KR100560281B1 - Positive-type photosensitive composition - Google Patents

Abstract

Alkali-soluble positive photosensitive composition having infrared wavelength laser photosensitivity. It is not necessary to burn and is applied under the condition of 25 ~ 60% of the temperature in the work room, so that sufficient adhesiveness can be obtained, and a high sensitivity is maintained so that no residue can be formed, it is cut to a sharp outline, and the resist film is hard The positive photosensitive composition which improves the scratch resistance in handling before image development.

Alkali-soluble organic polymer material which has a phenolic hydroxyl group, the photothermal conversion material which absorbs infrared rays which are image exposure light sources, and converts into heat, and adhesive modifiers, such as a polyvinyl polypyrrolidone / polyvinylacetate copolymer, are contained.

Description

Positive type photosensitive composition {POSITIVE-TYPE PHOTOSENSITIVE COMPOSITION}

The present invention relates to an alkali-soluble positive photosensitive composition having infrared wavelength laser photosensitivity in which exposure light sources are exposed to a laser beam having a wavelength of 700 to 1,100 nm and are available to a developer.

The conventional old positive type photosensitive flat plate printing plate contains o-quinone diazide compound which is a substance which photosensitizes a novolak resin and white light, As shown by following formula (1), photodegradation of o-quinone diazide compound is carried out. (Chemical change) causes an Arndt-Eistert type potential to form a ketene structure, generating 5-membered cyclic carboxylic acid in the presence of water, and ketene on the photosensitive layer in the exposed portion reacts with naphthoquinone diazide under the photosensitive layer to form a lactone. And the lactone ring is opened at the time of development by the aqueous alkali solution to form sodium carbonate, and the coexisting novolac is also alkali-soluble so that the photosensitive layer of the unexposed part coexists with the alkali at the time of development. Coupling reaction occurs with the novolac, which becomes alkaline poorly soluble and remains as a resist image. Thus, when the o-quinone diazide compound is included, the development latitude can be largely obtained.

Here, the development latitude can be defined as that development operation can be performed because there is a difference between the time until the exposure part is completely removed from the developer and the time when the remaining film ratio of the unexposed part is sufficiently secured even when the developer is lost. .

On the other hand, in order to make the plate making under white light, the positive type photosensitive composition which utilizes changes other than chemical change was invented, the positive image is printed by laser light of an infrared wavelength range, and the solubility to the developing solution of an exposure part is improved. The method of forming a positive image by increasing it is devised, and it is implemented by offset plate making and flexographic plate making.

As technical documents, for example, Japanese Patent Application Laid-Open No. 10-268512, Japanese Patent Application Laid-Open No. 11-194504, Japanese Patent Application Laid-Open No. 11-223936, Japanese Patent Application Laid-Open No. 11-84657, and Japanese Patent Publication Japanese Patent Laid-Open No. 11-174681, Japanese Patent Laid-Open No. 11-231515, WO97 / 39894, WO98 / 42507, Japanese Patent Laid-Open No. 2002-189293, Japanese Patent Laid-Open No. 2002-189294, and the like.

The positive photosensitive flat panel described in each of the above documents is produced by infrared laser light exposure using a substance which absorbs infrared light such as infrared absorbing dye and converts it into heat and an alkali soluble resin such as novolac resin as a main photosensitive layer component. The heat causes physical changes such as the conformation change of the resin to increase the solubility in the developer.

However, a positive photosensitive plate printing plate which does not contain an o-quinonediazide compound and which prints a positive image by laser light in an infrared wavelength region, causes physical changes such as a conformation change of a resin and seeks to increase solubility. In this case, burning (heating operation) is required after the coating film, and even if burning, the difference in dissolution rate between the exposed portion and the unexposed portion is small, and the basic performance of the printing plate such as sensitivity and developing latitude is inferior, and thus the number of developing treatments is increased. It is under the circumstances that it is difficult to satisfy the development stability at the time.

On the other hand, the gravure plate making differs at all. In Japan, where gravure engraving and printing are most prevalent, a gravure engraving method is conventionally performed in which gravure engraving is performed using a positive thermal resist that can be developed without heating after coating film formation. There is no experimental literature at all.

In the past, the gravure engraving process of the plated roll by the corrosion method or the laser engraving method is carried out, for example, carrying in, degreasing, washing, pickling, washing, ballad treatment, washing, ballad copper plating, washing, and grinding. Polishing, washing, photosensitizer coat, antioxidant coat, image printing by infrared laser exposure apparatus, developing, washing, etching, washing, washing, resist peeling, washing, washing, chrome plating, washing, polishing, washing, washing It is.

As a technical document that discloses a gravure engraving process for a plated roll by the corrosion method / laser making method, Japanese Patent Application Publication No. 10-193551, Japanese Patent Application Form No. 10-193552, Japanese Patent Application Publication 2000-062342, Japanese Patent Application Publication 2000- 062343, Japanese Patent Publication 2000-062344, Japanese Patent Publication 2001-179923, Japanese Patent Publication 2001-179924, Japanese Patent Publication 2001-187440, Japanese Patent Publication 2001-187441, Japanese Patent Publication 2001-191475, Japanese Patent Publication 2001-191476 Japanese Patent Publication 2001-260304, Japanese Patent Publication 2002-127369, Japanese Patent Publication 2002-187249, Japanese Patent Publication 2002-187250, Japanese Patent Publication 2002-200728, Japanese Patent Publication 2002-200729, Japanese Patent Publication 2002-307640, Japanese Patent Laid-Open No. 2002-307641 is mentioned.

In the gravure engraving process described in the above-mentioned document, either of which coats the photosensitive film which consists of a negative photosensitive composition agent, and does not coat the photosensitive film which consists of a positive photosensitive composition agent. In the conventional etching method, a negative photosensitive film is applied to a platen roll, and the coating film is dried at room temperature to form a negative photosensitive film, which is printed by an argon ion laser, and a positive photosensitive film is applied to the platen roll. The formation and printing of the positive photosensitive agent image by the infrared light laser beam are not performed.

The high power semiconductor laser head of CreoScitex Co., Ltd. of Canada emits an infrared wavelength region laser, and is widely used worldwide because it can be mounted on an offset printing machine and irradiated to a positive photosensitive composition to perform good development.

If the beam diameter of the argon ion laser beam and the beam diameter of the laser beam having a wavelength of 700 to 1,100 nm are the same size, the resolution of the laser becomes higher in the positive type than in the negative type, and the processing time is greatly shortened.

Further, the method of printing the positive image of the photosensitive film of the positive photosensitive composition with the laser of the infrared wavelength region is more preferable to cut the pattern than to print the image of the photosensitive film of the negative photosensitive composition with an argon laser. This is considered to be the difference of the cutting of a pattern by the difference of the composition of a positive photosensitive composition and a negative photosensitive composition.

