

[0009]

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In the chemical formula ₁ , R ₁ represents hydrogen or a methyl group, L represents an arbitrary linking group for linking the polymer main chain and the oxazoline group, and the oxazoline group is directly linked to the main chain without L. May be. R ₂ and R ₃ represent a hydrogen atom or an alkyl group.

The polymer having a repeating unit represented by Chemical Formula 1 is combined with an azide compound or a photoacid generator to form a cross-linking reaction of an oxazoline group in a light-irradiated portion to give a negative photosensitive composition. Is the feature. Further, it is basically possible to form a negative type lithographic printing plate by applying a polymer having a repeating unit represented by Chemical formula 1 and an azide compound on a film or an aluminum support and forming a film. .

The proportion of the repeating unit containing an oxazoline group represented by Chemical Formula 1 present in the polymer is preferably at least 1 part by weight based on 100 parts by weight of the total amount of the polymer.
It is particularly preferred that the amount be in the range of 50 parts by weight to 50 parts by weight.

As preferred examples of the azide compound according to the present invention, compounds having at least two azide groups in the molecule as shown in Chemical formulas 2 and 3 are preferable. In it,
As shown in the above, those having a polar group such as a sulfonate group in the molecule and having solubility in water are particularly preferable. In Chemical Formula 2, X represents an alkali metal ion or an ammonium salt.

[0014]

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[0015]

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The azide compound mentioned in the above example is sensitive only to the ultraviolet region, and a polymer having an oxazoline group in the side chain as shown in Chemical formula 1 is produced by an intermediate nitrene generated by ultraviolet light exposure using a UV lamp or the like. It is characterized by crosslinking.

Preferred examples of the photoacid generator according to the present invention include, as onium salts, diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, or trihalomethyl-substituted triazine and oxadiazole derivatives, or nitro compounds. Examples include benzyl ester derivatives, aryl sulfonic acid ester derivatives, iron arene complexes, and the like. Among these, examples of photoacid generators which are particularly preferable are shown in Chemical formulas 4 and 5.

[0018]

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[0019]

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The photoacid generators mentioned in the above examples are sensitized only to the ultraviolet region, and a polymer having an oxazoline group in the side chain as shown in Chemical formula 1 is produced by an acid generated by ultraviolet light exposure using a UV lamp or the like. It is characterized by crosslinking. In order to sufficiently complete crosslinking, after exposure, for example, 100 to 130
By heating at about 1 ° C. for about 1 minute, the exposed portion can be selectively and sufficiently crosslinked.

The photosensitive composition and the photosensitive lithographic printing plate material can be made visible by adding a dye having an absorption in the visible to near infrared region together with the azide compound or the photoacid generator as described above. Photosensitivity can be imparted to any wavelength range from light to near infrared. Preferred examples of the dye used for such a purpose include cyanine, merocyanine, rhodanine, coumarin, and porphyrin dyes. In particular, when a high-output semiconductor laser or the like is used in the near-infrared light region, examples of the dye include a squarylium dye, a pyrylium dye, a dithiobenzylnickel complex, carbon black, and phthalocyanines in addition to the above examples. Examples of preferably used dyes are shown in Chemical formulas 6 to 9.

[0022]

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[0023]

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[0024]

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[0025]

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A high-power semiconductor laser having an oscillation wavelength in the near-infrared region is particularly preferred as a light source for sensitizing the photosensitive material according to the present invention, particularly a lithographic printing plate material, and the light energy exposed on the plate surface is several mW. / Cm ² or more is preferable. Specifically, 1 which emits light around 830 nm
A W-class high-power semiconductor laser or a YAG laser emitting at 1064 nm can be cited as a preferred laser light source according to the present invention.

It is preferable to use an aqueous developer for developing the photosensitive composition and the lithographic printing plate material using the polymer according to the present invention after exposure. When an alkaline developer is used as the aqueous developer, a polymer having a phenolic hydroxyl group is preferable. In this case, particularly preferred examples include various examples shown in Chemical formulas 10 and 11. Numerical values in the formula represent parts by weight.

[0028]

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[0029]

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In the above various examples, the molecular weight of the polymer is not particularly limited, but the degree of polymerization is 100 to 200.
It is preferable to use the one in the range of about 0 because the solubility is good and the viscosity of the solution is in an appropriate range.

Another preferred embodiment of the polymer according to the present invention is to use a water-soluble polymer having an oxazoline group. In this case, an alkali developing solution is not used as a developing solution, and water development can be simply performed. Examples of such a polymer include those represented by Chemical formulas 12 and 13, and a water-soluble resin having an oxazoline group obtained from Nippon Shokubai under the trade name of Epocros WS-500 is also preferably used. I can do it.

[0032]

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[0033]

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A further example of the polymer according to the present invention is a case where the polymer having an oxazoline group is a water-dispersible latex. In this case, the latex is used alone or together with another water-soluble polymer. To provide a photosensitive composition and a lithographic printing plate material which can be subjected to aqueous development. The water-dispersible latex used for such a purpose is Epocross K-20 from Nippon Shokubai Co., Ltd.
10E, K-2020E, K-2030E and the like are preferably used.

Although the components constituting the photosensitive compositions (1) and (2) according to the present invention have been described, there is a preferable range for the proportion of each component in the photosensitive layer. A preferable ratio of the photoacid generator is from 1 part by weight to 50 parts by weight, and a more preferable range is from 1 part by weight to 20 parts by weight based on 100 parts by weight of the polymer. The preferred ratio of the dye is from 0.1 part by weight to 2 parts.
The range is 0 parts by weight, and a more preferred range is 1 to 10 parts by weight.

Next, the photosensitive composition shown in the above (3), which is another embodiment of the present invention, will be described. This photosensitive composition comprises a polymer having a phenolic hydroxyl group, a compound having two or more oxazoline groups in the molecule, and a photoacid generator. Here, preferred examples of the polymer having a phenolic hydroxyl group include the following general formula 1
A polymer containing a repeating unit represented by Chemical formula 4, Chemical formula 15, or Chemical formula 16 is exemplified.

[0037]

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In the formula, R ₁ represents any substitutable group or atom, and p represents an integer of 1 to 3.

[0039]

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In the formula, R ₂ represents hydrogen or a methyl group.

[0041]

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In the chemical formula 16, R _{3 to} R ₆ represent hydrogen or carbon number 7
Represents the following alkyl groups.

Any polymer having a repeating unit represented by the above general formula undergoes a cross-linking reaction under acidic conditions with a compound having two or more oxazoline groups in a molecule described below, and is dissolved in an alkali developing solution. It is characteristic that the property decreases. In addition to the above examples, examples of the polymer further having a phenolic hydroxyl group include various novolak resins and resole resins other than those described in Chemical formula 16. A particularly preferred example of the polymer is shown in Chemical formula 17.

[0044]

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The molecular weight of the polymer having a phenolic hydroxyl group is not particularly limited.
It is particularly preferable to use the one in the range of about 2000 because the solubility is good and the viscosity of the solution is in an appropriate range.

As the compound having two or more oxazoline groups in the molecule, for example, an example shown in Chemical formula 18 is preferable.

[0047]

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The polymer having a repeating unit represented by Chemical Formulas 14 to 17 is used in combination with the above-described photoacid generator to cause a cross-linking reaction of the polymer with an oxazoline compound by an acid generated in a light irradiation portion. It is characterized by providing a negative photosensitive composition. Further, a polymer having a repeating unit represented by Chemical formulas 14 to 17, an oxazoline compound and a photoacid generator are applied on a film or an aluminum support to form a film, whereby a negative type lithographic printing plate can be obtained. Basically it is possible.

The photoacid generators mentioned in the above examples are sensitive only to the ultraviolet region, and are characterized in that the polymer is cross-linked in the presence of an oxazoline compound by an acid generated by ultraviolet light exposure with a UV lamp or the like. It is. In order to complete the crosslinking sufficiently, the exposed portion can be selectively and sufficiently crosslinked after exposure by heating, for example, at about 100 to 130 ° C. for about 1 minute. When sufficiently applied, a good negative image can be obtained by alkali development without performing heat treatment.

The photosensitive composition and the photosensitive lithographic printing plate material are prepared by adding a dye having an absorption in the visible to near infrared region as described above together with the above-mentioned photoacid generator. Can have photosensitivity in any wavelength range from visible light to near infrared region.

Although the components constituting the photosensitive composition (3) according to the present invention have been described, the ratio of each component in the photosensitive layer has a preferable range. The preferred range of the oxazoline compound is 1 part by weight to 50 parts by weight, and the preferred ratio of the photoacid generator is 1 part by weight to 50 parts by weight, more preferably 100 parts by weight of the polymer. Is 1 part by weight to 2
The range is 0 parts by weight. The preferred ratio of the dye is in the range of 0.1 to 20 parts by weight, and the more preferable range is in the range of 1 to 10 parts by weight.