In the past, the reason why the negative photosensitive composition was not used in the gravure plate even though the positive photosensitive composition agent is used in the offset plate and the flexographic plate is because the negative type photosensitive agent can be used in the gravure plate. Since the negative photosensitive agent is used to fix the degree of polymerization of the resin in the exposed portion by irradiating the magnetic lines, the development latitude can be sufficiently secured regardless of the material of the surface to be coated.

On the other hand, there was no positive photosensitive composition agent having a developing latitude which was satisfactory in the relationship with the copper sulfate plating of the gravure printing roll. In particular, the photosensitive composition which does not burn after application | coating did not exist at all. Even if a positive photosensitive composition agent used in offset or flexographic plates is applied to a toner for rolls for gravure, there are almost no conditions under which film can be formed. In most cases, the coating film of the positive photosensitive composition agent to the to-be-rolled roll for gravure flows in the alkali developing solution entirely. The same applies to burning after coating.

The high-resolution gravure engraving system using a positive photosensitive film using a semiconductor laser or a YAG laser capable of high output of laser light in the infrared wavelength range is smaller in size and engraving than an argon ion laser. The realization is strongly desired from the viewpoint of environmental light, resolution, and clipping of the city.

MEANS TO SOLVE THE PROBLEM In view of the above situation, the present inventors started development of the positive photosensitive composition agent which has sufficient development latitude because it does not burn after application | coating in relationship with copper sulfate plating of a gravure printing roll.

And about the etching method as one of the gravure printing roll making methods, the stock solution of the positive photosensitive composition which mix | blended novolak resin and cyanine pigment | dye was made, and the positive photosensitive agent which diluted this stock solution with the solvent was used for the gravure roll roller. The coating was formed on the surface of copper sulfate plated. For the application of the positive photosensitive agent, a photosensitive film coating apparatus (manufactured by Sink Laboratories Co., Ltd.) according to Japanese Patent Publication No. 07-109511 was used. Then, a photosensitive film was tested by irradiating a laser in the infrared wavelength region by using an infrared laser exposure apparatus (manufactured by Sink Laboratories Co., Ltd.) equipped with a Creoscitex high-power semiconductor laser head to print a positive image. This entirety deviated and no satisfactory resist image could be obtained.

Evaluation of the film formation by the photosensitive film coating apparatus according to Japanese Patent Publication No. 07-109511, the spiral coating method of the contact coating method in which the coating roll was immersed in the photosensitive agent in the tank and painted the photosensitive agent on the surface to be coated many times. In addition, it is thought that air is drawn into the photoresist film, and furthermore, since the tank is open, the solvent in the photoresist stored in the tank is evaporated, the latent heat of evaporation is taken away, and the application roller becomes cold, resulting in application with bleaching phenomenon. It was also found that the solvent concentration constantly decreased, and the viscosity gradually increased, so that it was impossible to coat the film with a uniform film thickness. As a result, it was concluded that the positive photoresist film was extremely inadequate even if the negative photosensitive agent was applied and formed by the photosensitive film coating apparatus according to Japanese Patent Publication No. 07-109511.

Therefore, by changing to the photosensitive film coating apparatus according to Japanese Patent Publication No. 07-109511, it is possible to apply non-contact to the toner plate roll in a closed state in which the solvent in the photosensitive agent in the tank does not increase. A photosensitive film coating apparatus has been developed in which coating is avoided.

Although the said photosensitive film coating apparatus is mentioned above in the item of embodiment of this invention, in summary, it is a method of manufacturing a film | membrane by apply | coating a positive photosensitive agent to a toner plate roll, Comprising: The upper end of the photosensitive agent outflow pipe which is a vertical pipe is carried out horizontally at both ends. The chuck is moved close to the lower surface of one end of the platen roll to be rotated, and the photosensitive agent is supplied so as to flow out of the top of the photosensitive agent outlet pipe and overflows so as to move the photosensitive agent outlet tube from one end of the platen roller to the other end. The coating liquid is applied to the plated roll by the spiral scanning method, and the rotation of the roll is continued until the coating film is naturally dried.

Therefore, as a result of the study, strong adhesion to the copper sulfate-plated surface of the positive photosensitive composition could not be obtained, and when developed, it immediately flowed out of the alkaline developer without distinction between the caustic and non-caustic portions.

For this reason, it was thought that burning after heating a film surface at high temperature after a coating film and giving adhesive force cannot be avoided.

It is thought that the need for burning does not occur due to the extremely insufficient adhesion of the positive photosensitive composition to the copper sulfate plated surface. This is because it was thought that the adhesion could be enhanced by strengthening the hydrogen bond of the alkali-soluble organic polymer material.

The surface was burned, and the study was continued. After the positive photosensitive composition containing the above-described novolak resin and cyanine pigment was applied to the platen roll, the film was burned for 30 minutes so that the film surface temperature was 60 ° C. When developed by laser exposure, the phenomenon became defective.                         

Therefore, the film was burned for 30 minutes so that the film surface temperature was 130 ° C. Nevertheless, the phenomenon of total deviation from the non-fired part also occurred.

It was concluded that the poor development even when burning was caused by the too low adhesion of the positive photosensitive composition to copper sulfate plating.

Then, as a silane coupling agent was added as an adjuvant which raises adhesive force to a positive photosensitive composition, the adhesive force of the photosensitive film was made to increase, and exposure and image development were able to be performed slightly satisfactorily.

Specifically, for example, a 200 mm diameter platen roll is rotated at a low speed of 25 r.pm to apply a positive photosensitive agent, and the rotation is continued so as not to produce a liquid flow, and 5 minutes are passed under natural drying conditions so that liquid flow does not occur. After drying the solvent-vaporized photosensitive film | membrane in the state set, the solvent residual density | concentration when burning at 130 degreeC for 30 minutes was less than 2%, the image could be printed by a laser, and it could develop.

However, the adhesion to the film was not the best, and the exposure and development did not exceed the slightly favorable region.

In addition, when the film surface temperature was set to 130 ° C, burning and subsequent cooling required a time of 100 minutes or more, a large amount of thermal energy was required, and the running cost was high, indicating that the practicality was insufficient.

In addition, when the film surface temperature is 130 ° C, hydrogen bonding of alkali-soluble organic polymers having phenolic hydroxyl groups becomes stronger and harder to develop, and deterioration in sensitivity due to denaturation of cyanine pigments results in poor pattern cutting. I could feel it.