The components constituting the photosensitive compositions (1), (2) and (3) of the present invention can contain other components in addition to the components described above for various purposes. . It is also preferable to add various dyes and pigments for the purpose of enhancing the visibility of images, and to add inorganic fine particles or organic fine particles for the purpose of preventing blocking of the photosensitive composition. Further, another layer may be provided adjacent to the photosensitive layer for the purpose of protecting the photosensitive layer.

Regarding the thickness of the photosensitive layer itself when used as a lithographic printing plate material, it is preferable to form the photosensitive layer on a support with a dry thickness in the range of 0.5 to 10 microns, and more preferably 1 to 5 microns. It is extremely preferable that it is within the range, in order to greatly improve the printing durability.
The photosensitive layer is prepared by preparing a solution in which the above three components are mixed, coating the solution on a support using various known coating methods, and drying the solution. As the support, for example, a film or a polyethylene-coated paper may be used, but a more preferable support is an aluminum plate having a polished and anodized film.

In order to use the material having the photosensitive layer formed on the support as described above as a printing plate, the material is subjected to contact exposure or laser scanning exposure, and the exposed portions are crosslinked. Since the solubility in the alkaline developer decreases, pattern formation is performed by eluting the unexposed portions with the alkaline developer described below.

After the exposure, it is also preferable to carry out a heat treatment for the purpose of completing the crosslinking reaction and strengthening the resistance to an alkali developing solution.
To 150 ° C., and the heating time is preferably in the range of several seconds to several minutes.

The alkaline developer is not particularly limited as long as it is a solution for dissolving the polymer according to the present invention, but is preferably an alkaline developer such as sodium hydroxide, potassium hydroxide, sodium silicate and sodium metasilicate. The aqueous developer in which the compound is dissolved is very preferable because it can satisfactorily selectively dissolve the unexposed portion and expose the lower support surface. After performing development processing using such an alkali developing solution, normal gumming is preferably performed using gum arabic or the like.

[0057]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as well as the effects. Parts in Examples are parts by weight.

Example 1 Synthesis Example (Synthesis Example of P-4 in Chemical Formula 11) 100 g of polyvinyl alcohol (Kuraray PVA-105, degree of saponification 98.5 mol%) was converted into 500 g of dimethylformamide (DMF) and 100 g of benzene. After suspending, 3 grams of p-toluenesulfonic acid was added.
At an internal temperature of 50 ° C., 70 g of o-hydroxybenzaldehyde and 16 g of 4-cyanobenzaldehyde were added, and the mixture was stirred for 6 hours while refluxing benzene at reflux temperature while removing azeotropic water, followed by cooling to room temperature. . Then, after neutralizing the reaction system by adding triethylamine,
The whole was added to a large amount of water, and the precipitated polymer was separated and dried in a vacuum dryer. The obtained polymer was dissolved in 500 ml of methoxypropanol while heating, and 5 g of zinc acetate was added.
2 g was added, and the mixture was heated and stirred on an oil bath heated to 130 ° C. for 25 hours. A small amount was sampled, no absorption by a cyano group was observed by an infrared spectrophotometer, and 6 μm
After confirming that absorption by the oxazoline ring was observed in the vicinity, the mixture was cooled to room temperature and the whole was poured into a large amount of ion-exchanged water. The deposited precipitate was sufficiently washed with running water and dried by heating under reduced pressure. A small amount of the obtained polymer was collected, dissolved in deuterated DMSO, and subjected to structural analysis by proton NMR. As a result, it was analyzed that each repeating unit was contained at the ratio indicated by P-4.

Using the polymer (P-4) obtained in the above synthesis example, a photosensitive composition solution having the following formulation was prepared, and a dry film thickness was formed on a 100-micron polyester film using a wire bar. Coating was performed so as to have a thickness of 3 μm to prepare a photosensitive film. Polymer (P-4) 10 parts by weight Azide compound (A-12) 1 part by weight Dioxane 70 parts by weight DMF 20 parts by weight

The obtained photosensitive film was exposed for 1 second through a mask film having a step wedge with a density difference of 0.15 at a light intensity of 220 mW using a photometer using a high-pressure mercury lamp as a light source. After heating for 1 minute in a dryer heated to 130 ° C., development was performed using a developing solution in which sodium metasilicate was dissolved at 6% by weight, and a portion giving an exposure amount of about 10 mJ / cm ² or more was obtained. Remained as an image, and a relief pattern was formed.