And when a good observation was carried out regarding a resist image, it turned out that many pinholes generate | occur | produce. There was no such pinhole in the negative resist image. On the other hand, only the washing after the fine grinding by the grinding wheel cannot wash away the abrasive powder adhering to the platen roll completely. If the platen room is not a high clean room, the dust adheres to the platen rolls during transportation of the platen roll. It is thought that the positive resist image and the positive resist image are more sensitive to the film production conditions than the negative resist image.

Therefore, as a result of various examinations, when wiping cross was fully planted before apply | coating a photosensitive agent to a to-be-rolled roll, generation | occurrence | production of a pinhole was able to be suppressed.

Next, the gravure roll for gravure rolls are made of aluminum and iron, and in addition, if the roll diameters are different and the roll diameters are different, the thicknesses are all different. Even if heated, the heat is transferred to the roll base, so the temperature is not always heated to 130 ° C, but an imbalance is generated at different temperatures. Therefore, it is important to lower the temperature to eliminate the problem of specific heat capacity.

It was thought that burning to significantly reduce the solvent concentration could be achieved even if the film surface temperature was much lower than 130 ° C by selecting a composition having good solvent release.

When the heating time was shortened and the burning temperature of the membrane surface was reduced to 80 to 100 ° C. and burned for 50 minutes, it was confirmed that the solvent concentration was 6% or less, but the result was development failure. As a cause, it was concluded that sufficient adhesive force as said silane coupling agent could not be obtained.

Subsequently, the imidazole which is a hardening accelerator was put in place of a silane coupling agent as an adhesive agent, but it did not change in particular with the case of a silane coupling agent, and the burning temperature of a film surface was also the same as the case of a silane coupling agent.

Subsequently, various adhesives were added to the stock solution of a positive photosensitive composition comprising an alkali-soluble organic polymer material having a phenolic hydroxyl group and a photothermal conversion material that absorbs infrared light as an image exposure light source and converts it into heat. The photoresist was formed by using a copper sulfate-plated roller at and the test image was exposed and developed by the infrared laser exposure apparatus (manufactured by Sink Laboratories Co., Ltd.), and the photosensitive film of the positive photosensitive composition containing titanium organic compound was added. As for, the burning temperature could be significantly reduced.

In the case of the photosensitive film | membrane of the positive photosensitive composition which added the titanium organic compound, even if burning temperature was 46 degreeC, it could form favorable, a sensitivity became favorable, and image development could be performed easily.

However, in the test which was not burned out, favorable film formation was not possible, resulting in poor development.

Even if the burning temperature can be reduced to around 50 ° C, burning requires the cooling after burning, the time and energy required for burning and subsequent cooling, and the line of the device being burned. It becomes long, and it becomes disadvantageous that equipment cost and running cost become high. Again, I thought that making burning unnecessary was a problem to be solved.

When burned, the roll, unlike thin boards, takes 30 to 60 minutes to heat up to the required temperature and takes 50 to 100 minutes to cool down to room temperature. Since it depends on the size, uniform control is not possible. Further, burning causes one of the causes of denaturation of the cyanine dye, deterioration of sensitivity, worsening of the pattern being cut off, and thinning of the resist at the time of development, leading to retraction of the contour and pinholes.

Therefore, development of a positive photosensitive film which does not require burning is strongly desired.

As a result of repeating several tests, if the total solvent residue concentration of MEK, IPA, PM, etc. during the film formation is high, the image is not printed by the laser (the main chain or the side chain of the molecules of the photoresist film-forming resin in the exposed part). It was found that the part of was cut into a low molecule having a higher alkali solubility, and that a latent flaw in the state in which the photosensitive layer was scattered properly could not be formed.

After the positive type photosensitive agent was applied to the copper sulfate plated plate and the product was blown at a room temperature of 25 ° C. for 15 minutes under natural drying conditions, the solvent residue concentration was 11% and the solvent residue concentration after 25 hours was 9%. After the positive photosensitive agent was applied to the platen roll rotating at 45r.p.m, and measured after 10 minutes, it was found that the solvent residual concentration was reduced to only 7%.

Therefore, in order to regenerate the stock solution of the positive photoresist film which does not require burning by reforming including the preparation that enhances adhesion to the positive photoresist, and to confirm the result by exposure and development, the solvent residual concentration is parallel to this. It was proved that the technology that can greatly reduce the amount of energy must be devised first.

Therefore, the present inventors, for the first time, make practical use of a positive photosensitive film that does not require burning, and can drastically reduce the solvent residual concentration easily and easily in a short time by other means that do not rely on burning after film formation. The development of a film-forming drying technique and the addition of an agent for enhancing adhesion can greatly improve the adhesion of the positive photoresist film itself, and conceptually distinguish the development of a positive photoresist film with a large development latitude. The study was continued to solve the problem first.

The solvent volatilized from the coating film was considered. Since the coating film touches the air and is dried from the surface to increase its hardness and the structure is tightened, it is considered that the more the surface dries over time, the lower the diffusion property of the solvent present in the inner layer. On the other hand, the degree to which the solvent volatilizes from the coating film varies depending on the pressure of the atmosphere, and when the pressure is negative, the degree of volatilization of the solvent from the coating film is large, and it is considered that the residual solvent can be effectively reduced. However, it is not possible to place a roll formed in a chamber by vacuum using a vacuum pump.

Here, the inventors of the present application found that, after the coating film was not drenched in liquid, the plated rolls were rotated at high speed, thereby reducing the solvent residual concentration to 3% or less in a short time.

According to this knowledge, the plated rolls are horizontally supported at both ends by a photosensitive film applying apparatus according to Japanese Patent Publication No. 07-109511, and rotated at a low speed as required, so that the test photosensitive liquid is uniformly applied by a spiral scanning method or a non-contact coating method. As a technique that can apply a coating and then continue rotating to set the photoresist film of the degree of drying vaporized in a state where liquid flow does not occur, and then continuously reduce the concentration of the solvent in a very short time without burning. A low solvent that rotates the toner plate roll at a required high speed for a necessary time, exerts centrifugal force on the residual solvent in the film and rubs the surface of the film with air to diffuse away the residual solvent in the film into the air, thereby causing image flammability by a laser. The technique of obtaining film | membrane of residual concentration was established.

Apply the photoresist uniformly to the test roll of 200φmm, continue the rotation at 25r.pm for 5 minutes from the end of the application, stop the rotation, wait for 5 minutes, observe the liquid flow, and confirm that no liquid flow occurred The test roll was rotated and stopped for 20 minutes at 100 r.pm, and the solvent residue concentration in the photosensitive film was measured and found to be 2.3%.

By the way, we developed a technology that can significantly reduce the concentration of solvent in a very short time even without burning, and it has developed latitude by exposing and developing positive type photosensitive agent by adding various strengthening agents. The study was continued.

As a result, cellulose derivatives, titanium alkoxides, titanium acylates, and the like are prepared in a stock solution of a positive photosensitive composition comprising an alkali-soluble organic polymer material having a phenolic hydroxyl group and a photothermal conversion material that absorbs infrared rays, which are image exposure light sources, and converts them into heat. Alternatively, as a result of testing with at least one titanium organic compound of titanium chelate, the development was poor when the burning process was performed, and the development was excellent when the burning process was not performed, thereby obtaining the best resist pattern. At this time, room temperature was 25-27 degreeC, and humidity was about 50-55%.

However, when the maximum temperature of the day was about 16 ° C. and the humidity was extremely lower than 21 to 23%, the photoresist was completely removed when developed.

It is known that positive type photosensitizers generally have a humidity dependency that whitening occurs at a high humidity of 60% or more, and thus a film cannot be produced.

However, as a result of the above results, it has been found that the adhesion of the positive photosensitive agent does not develop even when the temperature is low and the humidity is extremely low. In addition, it was not possible to explain why the whitening phenomenon could not be produced.

Thus, by installing a humidity removing device and a humidifying device in the casing of the photosensitive film coating device according to the above Patent Publication No. 07-109511, the humidity is controlled, then thoroughly searching for a material that enhances the adhesion and adding a small amount. As a result of successive tests of film formation and exposure and development, an alkali-soluble organic polymer material having a phenolic hydroxyl group or an epoxy resin reacted with a phenolic hydroxyl group and a photothermal conversion material absorbing infrared rays as an image exposure light source and converting them into heat To the stock solution,

As an adhesive modifier,                         

(1) polyvinyl polypyrrolidone / polyvinyl acetate copolymer,

(2) polyvinyl butyral,

(3) styrene / maleic acid copolymer,

(4) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer,

(5) terpolymers of vinylpyrrolidone / caprolactam / dimethylaminoethyl methacrylate,

(6) terpene phenol resins,

(7) alkylphenol resins,

(8) polyvinyl formal resin,

(9) melamine / formaldehyde resin,

(10) polyvinyl acetate,

(11) ketone resin

The development latitude was largely obtained with respect to each positive photosensitive agent added by mixing any one of these.

More specifically, the conditions in which the room temperature in the laboratory was 25 ° C. and the humidity was changed to 25%, 30%, 55%, and 60% of the casing of the photoresist coating device were applied. Support both ends, rotate at 25r.pm, fix with wiping cross, then apply positive type photosensitive agent, and continue to rotate for 5 minutes under natural drying conditions to prevent liquid flow after completion of film formation. 10 minutes was rotated at 100 r.pm to reduce the residual solvent, and rotation was stopped.

As the controlled plate roll picked up from the photosensitive film coating device, a test roll obtained by coating and forming an extremely hard photosensitive film having a glossy and very strong adhesiveness was obtained.

The film thickness of the resist was 3.5 to 3.8 mu m. Solvent residual concentration was measured, and both test rolls were around 2.3%.

Subsequently, the infrared laser exposure apparatus (manufactured by Sink Laboratories Co., Ltd.) exposes the test image (infrared line portion) to a laser in the infrared wavelength region, and then a decrease in film that elutes the non-radiated portion occurs due to alkali development. In either case, a resist pattern extremely sharp and free of residue was obtained at the time when it was immersed in the alkaline developing solution for 60 to 70 seconds. In addition, it was confirmed that the resist pattern naturally dried after the development of the time passed was extremely hard. The film thickness of the resist after image development was 1.8-2.5 micrometers. There was no occurrence of pinholes due to membrane reduction.

From the above, the present invention has been developed.

The present invention relates to a positive photosensitive composition in which an exposure light source is exposed to a laser light having a wavelength of 700 to 1,100 nm and the sensitive portion is soluble in an alkaline developer, and when the humidity in the coating chamber is applied in the range of 25 to 60%, it is to be avoided. Not only can it be applied to the coating object, and subsequent burning is not necessary, and sufficient adhesion to aluminum can be obtained, of course, in particular, sufficient adhesion to copper or copper sulfate plating, which requires much stronger adhesion to aluminum, can be obtained. It is possible to perform good alkali development without any residue at an appropriate time of about 60 to 70 seconds, and to maintain a high sensitivity by not burning, and extremely good that the edge of the resist image is cut into a sharp outline like an exposure pattern of exposure. Phenomena and pinholes caused by membrane reduction due to less membrane reduction This little development is extremely good, the resist image is glossy, and even if used as it is for printing, a very hard resist image that can be printed to thousands of sheets can be obtained. It is an object of the present invention to provide a positive photosensitive composition having improved properties and excellent laser image printing and developing latitude.

An object of the present invention is to absorb an alkali-soluble organic polymer material having an phenolic hydroxyl group or an epoxy resin reacted with a phenolic hydroxyl group and infrared rays as an image exposure light source, as described in [Claim 1]. A light modifier that converts to heat and is also used as an adhesion modifier, including (1) polyvinylpolypyrrolidone / polyvinylacetate copolymer, (2) polyvinylbutyral, (3) styrene / maleic acid copolymer, (4) vinyl Pyrrolidone / dimethylaminoethyl methacrylate copolymer, (5) terpolymer of vinylpyrrolidone / caprolactam / dimethylaminoethyl methacrylate, (6) terpene phenol resin, (7) alkylphenol resin, (8 A polyvinyl formal resin, (9) melamine / formaldehyde resin, (10) polyvinyl acetate, and (11) a positive photosensitive composition, which comprises any one of ketone resins. do.

[Embodiment of the Invention]

The positive photosensitive composition which concerns on embodiment of invention of Claim 1 has an absorption band in part or all of the alkali-soluble organic polymer material which has a phenolic hydroxyl group, and the wavelength range 700-1100 nm, and absorbs infrared rays. Including a photo-thermal conversion material that is converted into heat by the adhesion modifier,

Polyvinylpolypyrrolidone / polyvinylacetate copolymer, polyvinyl butyral, SM copolymer, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, vinylpyrrolidone / caprolactam / dimethylaminoethyl methacrylate It comprises a positive photosensitive composition characterized by containing any one of terpolymer, terpene phenol resin, alkyl phenol resin, polyvinyl formal resin, melamine / formaldehyde resin, polyvinyl acetate and ketone resin.

In addition, a developing accelerator or a dissolution inhibiting agent may be contained.

It is preferable that it is 80-96 weight%, and, as for solid content content rate in the positive photosensitive composition of the alkali-soluble organic polymer material which has a phenolic hydroxyl group, it is more preferable that it is 90-94 weight%.

It is preferable that it is 1-10 weight%, and, as for solid content content rate in the positive photosensitive composition of a photothermal conversion material, it is more preferable that it is 2-4 weight%.