Example 2 In the same manner as in Example 1, a photosensitive composition solution having the following formulation was prepared using the polymer (P-4) obtained in the above Synthesis Example, and was prepared using a wire bar. A photosensitive film was prepared by coating a 100 μm thick polyester film so that the dry film thickness was 3 μm. Polymer (P-4) 10 parts by weight Photoacid generator (PAG-5) 1 part by weight Dioxane 70 parts by weight DMF 20 parts by weight

The obtained photosensitive film was exposed for 1 second through a mask film having a step wedge with a density difference of 0.15 at a light intensity of 220 mW using a photometer using a high-pressure mercury lamp as a light source. After heating for 1 minute in a dryer heated to 130 ° C., development was performed using a developing solution in which 6% by weight of sodium metasilicate was dissolved. As a result, a portion giving an exposure amount of about 6 mJ / cm ² or more was obtained. Remained as an image, and a relief pattern was formed.

Example 3 Using the photosensitive composition liquids used in Examples 1 and 2, each was subjected to graining treatment, and was similarly coated on an anodized aluminum plate and dried to prepare a photosensitive lithographic printing plate. Exposure was performed through a negative film original having a step wedge and a resolution pattern in exactly the same manner as in Example 1, and heating was further performed for 1 minute in a dryer heated to 130 ° C. Development was performed in the same manner as in Example 1, and a pattern was formed on the anodized aluminum plate. This was coated on the surface with a gum arabic solution and subjected to a printing test as a lithographic printing plate. Ryobi 3200 (Molton type printing machine) is used as the printing machine, and ink is used for new offset printing using New Champion Boku H (manufactured by Dainippon Ink Co., Ltd.) and dampening water is 1% Toho etch liquid. Was done. Example 1
And both of the lithographic printing plates using the photosensitive composition liquid used in Example 2 had better ink inking property than the beginning of printing,
In addition, in the non-image area, a good printed matter was obtained without occurrence of background stain, and a good result of 100,000 or more in printing durability was obtained.

Example 4 A liquid having the following composition was used as a photosensitive composition liquid. Polymer (P-4) 10 parts by weight Azide compound (A-12) 1 part by weight Dye (S-8) 0.1 part by weight Dioxane 100 parts by weight DMF 10 parts by weight

The photosensitive composition solution was applied and dried on an anodized aluminum plate to a dry film thickness of 1.2 μm in the same manner as in Example 3 to prepare a photosensitive lithographic printing plate precursor. This is wound around a drum, and has a wavelength of 830 nm.
Using a W output semiconductor laser, perform pulse exposure,
A resolution test pattern was printed. The exposure energy on the surface of the photosensitive lithographic printing plate was 200 mJ / cm ² . After exposure, the photosensitive lithographic printing plate was removed from the drum and
After heating at 1 ° C. for 1 minute, development was performed in exactly the same manner as in Example 1 to produce a lithographic printing plate. A printing test was performed in exactly the same manner as in Example 3, and similarly good results were obtained.

Example 5 A liquid having the following composition was used as a photosensitive composition liquid. Polymer (P-4) 10 parts by weight Photoacid generator (PAG-1) 1 part by weight Dye (S-6) 0.1 parts by weight Dioxane 100 parts by weight DMF 10 parts by weight

The photosensitive composition solution was applied and dried on an anodized aluminum plate to a dry film thickness of 1.2 μm in the same manner as in Example 3 to prepare a photosensitive lithographic printing plate precursor. This is wound around a drum, and has a wavelength of 830 nm.
Using a W output semiconductor laser, perform pulse exposure,
A resolution test pattern was printed. The exposure energy on the surface of the photosensitive lithographic printing plate was 100 mJ / cm ² . After exposure, the photosensitive lithographic printing plate was removed from the drum and
After heating at 1 ° C. for 1 minute, development was carried out in exactly the same manner as in the example to prepare a lithographic printing plate. A printing test was performed in exactly the same manner as in Example 3, and similarly good results were obtained.