As alkali-soluble resin, it is preferable that solid content ratios, such as a polyvinyl polypyrrolidone / polyvinylacetate copolymer, are 1-10 weight%, and it is more preferable that it is 2-4 weight%.

The positive photosensitive composition of the present invention is used after dilution with a solvent. The use ratio of a solvent is the range of about 1 to 20 times by weight ratio normally with respect to the total amount of the photosensitive composition.

Examples of the alkali-soluble organic polymer having a phenolic hydroxyl group include novolak resins, resol resins, polyvinylphenol resins, copolymers of acrylic acid derivatives having phenolic hydroxyl groups, alkali-soluble epoxy resins having epoxy resins reacted with phenolic hydroxyl groups, and the like. In addition, all alkali-soluble organic polymer materials having a phenolic hydroxyl group described in Japanese Patent Application Laid-Open No. 11-231515 can be used. Particularly, novolak resins or polyvinylphenol resins are preferable.

Novolak resin is resin which polycondensed at least 1 sort (s) of phenols with at least 1 sort (s) of aldehydes or ketones under an acidic catalyst. In particular, mixed phenols of m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and resorcinol, or mixed phenols of phenol, m-cresol and p-cresol, As a polycondensation product with formaldehyde, it is preferable that the polystyrene conversion weight average molecular weight (MW) by gel permeation chromatography measurement is 1,500-10,000.

Resol resin is resin polycondensed similarly except using an alkali catalyst instead of the acid catalyst in the polycondensation of a novolak resin.

The polyvinyl phenol resin is, for example, a resin polymerized in the presence of hydroxystyrene alone or in combination of two or more thereof with a radical polymerization initiator or a cationic polymerization initiator. The polymer of the hydroxy styrene which has a C1-C4 alkyl group as a substituent in the benzene ring, and the polymer of the hydroxy styrene of an unsubstituted benzene ring are preferable.

The photothermal conversion material has an absorption band in part or all of the infrared wavelength region having a wavelength of 700 to 1,100 nm, and has the property of absorbing and thermally decomposing the laser light of the infrared wavelength region, and the alkali-soluble organic polymer having the phenolic hydroxyl group. It is involved in alkali-soluble low molecular weight and ablation by thermal cleavage of molecules. Some of the addition amount of the photothermal conversion material is related to the excessive and insufficient heat generated in the exposure, and the intensity of the infrared laser light is related to the excessive and insufficient thermal decomposition of the alkali-soluble organic polymer material present in the exposed part. Set to positive.

Photothermal conversion materials are organic or inorganic pigments or dyes, organic pigments, metals, metal oxides, metal carbides, and metal borides having absorption bands in part or all of the infrared region having a wavelength of 700 to 1,100 nm. All of the photothermal conversion materials described in -231515 can be applied, and heterocyclic rings containing nitrogen atoms, oxygen atoms, sulfur atoms, etc. are combined with polymethine (-CH =) n, so-called cyanine series. A pigment | dye can be mentioned as a typical thing, For example, quinoline system (so-called cyanine system), indole system (so-called indyanine system), benzothiazole system (so-called thiocyanine system), and imino, for example. Cyclohexadiene-based (so-called polymethine-based), pyryllium-based, thiapyryllium-based, squarylium-based, croconium-based, azlene-based and the like, among which, quinoline-based, indole-based, benzothiazole-based and imino-based compounds. Cyclohexadiene-based, pyryllium-based, or thia Rilryum boundaries is preferred. In particular, phthalocyanine and cyanine are preferable.

The solvent is not particularly limited as long as it has sufficient solubility in the used component and gives good coating properties. A cellosolve solvent, a propylene glycol solvent, an ester solvent, an alcohol solvent, a ketone solvent, or a high polar solvent can be used. Can be.

Cellosolve solvents include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, and the like.

Examples of propylene glycol solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol. Dimethyl ether and the like.

Examples of the ester solvent include butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl fibrate, ethyl-2-hydroxybutylate, ethyl acetate acetate, methyl lactate, ethyl lactate, and 3-methoxypropionic acid. Methyl and the like.

Examples of the alcohol solvent include heptanol, hexanol, diacetone alcohol, diethyl oxalate, furfuryl alcohol and the like.

High polar solvents include ketone solvents such as cyclohexanone and methyl amyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

In addition, an acetic acid, or a mixed solvent thereof, or an aromatic hydrocarbon added thereto are mentioned.

The positive photosensitive composition may contain a development accelerator and a dissolution inhibiting agent.

It is preferable that a developing accelerator adds a trace amount of dicarboxylic acid, amines, or glycols, for example.

The dissolution inhibiting agent is preferably an acid-chromic dye having a lactone skeleton, and a hydrogen bond with an alkali-soluble organic polymer material is used for the purpose of increasing the time difference of solubility in the alkaline developer of the exposed portion and the non-exposed portion. It has a function of forming and reducing the solubility of the polymer material, and has a function of absorbing little light in the infrared region and not decomposing in light in the infrared region.

Examples of other dissolution inhibitors include thiollactone skeletons, N, N-diarylamide skeletons, such as sulfonic acid esters, phosphoric acid esters, aromatic carboxylic acid esters, aromatic disulfones, carboxylic anhydrides, aromatic ketones, aromatic aldehyde aromatic amines and aromatic ethers. , Acid-chromic dyes having a diarylmethylimino skeleton, base-chromic dyes having a sulfolactone skeleton, nonionic surfactants and the like can be used.

The positive photosensitive composition of the present invention is usually a solution obtained by dissolving each of the above components in a solvent such as a cellosolve solvent, a propylene glycol solvent, or the like and applied to a copper plated surface or a copper sulfate plated surface of a gravure printing object plate roll which is a support surface. After drying naturally, it is rotated at high speed to be winded on the surface of the platen roll, and the mass action by the centrifugal force in the photoresist film and the vicinity of the surface become a slight negative pressure state, thereby reducing the solvent residual concentration to 6% or less. It becomes the positive photosensitive film in which the photosensitive composition layer was formed.

As the coating method, it is preferable to use the photosensitive film coating device 6 which is the fountain coat shown in FIG. 1, but it is not limited to this. Meniscus coats or dipcoats with vertical dipcoat devices can be used. The thickness of a coating film can be 1-6 micrometers, and it is preferable to set it as 3-5 micrometers.

As a light source which image-exposes a positive photosensitive composition layer, the semiconductor laser which generate | occur | produces an infrared laser beam of wavelength 700-1,100 nm, and a YAG laser are preferable. In addition, solid lasers, such as a ruby laser and LED, can be used.

As light intensity of a laser light source, it is preferable to set it as 2.0x10 <^6> mJ / s * cm <2> or more, and it is especially preferable to set it as 1.0 * 10 <^7> mJ / s * cm <2> or more.

As a developer used for the photosensitive film formed using the positive photosensitive composition of this invention, the developer which consists of inorganic or organic alkalis, such as an inorganic alkali, a salt of Na, K, or organic alkali, TMAH, or choline, is preferable. In the experiment, an original developer made of (a) sodium ortho silicate, (b) trisodium phosphate, and (c) a surfactant was used.

The development is usually performed at a temperature of about 15 to 45 ° C., preferably at 27 to 32 ° C., by immersion, spray development, brush development, or ultrasonic development.

[Developed Latitude of Positive Photosensitive Composition]

The development latitude of the positive photosensitive composition is

(1) The degree of bonding of the film is appropriate, and the exposure to infrared laser light causes the main portion of the molecule or the side chain to be cleaved in the exposed portion, and at the same time, the physical change such as a conformation change such as a low molecule with higher alkali solubility, and photosensitive. To produce a layer of abrasion properly so that it becomes a thin film and change so that it can be dissolved in an alkaline developer in a short time;

(2) The unexposed portion is obtained by being in close contact with the surface to be coated without being dissolved for a relatively longer time than the exposed portion until dissolved in an alkaline developer even if there is some change in temperature and humidity.

The development latitude is not obtained because the strong adhesion of the material (adhesive modifier) that enhances the adhesion can be strengthened against the weak adhesion of the alkali-soluble organic polymer having a phenolic hydroxyl group. The expression of the adhesion force due to the material for strengthening the adhesion in the positive photosensitive composition is relatively determined by the kind and the amount of the material for strengthening the adhesion.

For example, as a positive photosensitive composition in which a large amount of titanium alcohol is selected and added as a material for strengthening adhesion, the strength, stability, and adhesion of the entire film after burning are excessively strong, such as a conformation change due to exposure to infrared laser light. There is no physical change or photosensitive layer abrasion, and even when developing, the exposed portion is hardly dissolved in the developer and the entire film is not reduced. In other words, developing latitude cannot be obtained at all.

If the amount to be added is reduced little by little, the film decreases, and the area where the development latitude can be obtained is barely obtained, but the development latitude cannot be obtained immediately by only slightly different room temperature or humidity.

On the other hand, even if the silane coupling agent is added to the alkali-soluble organic polymer having a phenolic hydroxyl group, a strong adhesion cannot be obtained, and the positive photosensitive composition layer in the exposed portion is dissolved in the alkaline developer and the positive photosensitive property in the unexposed portion. Dissolution of the composition layer in the alkaline developer occurs simultaneously without time difference, and development is impossible.

By the way, the following positive photosensitive composition was made under the conditions of 25 degreeC room temperature and 25-60% of humidity, and this is apply | coated to a copper surface or a copper sulfate plating surface, and when the residual solvent concentration is 6% or less, about 60 to 70 second. Good development can be performed in which a sharp pattern without residues can be obtained.

The best developing latitude is expressed when the vinylpyrrolidone / dimethylamino ethylmethacrylate copolymer and the like are contained at a solid content ratio of about 3%.

[Positive Photosensitive Composition According to the Present Invention]

Positive type photosensitive composition which concerns on this invention,

An alkali-soluble organic polymer material having a phenolic hydroxyl group or an epoxy resin reacted with a phenolic hydroxyl group, and a photothermal conversion material that absorbs infrared rays, which are image exposure light sources, and converts them into heat;

In addition, as an adhesion modifier,

Polyvinylpolypyrrolidone / polyvinylacetate copolymer, polyvinylbutyral, styrene / maleic acid copolymer, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, vinylpyrrolidone / caprolactam / dimethylaminoethyl methacrylate Terpolymer, polyvinyl polymer resin or terpene phenol resin or alkylphenol resin, melamine / formaldehyde resin, polyvinyl acetate, or ketone resin.

In formula (5), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group, R3 represents a hydrogen atom or a hydroxyalkyl group, R4 and R5 are each independently a hydrogen atom, A lower alkyl group or a group having a reactive double bond, wherein m and n are integers of at least 1 and m ≧ n.

[Formula (2) represents polyvinyl polypyrrolidone / polyvinylacetate copolymer]

PVP / VA copolymers (Vinylpyrrolidone / Vinylacetate Copolymers) are transparent, thermoplastic, vinylpyrrolides having a molecular weight of 20,000 to 50,000 with free radical polymerization of vinylpyrrolidone and vinyl acetate at a ratio of 70/30 to 30/70. As the ratio of money increases, it is a straight random copolymer with increased hydrophilicity.

As for PVP / VA copolymer, it is preferable that vinyl pyrrolidone and vinyl acetate are the ratio of 60/40, molecular weight in this case is 45x10 <^3> , and Tg is 110 degreeC.

[Formula (3) represents polyvinyl butyral]

Polyvinyl butyral (formerly known chemical substance No. 6-708) is a substance obtained by butyralization in which butylaldehyde is reacted with polyvinyl alcohol, and a considerable amount of hydroxyl group and acetyl group remain, and is represented by the following general formula. It is represented by a structure.

PVB is a product of Denki Kagaku Kogyo Co., Ltd., 5000A and 6000 EP of Denka Butyral Co., Ltd., the product of Sekisui Kagaku Kogyo Co., Ltd., BL-1, BL-2, BL-2, BL- of low-polymerization type S, BX-L, BM-1, BM-2, BM-5, BM-S of high polymerization degree type, BH-3, BH-S, BX-1, BX-2, BX-5, There is BX-55, and from the experimental examples, the use of BL-S and BM-S having solubility in various kinds of solvents is preferable.

[Formula (4) and Formula (5) represent styrene / maleic acid copolymer]

The styrene / maleic acid copolymer (Styrene Maleic acid Resin) is a copolymer of styrene and maleic anhydride.

The styrene / maleic acid copolymer shown in Formula (4) is a brand name / oxy rack SH-101 which is a copolymer of styrene and maleic acid semiester. It is preferable to use the maleic acid semiester which controlled the acid value to 60-90 by alcohol reaction in a styrene solution.

The styrene / maleic acid copolymer shown in formula (5) is styrene, (alpha) -methylstyrene, m or p-methoxy styrene, p-methylstyrene, p-hydroxy styrene, 3-hydroxymethyl-4 hydroxy-styrene Styrene or derivatives thereof (styrene monomer) and maleic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-iso-propyl maleate, mono-n-butyl maleate and mono-iso maleate And a copolymer of maleic acid derivatives such as -butyl and mono-tert-butyl maleate (hereinafter referred to as copolymer (a)). Although the copolymer (a) is not shown in the above structural formula, alkyl methacrylates such as methyl methacrylate and t-butyl methacrylate, alkyl acrylates, and the like, and the copolymer (a) may be reacted with a reactive double bond. And a modified one (hereinafter referred to as copolymer (b)). M and n in this case are integers of 1 or more, m≥n, and preferably m / n = 1 to 1.1. As weight average molecular weight, 1,500-100,000 are preferable.

The said copolymer (b) is unsaturated alcohol, for example, aryl alcohol, 2-butene-1-2-ol, furryl alcohol, oleyl alcohol, cinnamil in the acid anhydride group or carboxy group in copolymer (a). Unsaturated alcohols such as alcohol, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, arylglycidyl ether, α-ethyl It can manufacture by making it react with the oxirane ring, such as glycidyl acrylate, clotonyl glycidyl ether, and monoalkyl monoglycidyl ester, and an epoxy compound which has one reactive double bond, respectively. In this case, it is necessary for the carboxyl group necessary for alkali development to remain in the copolymer.

In the copolymer (b) obtained as described above, a reactive double bond is introduced by unsaturated alcohol, and in order to further increase the concentration of the reactive double bond, the oxirane ring and one reactive double bond each have one. By reacting an epoxy compound, a reactive double bond concentration can be further increased (hereinafter referred to as copolymer (c)).

Polymers having carboxyl groups other than styrene / maleic acid copolymers can also introduce reactive double bonds as described above. The provision of the reactive double bond to a copolymer is preferable at the point of photosensitivity. The synthesis | combination of these copolymers (copolymer (a), copolymer (b), copolymer (c), etc.) is carried out by Unexamined-Japanese-Patent No. 47-25470, 48-85679, Japanese Patent No. 51-21572 This can be done according to the method described in a call.

[Formula (6) represents vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer]

[Formula (7) represents terpolymer of vinylpyrrolidone / caprolactam / dimethylaminoethyl methacrylate]

[Formula (8) represents polyvinyl formal]

Polyvinyl formal resin is used to polymerize vinyl acetate monomer using a catalyst to make polyvinylacetate, dissolve it in acetic acid, add formaldehyde and sulfuric acid to react with ketone (alkaline hydrolysis) and form At the same time, the hydrolysis reaction is carried out, dilute hydrochloric acid is added to the reaction solution to precipitate the polyvinyl formal resin, and the product can be obtained by solvent recovery, washing and drying.

Polyvinyl formal resin consists of a polyvinyl formal group, a polyvinyl alcohol group, and a polyvinyl acetate group, and is resin with favorable electrical insulation.

[The terpene phenol resin and the alkyl phenol resin did not show a formula]

Terpenephenol Resin and Alkylphenol Resin are products of Arakawa Kagaku Kogyo Co., Ltd., and are termed terpene phenol resins as: Tamanol 803L, 901, or as alkylphenol resins. Knol 520S, 521, 526, 586 and 572S are available.

[Equation (9) represents melamine / formaldehyde resin]

Melamine formaldehyde resin is made by reacting melamine (C ₃ H ₆ N ₆ ) with formaldehyde. This synthesis reaction is not 100%, and unreacted formaldehyde remains.

[Formula (10) represents polyvinyl acetate]

Polyvinyl acetate: The English name poly (vinyl acetate) is a polymer compound made by polymerizing vinyl acetate, and for example, Sacnol SN-09T (trade name) manufactured by Denki Chemical Co., Ltd. may be used. Polyvinyl acetate is a structure shown by following formula, and is a white-pale yellow solid which is insoluble in water, and is soluble in an alcohol type, an acetate ester type, and an aromatic solvent.

[Equations (11) and (12) represent ketone resins]

The ketone resin may be any one of methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone and methylcyclohexanone. Among these, cyclohexanone shown in Formula (11) and acetophenone shown in Formula (12) are preferable.

[Examples and Comparative Examples]

[Developed Latitude of Positive Photosensitive Composition According to the Present Invention]

The result of the Example plated by the above-mentioned plate making process using these positive photosensitive compositions is shown to [Table 1]-[Table 10].

The following four types were created from the stock solution of the positive photosensitive composition used in the Example of Table 1-Table 10, and the comparative example of Table 11. In addition, in Table 1-Table 11, a% value is the weight% with respect to solid content.

(a) Stock solution A: consisting of a novolak resin and a phthalocyanine pigment having an absorption band in part or all of the infrared region having a wavelength of 700 to 1,100 nm, and absorbing and pyrolyzing the laser beam;

This novolak resin used the mixed phenols of m-cresol, p-cresol, 2,5-xyleneol, 3,5-xyleneol, resorcinol, and the polycondensate of formaldehyde.

(b) Stock solution B: Stock solution consisting of the resol resin and the phthalocyanine pigment,

(c) Stock solution C: Stock solution consisting of polyvinylphenol resin and the phthalocyanine pigment,

(d) Stock solution D: Stock solution comprising a copolymer of an acrylic acid derivative having a phenolic hydroxyl group and a phthalocyanine dye.

Examples and comparative examples are the fountains in which the roll base material is iron and copper sulfate-plated and mirror-polished platelets rolled, and the solvent in the positive photosensitive composition is evaporated in the coating so that the proportion of the solvent is not changed. Precise both ends of coating device (dehumidifier and humidification device, which can control humidity as desired) and rotate at 25r.pm, sufficiently fix by wiping cross, and then Place the test sensitized pipe with the composition diluted in solvent (MEK) to a predetermined concentration so that there is a gap of about 500 μm at one end of the platen roll, and the test sensitizer is raised as necessary for the coating and the pipe The test photosensitive liquid is uniformly applied by the spiral scan method from one end of the rolled roll to the other end. After the rotation was continued at 25 r.p.m for 5 minutes from the end, the rotation was stopped. After waiting for 5 minutes and observing the flow, it was not possible to observe the appearance of the flow. Then, the film thickness was measured, and there was no difference between the lower surface and the upper surface of the roll. This confirmed that the dry photosensitive film can be set in a state where liquid flow does not occur.

Subsequently, the test roll was rotated at 100 r.p.m for 10 minutes to stop, and the solvent residual concentration in the photosensitive film was measured. As a result, it was 2.9%.

Subsequently, a test roll was attached to an infrared laser exposure apparatus 7 (manufactured by Sink Laboratories Co., Ltd.) equipped with a Creoscitex high-power semiconductor laser head, and the laser was irradiated with an infrared wavelength region to the test roller. The image was printed, and then a test roll was attached to the developing apparatus, rotated to raise the developing tank, and developed for about 60 to 70 seconds until the residue disappeared, followed by washing with water.

The edges of the resist image were cut off and the residue and the surface condition and hardness of the resist were examined under a microscope to determine the sensitivity of printing, the goodness of development, defects, film reduction, and development latitude.

These positive photosensitive compositions are developed for about 60 to 70 seconds before forming a coating film on a to-be-rolled roll and attaching it to a developing apparatus without heating and rotating to raise the developing tank to remove the residue, followed by washing with water and a microscope. The edges of the resist image were cut off, the residues, and the surface condition and hardness of the resist were examined to determine the sensitization of flammability, the goodness of development, defects, film reduction, and development latitude.

Experiments confirmed that the wires exposed by the alkaline developer were washed away and the unexposed non-exploded portions had a film decrease, but had a developing latitude that remained in a sharp pattern without being washed away.

As described above, the positive photosensitive composition containing no vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, polyvinyl butyral, or the like does not exhibit development latitude, and vinylpyrrolidone / dimethylaminoethyl methacrylate. The positive photosensitive composition comprising a copolymer or polyvinyl butyral is expressed by developing latitude, indicating that strong adhesion such as vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, polyvinyl butyral, etc. The weak adhesion of the alkali-soluble organic polymer having a hydroxyl group is appropriately reinforced, indicating that the development latitude is expressed.

[Comparative Example Latitude]

About the photosensitive film of the positive photosensitive composition which added the titanium organic compound to the stock solution of the positive photosensitive composition which consists of an alkali-soluble organic polymer material which has a phenolic hydroxyl group, and a phthalocyanine pigment | dye, as shown in Table 11, burning temperature is drastically reduced. I could make it.

In the case of the photosensitive film of the positive photosensitive composition to which the titanium organic compound was added, the burning temperature could be formed well at 46 degreeC, and the sensitivity became favorable and it was easy to develop.

However, in the test which was not burned out, favorable film formation was not possible, resulting in poor development.

From the above results, in the gravure plate, if a positive photosensitive composition which does not require burning after application is used,

(1) It is inappropriate to apply to the object to be coated and post-burn, and to have sufficient adhesion even if not burned. A glossy and very hard photoresist film can be obtained.

(2) Obtain sufficient adhesion when applying on a clear day when the humidity in the work room is 25 to 60%, or applying the humidity in the work room within the range of 25 to 60% using a dehumidifier and a humidifier. Can be.

(3) Good alkali development can be performed in which no residue is generated at an appropriate time. Although the photosensitive layer component does not substantially cause a chemical change by exposure, it can satisfy all the basic performances of the printing plate such as printing resistance, sensitivity and developing latitude.

(4) Since the development latitude can be widened even when the image is exposed at a lower exposure energy than the high exposure energy at which excessive heat is generated by the photothermal conversion material in the photosensitive layer, the degree of photosensitive layer scattering is suppressed to be low. The problem of layer scattering and contaminating the optical system of the exposure apparatus does not occur.

(5) By not burning, high sensitivity can be maintained and an extremely good phenomenon can be obtained in which the edge of the resist image is cut into a sharp outline like an exposure pattern of exposure.

(6) An extremely good phenomenon can be achieved in which film reduction hardly occurs. The occurrence of pinholes due to the reduction of the film can be avoided.

(7) The resist image has a gloss, and a very hard resist image that can be used as it is for printing and printing thousands can be obtained, and thus scratch resistance is improved in handling before development after the formation of the photosensitive film.

(8) The sensitivity of the image printing by the laser and the development latitude are excellent.

The positive photosensitive composition of the present invention is an alkali-soluble positive photosensitive composition having infrared wavelength laser photosensitivity in which the sensitive portion is made available to a developing solution upon exposure to laser light in an infrared wavelength region, and has excellent effects as follows. .

(1) It is inadequate to apply | coat to a to-be-applied object and to post-burn, and it has aptitude which can acquire sufficient adhesiveness even if it does not burn. A glossy and very hard photoresist film can be obtained.

(2) It is possible to obtain sufficient adhesion when applying on a clear day when the humidity in the work room is 25 to 60%, or applying the humidity in the work room to the range of 25 to 60% by using a dehumidifier and a humidifier. have.

(3) Good alkali development can be performed in which no residue is generated at an appropriate time. Although the photosensitive layer component does not substantially cause a chemical change by exposure, it has a high resistance to cracking, sensitivity, development latitude (the time until the exposure is completely removed during development, and the film residual ratio of the unexposed portion during development The basic performance of the printing plate, such as a sufficient time difference) can be satisfied.

(4) Even when image exposure is performed at a lower exposure energy than the high exposure energy at which excessive heat is generated by the photothermal conversion material in the photosensitive layer, the development latitude can be taken widely, so that the degree of photosensitive layer scattering is reduced. By layer abrasion, there is no problem of contaminating the optical system of the exposure apparatus.                     

(5) By not burning, high sensitivity can be maintained and an extremely good phenomenon can be obtained in which the edge of the resist image is cut into a sharp outline like an exposure pattern of exposure.

(6) An extremely good phenomenon with almost no film reduction can be achieved. The occurrence of pinholes due to the reduction of the film can be avoided.

(7) The resist image is glossy, and a resist image which is extremely hard to be printed even if it is used as it is for printing can be obtained, and the scratch resistance in handling before development after photosensitive film formation is improved.

(8) The sensitivity of image printing by laser and the development latitude are excellent.

The positive photosensitive composition according to the present invention is preferable to form a positive photosensitive film on the copper sulfate plated surface of the platen roll for gravure printing, but is not limited thereto. Metal plates such as aluminum, zinc, steel, aluminum, zinc, Adhesion at low temperatures even when applied to metal plates plated or deposited with copper, iron, chromium, nickel, etc., paper coated with resin, metal foil coated with aluminum foil, plastic film, hydrophilized plastic film, and glass plate It is favorable and high sensitivity can be obtained.

Therefore, it can be used suitably for the photosensitive flat plate, the proofing printing proof, the wiring board, the copper etching resist for gravure, the color filter resist used for flat display manufacture, the photoresist for LSI manufacture, etc.

Claims (1)

An alkali-soluble organic polymer material having a phenolic hydroxyl group or an epoxy resin reacted with a phenolic hydroxyl group, and a photothermal conversion material that absorbs infrared rays, which are image exposure light sources, and converts them into heat, and further include: (1) Polyvinylpolypyrrolidone / polyvinylacetate copolymer, (2) polyvinylbutyral, (3) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (4) vinylpyrrolidone / caprolactam / dimethylaminoethyl Terpolymer of methacrylate, (5) terpene phenol resin, (6) alkylphenol resin, (7) polyvinyl formal resin, (8) melamine / formaldehyde resin, (9) polyvinyl acetate and (10) ketone Positive type photosensitive composition characterized by containing any one kind of resin.