Example 6 The following photosensitive composition solution was prepared using Epocross WS-500 (Nippon Shokubai Co., Ltd.) as a water-soluble polymer having an oxazoline group. Epocross WS-500 (40%) 25 parts by weight Azide compound (A-3) 1 part by weight Dye (S-8) 0.2 parts by weight Ethanol 10 parts by weight Water 90 parts by weight

A photosensitive composition solution having the above composition was applied on a polyester film, and this was wound around a drum.
Using a 1 W output semiconductor laser having a transmission wavelength of nm, pulse exposure was performed, and a resolution test pattern was printed. The exposure energy on the photosensitive lithographic printing plate surface is 20
It was 0 mJ / cm ² . After the exposure, the photosensitive lithographic printing plate was taken out of the drum and heated at 130 ° C. for 1 minute. This was washed in running tap water to obtain a relief image on the film. When the formed image was observed with an optical microscope, a pattern of 10 μm in fine lines and a pattern of 15 μm in dots were clearly reproduced, and the non-image portions between the fine lines formed at intervals of 20 μm were also well dissolved and removed. It was confirmed that it was.

Example 7 As a water-soluble polymer having an oxazoline group,
The following photosensitive composition solution was prepared using medium P-6. P-6 (30%) 33 parts by weight Photoacid generator (PAG-3) 1 part by weight Dye (S-6) 0.2 parts by weight Ethanol 100 parts by weight

The photosensitive composition solution having the above composition is applied on an aluminum plate, and a contact printer using a tungsten lamp as a light source is used. went. After exposure for a time (60 seconds) corresponding to an exposure amount of about 200 mJ / cm ² , heating was performed at 130 ° C. for 1 minute. This was washed in running tap water to obtain a relief image on an aluminum plate. When the formed image was observed with an optical microscope, a pattern of 10 μm in fine lines and a pattern of 15 μm in dots were clearly reproduced, and the non-image portions between the fine lines formed at intervals of 20 μm were also well dissolved and removed. It was confirmed that it was.

Example 8 The following photosensitive composition solution was prepared using Epocross K-2010 (oxazoline equivalent 550, Nippon Shokubai) as a water-dispersible latex having oxazoline groups. Epocros K-2010 (40%) 20 parts by weight Polyvinyl alcohol (Kuraray PVA203) (10% aqueous solution) 20 parts by weight Azide compound (A-3) 1 part by weight Pigment (S-10) 0.2 parts by weight Dioxane 10 parts by weight DMF 1 part by weight

The photosensitive composition was prepared by dissolving the dye in a solvent in advance, and then dropping the solution in an aqueous dispersion containing an azide compound, epocross and PVA under ultrasonic irradiation.
The obtained photosensitive composition solution was applied and dried on an anodized aluminum plate in exactly the same manner as in Example 3 to prepare a photosensitive lithographic printing plate precursor, and was exposed using a high-power semiconductor laser emitting at 830 nm. Was. After exposure, heat treatment at 130 ° C. for 1 minute, wash out unexposed areas with tap water,
A printing test was performed in exactly the same manner as in Example 3. The printing performance was as good as that of Example 3 and good results were obtained.

Example 9 The following photosensitive composition solution was prepared using Epocross K-2030 (oxazoline equivalent 550, Nippon Shokubai) as a water-dispersible latex having oxazoline groups. Epocros K-2030 (40%) 20 parts by weight Polyvinyl alcohol (Kuraray PVA203) (10% aqueous solution) 20 parts by weight Photoacid generator (PAG-4) 1 part by weight Pigment (S-12) 0.2 parts by weight Dioxane 10 Parts by weight DMF 1 part by weight

The photoacid generator and the dye were dissolved in a solvent in advance, and then dropped into an aqueous dispersion containing epocross and PVA under ultrasonic irradiation to prepare a photosensitive composition solution. The obtained photosensitive composition solution was applied and dried on an anodized aluminum plate in exactly the same manner as in Example 3 to prepare a photosensitive lithographic printing plate precursor, and was exposed using a high-power semiconductor laser emitting at 830 nm. Was. After exposure, 130 ℃ 1
After performing a heat treatment for 1 minute and washing out unexposed portions with tap water, a printing test was performed in exactly the same manner as in Example 3. The printing performance was as good as that of Example 3 and good results were obtained.

Example 10 Synthesis Example (Synthesis Example of P-9 in Chemical Formula 17) 120 g of polyvinyl alcohol (Kuraray PVA-105, saponification degree 98.5 mol%) was converted into 500 g of dimethylformamide (DMF) and 100 g of benzene. After suspending, 5 grams of p-toluenesulfonic acid was added.
P-Hydroxybenzaldehyde 120 at an internal temperature of 50 ° C
Grams were added, and the mixture was stirred for 6 hours while refluxing benzene at reflux temperature while removing azeotropic water, and then cooled to room temperature. Next, the reaction system was neutralized by adding triethylamine, and then the whole was added to a large amount of water, and the precipitated polymer was separated and dried in a vacuum dryer.

Using the polymer (P-9) obtained in the above synthesis example, a photosensitive composition solution having the following formulation was prepared, and a dry film thickness was formed on a 100-micron-thick polyester film using a wire bar. Coating was performed so as to have a thickness of 3 μm to prepare a photosensitive film. Polymer (P-9) 10 parts by weight Oxazoline compound (OX-1) 2 parts by weight Photoacid generator (PAG-5) 1 part by weight Dioxane 70 parts by weight DMF 20 parts by weight

The obtained photosensitive film was exposed for 1 second through a mask film having a step wedge with a density difference of 0.15 at a light intensity of 220 mW using a photometer using a high-pressure mercury lamp as a light source. Immediately after the exposure, development was performed using a developing solution in which sodium metasilicate was dissolved at 6% by weight. As a result, a portion having an exposure amount of about 300 mJ / cm ² or more remained as an image, and a relief pattern was formed. .

Example 11 Using the photosensitive composition solution used in Example 10, graining treatment was performed, and coating and drying were similarly performed on an anodized aluminum plate to prepare a photosensitive lithographic printing plate. Exposure was performed through a negative film original having a step wedge and a resolution pattern in the same manner as in Example 1. Immediately thereafter, development was performed in the same manner as in Example 10, and a pattern was formed on the anodized aluminum plate. This was coated on the surface with a gum arabic solution and subjected to a printing test as a lithographic printing plate. The printing machine is Ryobi 3200 (Molton printing machine)
The offset printing was performed by using New Champion Boku H (manufactured by Dainippon Ink Co., Ltd.) as the ink and 1% Toho etch liquid as the dampening solution. Ink adhesion was better than that at the beginning of printing, and good printed matter was obtained without occurrence of background smear in non-image areas, and good results of printing durability of 100,000 or more were obtained.

Example 12 A liquid having the following composition was used as a photosensitive composition liquid. Polymer (P-10) 10 parts by weight Oxazoline compound 2 parts by weight Photoacid generator (PAG-1) 1 part by weight Dye (S-6) 0.1 part by weight Dioxane 100 parts by weight DMF 10 parts by weight

The photosensitive composition solution was applied and dried on an anodized aluminum plate to a dry film thickness of 1.2 μm in the same manner as in Example 11 to prepare a photosensitive lithographic printing plate precursor. This was wound around a drum and pulse exposure was performed using a 1 W output semiconductor laser having an emission wavelength of 830 nm to print a resolution test pattern. The exposure energy on the surface of the photosensitive lithographic printing plate was 300 mJ / cm ² . After exposure, remove the photosensitive lithographic printing plate from the drum,
Development was carried out in exactly the same manner as in Example 10 to produce a lithographic printing plate. A printing test was performed in exactly the same manner as in Example 11,
Similarly good results were obtained.

[0082]

According to the present invention, a photosensitive composition having high sensitivity as a photosensitive material, a light source including a high-output semiconductor laser can be used, and a water-developable photosensitive composition, and excellent image quality and printing durability can be obtained. Give lithographic printing plate material.

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Claims (7)

[Claims] 1. A photosensitive composition comprising a polymer having an oxazoline group in a side chain and an azide compound. 2. A photosensitive composition comprising a polymer having an oxazoline group in a side chain and a photoacid generator. 3. A photosensitive composition comprising a polymer having a phenolic hydroxyl group, a compound having two or more oxazoline groups in a molecule, and a photoacid generator. 4. The photosensitive composition according to claim 1, wherein the polymer is a water-soluble resin. 5. The photosensitive composition according to claim 1, wherein the polymer is a water-dispersible latex. 6. The photosensitive composition according to claim 1, wherein the photosensitive composition further contains a dye having absorption in a wavelength range from visible light to near-infrared light. object. 7. A photosensitive lithographic printing plate material utilizing the photosensitive composition according to claim 1. Description: