JP4732419B2 - Positive photosensitive composition - Google Patents

Description

  The present invention relates to a positive photosensitive composition. More specifically, the present invention has an infrared wavelength region laser sensitivity in which the sensitive part is soluble in an alkali developer by exposure to laser light having a wavelength of 700 to 1,100 nm. The present invention relates to an alkali-soluble positive photosensitive composition. The positive photosensitive composition of the present invention can be used effectively in photofabrication, and is particularly suitable for photofabrication applied to the production of printing plates, electronic parts, precision instrument parts, anti-counterfeiting related members and the like. It is suitably used in the field.

  A conventional old positive photosensitive lithographic printing plate contains a novolak resin and an o-quinonediazide compound that is a substance sensitive to white light. As shown in the following formula (I), photolysis of the o-quinonediazide compound (Chemical change) causes an Arndt-Eistert-type rearrangement to form a ketene structure to form a 5-membered carboxylic acid in the presence of water, and as shown in the following formula (II), the photosensitive layer in the exposed area The upper ketene reacts with the naphthoquinone diazide at the lower part of the photosensitive layer to form a lactone, which opens during the development with an aqueous alkali solution to form a lactone ring and becomes sodium carboxylate, and the coexisting novolak is also soluble in alkali and is eluted together. On the other hand, the photosensitive layer in the unexposed area is coupled with a novolak that coexists with alkali during development as shown in the following formula (III). Cause response, become alkali-soluble is known to remain as a resist image (see Non-Patent Document 1.). As described above, when the o-quinonediazide compound is contained, a large development latitude can be obtained.

  In the specification of the present application, there is no change in the film thickness during development (thin film loss is small), there is no change in the halftone dot area during the predetermined development time, and there is no sudden residue (residue). It is said that there is a development latitude that the plate can be made.

  On the other hand, a positive photosensitive composition that uses changes other than chemical changes was invented so that plate making can be performed even under white light, and a positive image was developed by laser light in the infrared wavelength region and developed in the exposed portion. A method for forming a positive image by increasing the solubility in a liquid has been devised, and is practiced by offset plate making and flexo plate making (see, for example, Patent Documents 1 to 10).

  The positive-type photosensitive lithographic printing plate described in each of the above-mentioned documents is mainly composed of a photosensitive layer component containing a substance that absorbs infrared light such as an infrared-absorbing dye and converts it into heat and an alkali-soluble resin such as a novolak resin. The heat generated by the infrared laser light exposure causes a physical change such as a conformational change of the resin to increase the solubility in the developer.

  However, a positive photosensitive lithographic printing plate that does not contain an o-quinonediazide compound and causes a physical change such as a conformational change of the resin by baking a positive image with a laser beam in the infrared wavelength region to increase the solubility. In the present situation, burning (heating operation) is required after the coating, and even if burning is performed, the difference in dissolution rate between the exposed and unexposed areas is small, and the basic performance of the printing plate such as sensitivity and development latitude is inferior. Therefore, it is difficult to satisfy the development processing stability when the number of development processing sheets is increased.

  On the other hand, the situation is completely different in gravure plate making. In Japan, where gravure plate-making and printing are most prevalent, gravure plate-making methods that can perform gravure plate-making using a positive thermal resist that can be developed without heating after coating film formation have not been carried out at all. There is no patent literature or experimental literature.

  Conventionally, the gravure plate making process of the plate making roll by the corrosion method / laser plate making method includes, for example, carry-in, degreasing, water washing, pickling, water washing, ballad treatment, water washing, ballad copper plating, water washing, grinding stone polishing, water washing, and photosensitizer. Coating-antioxidant coating-image printing with an infrared laser exposure apparatus-development-washing-etching-washing-resist peeling-washing-chromium plating-washing-polishing-washing-unloading. Patent Documents 11 to 29 can be cited as technical documents in which a gravure plate making process of a plate making roll by a corrosion method / laser plate making method is disclosed.

  All of the gravure plate-making processes described in the above-mentioned documents are coated with a photosensitive film made of a negative photosensitive composition, and are not coated with a photosensitive film made of a positive photosensitive composition. In the conventional etching method, a negative photosensitive film is applied to a plate-making roll, and the coating film is dried at room temperature to form a negative photosensitive film, which is baked with an argon ion laser. No film is formed and a positive-type photosensitive agent image is not printed by an infrared wavelength laser beam.

  The high-power semiconductor laser head of Creositex, Canada, emits laser light in the infrared wavelength range, and can be mounted on an offset printing press to irradiate a positive photosensitive composition for good development. And is in practical use worldwide.

  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 is higher in the positive type than in the negative type and the processing time is increased. Can be greatly shortened.

  Furthermore, the pattern of the positive type photosensitive composition photosensitive film is baked with a laser in the infrared wavelength region than the negative type photosensitive composition photosensitive film is baked with an argon ion laser. good. This is considered to be a difference in pattern cut due to a difference in composition between the positive photosensitive composition and the negative photosensitive composition.

  The reason why a positive photosensitive composition has not been used in gravure printing, although it has been used in offset printing or flexo printing, is that a negative photosensitive agent can be used for gravure printing. Since the negative type photosensitizing agent cures the degree of polymerization of the resin in the exposed portion by irradiating ultraviolet rays, the development latitude can be ensured sufficiently and sufficiently regardless of the material of the coated surface.

  On the other hand, there was no positive photosensitive composition having a development latitude that was satisfactory in relation to the copper sulfate plating of the gravure printing roll. In particular, there was no photosensitive composition that did not burn after coating. Even if a positive photosensitive composition used in offset plate making and flexographic plate making is coated on a plate roll for gravure, there are almost no conditions for film formation. In many cases, the coating film of the positive photosensitive composition on the plate-making roll for gravure flows entirely with an alkaline developer. The same applies if burning is performed after coating.

High-resolution gravure plate making system using positive type photosensitive film using semiconductor laser or YAG laser that can output laser light in the infrared wavelength range, compared to the case of using argon ion laser, downsizing of equipment and plate making work Realization of this is strongly desired from the standpoints of ambient light, resolution, and pattern cuts.
Japanese Patent Laid-Open No. 10-268512 JP-A-11-194504 JP 11-223936 A Japanese Patent Laid-Open No. 11-84657 Japanese Patent Laid-Open No. 11-174681 Japanese Patent Laid-Open No. 11-231515 International Publication No. 97/39894 International Publication No. 98/42507 JP 2002-189293 A JP 2002-189294 A Japanese Patent Application No. 10-193551 Japanese Patent Application No. 10-193552 JP 2000-063422 A JP 2000-062343 A JP 2000-062344 A JP 2001-179923 A JP 2001-179924 A JP 2001-187440 A JP 2001-187441 A JP 2001-191475 A JP 2001-191476 A JP 2001-260304 A JP 2002-127369 A JP 2002-187249 A JP 2002-187250 A Japanese Patent Laid-Open No. 2002-200728 JP 2002-200729 A JP 2002-307640 A Japanese Patent Laid-Open No. 2002-307641 Japanese Patent Publication No. 07-109511 JP 2004-133025 A Japanese Patent Publication No. 47-25470 Japanese Patent Publication No. 48-85679 Japanese Patent Publication No.51-21572 Mototaro Nagamatsu and Hideo Inui, “Photosensitive Composition” Kodansha Publishing, September 1, 1978, p. 104-122

  In view of the above-mentioned circumstances, the present inventor has started development of a positive photosensitive composition having a necessary and sufficient development latitude without performing burning after coating in relation to copper sulfate plating of a gravure printing roll.

  Then, for the etching method as one of the plate making methods of the gravure printing roll, a stock solution of a positive photosensitive composition containing a novolak resin and a cyanine dye is prepared, and a positive photosensitive agent obtained by diluting the stock solution with a solvent is used for gravure. It was applied to the copper sulfate plating surface of the plate making roll. For the application of the positive photosensitive agent, a photosensitive film coating apparatus (manufactured by Sink Laboratory Co., Ltd.) according to Patent Document 30 was used. And, when I developed a test after burning a positive image by irradiating a laser in the infrared wavelength range with an infrared laser exposure device (manufactured by Sink Laboratories) equipped with a high-power semiconductor laser head of Creositex, The photosensitive film was completely removed and no satisfactory resist image was obtained.

  Evaluation of film formation by a photosensitive film coating apparatus according to Patent Document 30 reveals that a spiral of a contact coating method in which a coating roll is immersed in a photosensitive agent in a tank and a photosensitive agent is applied to the coated surface many times. It is a scanning method, and it is thought that air is kneaded into the photosensitive film, and because the tank has an open structure, the solvent in the photosensitive agent stored in the tank evaporates, taking away the latent heat of evaporation and cooling the coating roll. As a result, it was found that the coating was accompanied by a whitening phenomenon, and the solvent concentration was constantly decreased, the viscosity gradually increased, and it was impossible to form a coating with a uniform film thickness. As a result, it was concluded that the positive photosensitive film is extremely unsuitable even if the negative film is properly applied and formed by the photosensitive film coating apparatus according to Patent Document 30.

  Therefore, in place of the photosensitive film coating apparatus according to Patent Document 30, the solvent in the photosensitizer in the tank can be applied in a sealed state without causing evaporation, and can be applied in a non-contact manner to the plate-making roll. We have developed a photosensitive film coating device that can avoid coatings involving water.

  The schematic configuration of the photosensitive film coating apparatus will be described. As a method for forming a film by applying a positive photosensitive agent to a plate-making roll, the upper end of a photosensitive agent outlet pipe which is a vertical pipe is horizontally chucked and rotated at both ends. Spiral by moving the photosensitive agent outflow pipe from one end of the plate-making roll to the other end while supplying the photosensitive agent so that it slightly rises and overflows from the upper end of the photosensitive agent outflow pipe. The coating liquid is applied to the plate-making roll by a scanning method, and the rotation of the roll is continued until the coating film is naturally dried.

  Therefore, when research was continued, strong adhesion to the copper sulfate plated surface of the positive photosensitive composition could not be obtained, and when developed, it flowed quickly with an alkaline developer without distinction between the image area and the non-image area. It continued. For this reason, it was thought that it was inevitable to perform adhesion by heating the film surface to a high temperature after the coating to provide adhesion.

  We thought that it was necessary to perform the burning because it was considered that the film was not formed due to the poor adhesion of the positive photosensitive composition to the copper sulfate plating surface. This is because it is considered that the adhesiveness can be enhanced by strengthening the hydrogen bond of the alkali-soluble organic polymer substance having a phenolic hydroxyl group by performing the burning.

  For the time being, when research was continued by performing burning, the positive photosensitive composition containing the prepared novolak resin and cyanine dye was applied to a plate-making roll, and the film surface temperature was adjusted to 60 ° C. Burning for a minute and then developing with laser exposure resulted in poor development.

  Therefore, when the film surface was burned for 30 minutes so that the film surface temperature became 130 ° C., development failure occurred even when the film surface was completely removed including the non-image area. It was concluded that the development failure still occurred even after burning because the adhesion of the positive photosensitive composition to the copper sulfate plating was too low.

  Therefore, as a result of increasing the adhesion of the photosensitive film by adding a silane coupling agent as an auxiliary agent for enhancing the adhesion to the positive photosensitive composition, the exposure and development can be performed slightly better. Specifically, for example, a 200φ mm plate-making roll is set to 25 r. p. Rotate at a low speed of m, apply a positive photosensitive agent, continue to rotate so that no dripping occurs, let the solvent evaporate in a state where dripping does not occur after 5 minutes under natural drying conditions When a photosensitive film of a certain degree was set and then burned at 130 ° C. for 30 minutes, the residual solvent concentration was less than 2%, and the image could be printed with a laser and developed.

  However, the adhesion to the film was not the best and exposure / development did not exceed a slightly good range. Moreover, when the film surface temperature was set to 130 ° C., it took 100 minutes or more for burning and subsequent cooling, a large amount of heat energy was required, and the running cost was high, which proved impractical. . Further, when the film surface temperature is 130 ° C., the hydrogen bond of the alkali-soluble organic polymer substance having a phenolic hydroxyl group is strengthened and development is difficult, and the cyanine dye is denatured and sensitivity is lowered. It was felt from the badness of.

  When the resist image was observed closely, it was found that many pinholes were generated. There was no such pinhole in the negative resist image. For this, it is impossible to completely wash away the abrasive powder adhering to the plate making roll only by washing with water after precision polishing with a grindstone.If the plate making room is not made into an advanced clean room, dust will be covered during conveyance of the plate making roll. It was considered that it adheres to the plate-making roll and that the positive resist image is much more sensitive to film forming conditions than the negative resist image. As a result of various investigations, pinholes could be prevented from being generated when the plate-making roll was sufficiently wiped with a wiping cloth before applying the photosensitive agent.

  Next, the gravure plate making roll has a roll base made of aluminum and iron, and furthermore, since the roll diameter is different and the roll diameter is different, the thickness is all different, Due to the difference in specific heat capacity, even if the heater is heated for the same time, the heat is transferred to the roll base material and the film surface temperature is not always heated to 130 ° C. We thought it important to reduce the specific heat capacity by lowering the temperature. It was considered that the burning for greatly reducing the solvent concentration can be achieved even when the film surface temperature is set to a temperature much lower than 130 ° C. by selecting a composition with good solvent separation.

  A test was conducted to shorten the heating time, and when the burning temperature of the film surface was lowered to 80 ° C. to 100 ° C. for 50 minutes, it was confirmed that the solvent concentration was 6% or less. Became. As a cause, it was concluded that the above-mentioned silane coupling agent did not provide necessary and sufficient adhesion.

  Next, imidazole (including imidazole silane), which is a curing accelerator, was used instead of the silane coupling agent as an adhesion agent, but there was no particular difference from the case of the silane coupling agent. It was the same as that of the ring agent.

  Subsequently, various adhesives were replaced with 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 from an image exposure light source and converts it into heat. An experiment was conducted in which a photosensitive film was formed on a copper sulfate plating roll at room temperature of 25 ° C., and a test image was exposed and developed with the infrared laser exposure apparatus (manufactured by Sink Laboratories, Inc.). For the photosensitive film of the positive photosensitive composition to which the compound was added, the burning temperature could be remarkably lowered (see Patent Document 31).

  In the case of a photosensitive film of a positive photosensitive composition to which a titanium organic compound was added, the film could be formed well even at a burning temperature of 46 ° C., the sensitivity was good, and development was easy. However, in a test in which the burning process was not performed, good film formation was not possible and development was poor.

  Even if the burning temperature can be lowered to around 50 ° C., the necessity of the burning is that it is necessary to perform the cooling after the burning, the time and energy required for the burning and the subsequent cooling, the equipment line However, this is disadvantageous in that it becomes longer by the amount of the burning device and the equipment cost and running cost are increased. After all, I thought that the need to burn was an issue that had to be solved.

  When burning is performed, unlike a thin plate material, a roll has a large heat load and takes 30 to 60 minutes to heat to a necessary temperature, and takes 50 to 100 minutes or more to cool to room temperature. Since the time varies depending on the size of the roll, it cannot be uniformly controlled. In addition, the burning is a cause of denaturation of the cyanine dye, lowering the sensitivity, resulting in poor pattern cuts, thinning of the resist during development, receding contours, and pinholes. Accordingly, there is a strong demand for the development of a positive photosensitive film that does not require burning.

  As a result of repeating the test a number of times, if the total solvent residual concentration of MEK, IPA, PM, etc. when the film is formed is high, the image cannot be printed by the laser (the main chain of the photosensitive film forming resin molecules in the exposed portion) Alternatively, it was found that a latent image in a state in which the side chain portion was cut to form a low-molecular compound having further increased alkali solubility and appropriately caused scattering of the photosensitive layer) could not be formed.

  When a positive photosensitive agent added with the above-mentioned titanium organic compound is applied to a copper sulfate plated plate and the mixture is allowed to stand for 15 minutes under a natural drying condition in which air is not blown at room temperature of 25 ° C., the residual solvent concentration is 11% and 25 hours have elapsed. The residual solvent concentration was 9%. 45r. p. As a result of applying a positive photosensitive agent to a plate-making roll rotating at m and measuring 10 minutes later, it was found that the residual solvent concentration was only reduced to 7%. Therefore, in order to reconstitute a positive type photosensitive film stock solution that does not require burning by modifying the positive type photosensitive agent with an auxiliary agent that strengthens adhesion, this result can be confirmed by exposure and development. In parallel with this, it has been found that it is necessary to devise a technology that can greatly reduce the residual solvent concentration.

  Therefore, for the first time, the inventor of the present invention has developed a positive photosensitive film that does not require burning for the first time as a development theme, and greatly reduces the residual solvent concentration in a short time and easily by other means that does not rely on burning after film formation. Conceptual distinction between development of film-drying technology that can be reduced and development of a positive-type photosensitive film that can greatly improve the adhesion of the positive-type photosensitive film itself by adding an auxiliary agent that strengthens adhesion, and has a large development latitude. Research continued to solve the former problem first.

  The solvent was considered to evaporate from the coating film. Since the coating film is dried from the surface by contact with air and increases in hardness and tightens the structure, it is considered that the diffusibility of the solvent existing in the inner layer decreases as time passes and the surface is dried. On the other hand, the degree of volatilization of the solvent from the coating film differs depending on the pressure of the atmosphere. If the pressure is negative, the degree of volatilization of the solvent from the coating film is large, and the residual solvent can be effectively reduced. However, the roll formed into a film cannot be put in the chamber evacuated using the vacuum pump. Here, the present inventor has found that the residual solvent concentration can be lowered to 3% or less in a short time when the plate making roll is rotated at a high speed after the coating film stops dripping.

  Based on this knowledge, the plate-making roll is horizontally supported on the photosensitive film coating apparatus according to Patent Document 30 and rotated at a required low speed, and the test photosensitive liquid is uniformly applied by a spiral scan method and a non-contact coating method. Then, as the technology that can continue to rotate and set the photosensitive film with the degree of dryness that the solvent has evaporated in a state where dripping does not occur, and subsequently, the solvent concentration can be greatly reduced in a very short time without burning, The plate-making roll is rotated at a required high speed for a required time, and centrifugal force is applied to the residual solvent in the film, and the film surface is rubbed with air to diffuse and remove the residual solvent in the film into the air. We have established a technology to obtain a low solvent residual concentration film that can exhibit image sticking.

  A photosensitive solution is uniformly applied to a 200 mm mm test roll, and 25 r. p. After rotating at m, the rotation was stopped, waited for 5 minutes, observed for dripping, and confirmed that no dripping occurred with the naked eye. p. After rotating at m for 20 minutes and stopping, the residual solvent concentration in the photosensitive film was measured and found to be 2.3%.

  However, by developing a technology that can greatly reduce the solvent concentration in a very short time without burning, various assistants that strengthen the adhesion are added and the positive photosensitive agent is exposed and developed for development. Research continued to see if it had latitude.

  As a result, a cellulose derivative and a titanium alkoxide are added to a stock solution of a positive photosensitive composition comprising an alkali-soluble organic polymer substance having a phenolic hydroxyl group and a photothermal conversion substance that absorbs infrared rays from an image exposure light source and converts it into heat. As a result of testing by including a titanium organic compound of at least one of titanium acylate and titanium chelate, the development is poor when the burning treatment is performed, and the development is excellent when the burning treatment is not performed. A pattern was obtained. At this time, the room temperature was 25 to 27 ° C., and the humidity was about 50 to 55%.

  However, a test was conducted on a day when the maximum daytime temperature was about 16 ° C. and the humidity was extremely low, 21 to 23%. As a result, the development revealed that the photosensitive film was completely removed. It is known that a positive type photosensitizer generally has a humidity dependency that a whitening phenomenon occurs at a high humidity of 60% or more and a film cannot be formed. However, it was found from the above results that the adhesion of the positive photosensitive agent does not appear even when the temperature is low and the humidity is extremely low. It was not possible to elucidate why the film could not be formed due to whitening.

  Therefore, a search was made for a resin having a development latitude as a base instead of an alkali-soluble organic polymer substance having a phenolic hydroxyl group. Instead of the alkali-soluble organic polymer having a phenolic hydroxyl group, a styrene / maleic anhydride half ester resin obtained by esterifying a styrene / maleic anhydride copolymer with an alcohol is used to absorb infrared rays from an image exposure light source. As a result of making a positive photosensitive composition containing a photothermal conversion substance that converts it into heat, forming a film on a roll, and performing exposure and development tests one after another, a large development latitude was obtained.

  More specifically, a 200 φmm plate-making roll plated with copper sulfate is used under the conditions that the room temperature in the laboratory is 25 ° C. and the humidity is changed to 25%, 30%, 55%, and 60% in the casing of the photosensitive film coating apparatus. Is supported at both ends by a photosensitive film coating apparatus and 25r. p. Apply the above positive photosensitive agent to rotate after m, wipe with a wiping cloth and follow, and continue to rotate so that no dripping occurs even after the application is completed, and allow 5 minutes to pass under natural drying conditions. 100 r. p. After rotating at m for 10 minutes to reduce residual solvent, the rotation was stopped.

  Each of the plate-making rolls taken out from the photosensitive film coating apparatus was glossy and a test roll coated with an extremely hard photosensitive film having very strong adhesion was obtained. The film thickness of the resist was 3.5 to 3.8 μm. When the residual solvent concentration was measured, all the test rolls were around 2.3%. A film in which a test image is exposed with a laser in the infrared wavelength region (exposed to the image area) by the above infrared laser exposure apparatus (manufactured by Sink Laboratories, Inc.), and then the non-image area is eluted when alkali development is performed. In any case, a resist pattern that was extremely sharp and free of residue was obtained when immersed in an alkali developer for 60 to 70 seconds. It was confirmed that the resist pattern which was naturally dried after the development was extremely hard. The resist film thickness after development was 1.8 to 2.5 μm. There was no pinhole due to film loss. Thus, the present invention has been completed.

  The present invention relates to a positive photosensitive composition that is exposed to a laser beam having a wavelength of 700 to 1,100 nm so that the sensitive part is soluble in an alkali developer. 1) The humidity in the coating chamber is 25 to 60%. Of course, it is necessary to apply to the object to be coated when applying in the above range, and subsequent burning is not required, and necessary and sufficient adhesion to aluminum is obtained. Necessary and sufficient adhesion to copper or copper sulfate plating can be obtained. 2) Good alkali development with no residue occurring in an appropriate time of about 60 to 70 seconds can be performed, and the alkali strength of the developer is low. Since development is possible, work during development and waste liquid processing are easy. 3) High sensitivity is maintained by not performing the burning process, and the edge of the resist image is in accordance with the exposure irradiation pattern. 4) Very good development can be performed with sharp contours, 4) Less film loss after development, and very good development with less pinholes due to film reduction, 5) Glossy resist image, A resist image having printing durability enough to print several thousand sheets even if subjected to printing as it is is obtained, and scratch resistance in handling before development after formation of a photosensitive film is improved. 6) Image printing and development latitude by laser is improved. An object of the present invention is to provide an excellent positive photosensitive composition.

In order to solve the above problems, the positive photosensitive composition of the present invention comprises (A) a polymer substance having at least one carboxyl group in the molecule, and (B) absorbing infrared rays from an image exposure light source to heat. A photothermal conversion material to be converted , and (E) (1) a vinylpyrrolidone / vinyl acetate copolymer, (2) a vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) a vinylpyrrolidone / vinylcaprolactam / dimethylaminoethyl methacrylate copolymer, (4) Selected from the group consisting of polyvinyl acetate, (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenol resin, (8) alkylphenol resin, (9) melamine / formaldehyde resin, and (10) ketone resin. It is characterized in that it contains at least one resin .

  A polymer obtained from the unsaturated compound (a1) having at least one carboxyl group and / or carboxylic anhydride group, and the unsaturated compound (a1) and the unsaturated compound; It is preferably at least one polymer substance selected from the group consisting of copolymers obtained from the copolymerizable compound (a2).

  It is preferable that the unsaturated compound (a1) is at least one compound selected from the group consisting of maleic acid, (meth) acrylic acid, and derivatives thereof. In the present invention, acrylic and methacryl are collectively referred to as (meth) acryl.

  The polymer substance (A) is at least one copolymer selected from the group consisting of a maleic acid polymer, a (meth) acrylic acid polymer, a styrene / maleic acid copolymer and a derivative thereof. Is preferred.

  The polymer substance (A) is preferably a styrene / maleic acid copolymer obtained by reacting a styrene / maleic anhydride copolymer with a compound having a hydroxyl group. It is preferable that the compound having a hydroxyl group is an alcohol.

  The polymer substance (A) is preferably a copolymer represented by the following general formula (1).

[In Formula (1), R < ¹ > and R < ² > show a hydrogen atom or a substituted or unsubstituted alkyl group each independently, a is an integer of 1-3, b is an integer of 6-8. ]

  It is preferable that the positive photosensitive composition of the present invention further contains (C) a dissolution inhibitor.

  The dissolution inhibitor (C) is preferably a compound represented by the following chemical formula (2).

  The photothermal conversion substance (B) is preferably a compound represented by the following general formula (3).

[In the formula ( 3 ), R ^{3 to} R ⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms, and X represents a halogen atom, ClO ₄ , _{BF 4, p-CH 3 C} 6 H 4 SO 3, or an PF _6. ]

  The photothermal conversion substance (B) is preferably a compound represented by the following general formula (4).

Wherein ^{(4), R} 9 ~R ¹² independently represents a hydrogen atom, a methoxy group, -N _{(CH 3) 2,} or indicates _{-N (C 2 H 5) 2} , Y is _C 4 H _{9 -B (C 6 H 5)} 3, p-CH 3 C 6 H 4 SO 3, or an _CF 3 SO _3. ]

  It is preferable that the positive photosensitive composition of the present invention further contains (D) a photoacid generator. The photoacid generator (D) is preferably a compound represented by the following formula (5).

The positive photosensitive composition of the present invention comprises (E) (1) vinyl pyrrolidone / vinyl acetate copolymer, (2) vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) vinyl pyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate copolymer. , (4) polyvinyl acetate, (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenol resin, (8) alkylphenol resin, (9) melamine / formaldehyde resin, and (10) ketone resin It is preferable to contain at least one resin selected from:

  It is preferable that the positive photosensitive composition of the present invention further contains (F) a triarylmethane dye.

  The photofabrication method of the present invention is characterized by using the positive photosensitive composition of the present invention. The photofabrication method is preferably applied to produce printing plates, electronic parts, precision equipment parts, anti-counterfeiting related members, and the like.

  The plate-making method of the present invention is characterized by using the positive photosensitive composition of the present invention. By the plate making method of the present invention, printing plates such as intaglio plates (gravure), planographic plates, letterpress plates and stencil plates can be prepared.

A general plate making process of a gravure plate using the positive photosensitive composition of the present invention as a photosensitive solution is as follows.
1. Applying a photosensitive solution to the cylinder (preferably a dry film thickness of 2-5 μm. A thicker film is better to eliminate pinholes, but a thinner film will reduce the amount used and lower the cost.) → 2. Dry (15 minutes to touch dry → 15 to 20 minutes to finish) → 3. Exposure (light source: semiconductor laser 830 nm, 220 mJ / cm ² ) → 4. Development (60 to 90 seconds / 25 ° C.) → 5. Washing with water (spray 30 seconds) → 6. Etching (depth 10-30 μm, corrosive cupric chloride aqueous solution, copper equivalent 60 g / L) → 7. Resist stripping (alkali stripping) → 8. Washing with water → 9. Cr plating (chromic acid 250 g / L, sulfuric acid 2.5 g / L with respect to water) → 10. Washing with water → 11. printing.

A general plate making process of a lithographic plate (PS plate) using the positive photosensitive composition of the present invention as a sensitizing solution is as follows.
1. CTP (PS plate) (aluminum polishing → photosensitive solution coating → drying) → 2. Exposure (light source: semiconductor laser 830 nm, 220 mJ / cm ² ) → 3. Development → 4. printing.

The positive photosensitive composition of the present invention is an alkali-soluble positive photosensitive composition having an infrared wavelength range laser sensitivity that makes the sensitive part soluble in a developer upon exposure to an infrared wavelength range laser beam. It is a composition and has the following excellent effects.
(1) Necessary and sufficient adhesion can be obtained without performing burning on an object to be coated such as glossy mirror-like plated copper as well as aluminum and copper. In addition, a glossy photosensitive film equivalent to that obtained by conventional burning can be obtained without burning.
(2) Necessary and sufficient adhesion can be obtained even under conditions of humidity of 25 to 60%.
(3) Good alkali development can be carried out with no residue generated in an appropriate time. Despite the fact that the photosensitive layer components do not substantially undergo chemical changes upon exposure, all the basic performances of the printing plate such as printing durability, sensitivity, and development latitude can be satisfied. Further, a polymer substance having a carboxyl group is used, and development is possible even when the alkali strength of the developer is low. Since the developer can be developed at a pH of 10 to 12, the amount of the carbon dioxide gas in the air is less dissolved, so that the alkaline developer is less deteriorated with time. On the other hand, the phenol resin developer has a decrease in pH immediately after the bathing due to the influence of carbon dioxide gas, and if it is not made into a buffer solution (buffer solution), it will not develop continuously. A drop occurs. In such a situation, compared with a phenol resin type developed with a developer having a pH of 13.0 or higher, the management of the decrease in alkali concentration is easy. Moreover, since the range of the choice of the alkali main agent is widened and the strength of the alkali waste liquid is low, the waste liquid treatment is easy. Building bath: To make a developer by diluting a developer solution with water in a developer tank.
(4) Even if image exposure is performed with an exposure energy lower than the high exposure energy in which excessive heat is generated by the photothermal conversion substance in the photosensitive layer, the development latitude can be widened and the degree of scattering of the photosensitive layer is suppressed to a low level. The problem of scattering (ablation) of the photosensitive layer and contamination of the optical system of the exposure apparatus does not occur.
(5) By not performing the burning process, high sensitivity can be maintained, and extremely good development can be performed in which the edge of the resist image is cut with a sharp contour according to the exposure irradiation pattern. Further, the end face portion can maintain a uniform film thickness after development because there is no variation in heat capacity due to burning.
(6) The resist image has little film loss, is glossy, and even if it is corroded as it is, no pinhole is generated and gravure plate making is possible. In addition, a resist image having printing durability enough to print several thousand sheets or more for printing or the like can be obtained, generation of pinholes in handling before development after drying of the photosensitive film can be avoided, or scratch resistance can be obtained. improves.
(7) The rate of change with respect to image printing by a laser is small, and the development latitude is excellent.
(8) Since the film loss after development is small, the occurrence of pinholes is small.

  Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

  The positive photosensitive composition of the present invention is essential for (A) a polymer substance having at least one carboxyl group in the molecule, and (B) a photothermal conversion substance that absorbs infrared rays from an image exposure light source and converts it into heat. It is contained as a component, and if necessary, (C) dissolution inhibitor, (D) photoacid generator, (E) (1) vinylpyrrolidone / vinyl acetate copolymer, (2) vinylpyrrolidone / dimethylaminoethyl Methacrylate copolymer, (3) vinyl pyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate copolymer, (4) polyvinyl acetate, (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenol resin, (8) alkylphenol resin, (9) Group consisting of melamine / formaldehyde resin and (10) ketone resin At least one resin al selected, and (F) preferably further blended triarylmethane dyes.

  The polymer substance (A) is not particularly limited as long as it is a polymer substance having at least one carboxyl group in the molecule, but is an unsaturated compound having at least one carboxyl group and / or carboxylic anhydride group. Suitable examples include the polymer (a1) and the copolymer of the unsaturated compound (a1) and the compound (a2) copolymerizable with the unsaturated compound. The polymer substance (A) preferably contains a carboxyl group so that the acid value is 30 to 500, particularly 200 to 250. The weight average molecular weight is preferably 1,500 to 100,000, more preferably around 7,000 to 10,000.

  As the unsaturated compound (a1), maleic acid, (meth) acrylic acid, fumaric acid, itaconic acid, and derivatives thereof are preferable, and these can be used alone or in combination of two or more.

  Examples of maleic acid and its derivatives (referred to as maleic monomers) include maleic acid, maleic anhydride, maleic acid monoesters (for example, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate). Suitable examples include, for example, monoisopropyl maleate, mono-n-butyl maleate, monoisobutyl maleate and mono-tert-butyl maleate), and maleic acid diesters.

  (Meth) acrylic acid and its derivatives [referred to as (meth) acrylic monomers. ], For example, (meth) acrylic acid or (meth) acrylic acid ester (for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc.) Is a suitable example.

  The compound (a2) copolymerizable with the unsaturated compound (a1) is preferably a compound having an unsaturated double bond, such as styrene, α-methylstyrene, m or p-methoxystyrene, p-methylstyrene, p. Styrene such as -hydroxystyrene and 3-hydroxymethyl-4-hydroxy-styrene and derivatives thereof (referred to as styrene monomers) are particularly preferable. These can be used alone or in combination of two or more.

  Examples of the polymer substance (A) include a polymer of the maleic monomer, a copolymer having a maleic monomer as a main component, a polymer of the (meth) acrylic monomer, and ( A copolymer based on a (meth) acrylic monomer, a maleic acid monomer, and a copolymer of a (meth) acrylic monomer and another monomer such as a styrene monomer, Styrene / maleic acid copolymer (hereinafter referred to as copolymer (b1)) obtained by copolymerizing maleic monomer and styrene monomer, acrylic monomer and styrene A copolymer with a monomer, a derivative of these polymers, or a modified product thereof is preferable. A maleic acid polymer, a (meth) acrylic acid polymer, represented by the following general formulas (6) and / or (7) And a copolymer having a structure represented by the following general formula (8) More preferably a copolymer of the Le acid (meth) acrylic acid ester and the styrene monomer, and more preferably a copolymer represented by the following general formula (1).

In the formula (6), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent, and preferably a hydrogen atom, a lower alkyl group or a group having a reactive double bond.

In the formula (8), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a methyl group, R ¹⁷ represents a hydrogen atom or a monovalent substituent, and hydrogen An atom, a hydroxyl group, an alkyl group or an alkoxyl group is preferable. R ¹⁸ represents a hydrogen atom or a monovalent substituent, and a hydrogen atom or a hydroxyalkyl group is preferable.

In the formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a substituted or unsubstituted alkyl group, a hydrogen atom, a lower alkyl group or alkoxy When there are a plurality of R ¹ and R ^{2 in} which an alkyl group is more preferable, they may be the same or different. It is preferable that at least one of R ¹ and R ² is a hydrogen atom, a is 0 or an integer of 1 or more, 1 to 3 is preferable, b is an integer of 1 or more, and 6 to 8 are preferable.

  The method for producing the styrene / maleic acid copolymer is not particularly limited and can be carried out according to a known method. However, the styrene / maleic anhydride copolymer (that is, styrene monomer and anhydride It is preferable to obtain a product obtained by reacting a compound having a hydroxyl group with a maleic acid copolymer).

  The compound having a hydroxyl group is not particularly limited, but alcohols such as isopropanol, n-propanol, isopropanol / cyclohexanol, butyl alcohol, isooctanol and ethylene glycol, ethylene glycol ethers such as ethylene glycol butyl ether, diethylene glycol ethyl ether and the like And diethylene glycol ether.

  In addition, as the polymer substance (A), the copolymer (b1) is modified with a compound having a reactive double bond [hereinafter referred to as copolymer (b2). ] May be used. In this case, the ratio of the structure represented by the formulas (6) and (7) to the structure represented by the formula (8) is preferably about 1. Specifically, the copolymer (b2) can be produced by reacting a compound having a reactive double bond with the acid anhydride group or carboxy group in the copolymer (b1). . In this case, it is necessary that the carboxyl group necessary for alkali development remains in the copolymer.

  The compound having a reactive double bond is preferably a compound having a carbon-carbon double bond, specifically, an unsaturated alcohol (for example, allyl alcohol, 2-buten-1-ol, furfuryl). Alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, etc.), alkyl (meth) acrylate (eg, methyl methacrylate, t-butyl methacrylate, etc.), oxirane ring and reactive Epoxy compounds each having one heavy bond (for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl itaconate monoalkyl) Glycidyl ester etc.) and the like as a preferable example.

  In addition, in order to further increase the concentration of the reactive double bond in the copolymer (b2) into which the reactive double bond is introduced by the unsaturated alcohol, the oxirane ring and the reactive double bond described above are used. Alternatively, an epoxy compound having one each may be reacted to further increase the reactive double bond concentration.

  The manufacturing method of the said copolymers (b1) and (b2) is not specifically limited, It can carry out according to a well-known method (for example, refer patent document 32-34 etc.). Reactive double bonds can also be introduced in a polymer substance having a carboxy group other than the styrene / maleic acid polymer in the same manner as described above. Giving a reactive double bond to a polymer material is preferable from the viewpoint of increasing the degree of curing and improving printing durability.

  Although the content rate of the high molecular substance (A) in the positive photosensitive composition of this invention is not specifically limited, (A) component, (B) component, (C) component, (D) component, (E) component And it is preferable that it is 80 to 98 weight% with respect to the solid content total amount of (F) component, and it is still more preferable that it is 90 to 95 weight%. These polymer substances (A) may be used alone or in combination of two or more.

  The photothermal conversion substance (B) is not particularly limited as long as it is a compound capable of converting the absorbed light into heat, but is an organic having an absorption band in part or all of the infrared region having a wavelength of 700 to 1,100 nm. Examples include inorganic pigments and dyes, organic pigments, metals, metal oxides, metal carbides, metal borides, etc., which efficiently absorb light in the wavelength range and hardly or absorb light in the ultraviolet range. However, a light-absorbing dye that is substantially insensitive is preferable, and a compound represented by the following general formula (3) or (4) or a derivative thereof is preferably used.

[In formula (3), R ^{3 to} R ⁸ are each independently a hydrogen atom, a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms), or a lower alkoxyl group (an alkoxyl group having 1 to 3 carbon atoms). Is preferable). X ⁻ represents a counter anion, and examples of X include a halogen atom, ClO ₄ , BF ₄ , p-CH ₃ C ₆ H ₄ SO ₃ , or PF ₆ . ]

[In the formula (4), R ^{9 to} R ¹² each independently represents a hydrogen atom, a methoxy group, —N (CH ₃ ) ₂ , or —N (C ₂ H ₅ ) ₂ , and Y ⁻ represents a counter anion. Y represents C ₄ H ₉ -B (C ₆ H ₅ ) ₃ , p-CH ₃ C ₆ H ₄ SO ₃ , CF ₃ SO ₃ , or the like. ]

  As the compound represented by the general formula (4), near infrared absorbing dyes represented by the following chemical formulas (9) to (12) having a maximum absorption wavelength in the near infrared region are more preferable.

  In addition, as other light-absorbing dyes, for example, a heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as described in Patent Document 6 is bonded with polymethine (—CH═) n. Typical examples include so-called cyanine dyes in a broad sense. Specific examples include quinoline (so-called cyanine), indole (so-called indocyanine), and benzothiazole (so-called thiocyanine). , Iminocyclohexadiene series (so-called polymethine series), pyrylium series, thiapyrylium series, squarylium series, croconium series, azurenium series, etc., among which quinoline series, indole series, benzothiazole series, iminocyclohexadiene series, pyrylium System or thiapyrylium system is preferred. In particular, phthalocyanine and cyanine are preferable.

  The photothermal conversion substance (B) has an absorption band in a part or all of the infrared wavelength region having a wavelength of 700 to 1,100 nm, and has a characteristic of thermally decomposing by absorbing laser light in the infrared wavelength region. Involvement in alkali-soluble molecular weight reduction and ablation by thermal cleavage of molecules of the polymer substance (A) having a carboxyl group.

  The amount of the photothermal conversion material added is related to the excess and deficiency of heat generated by exposure, and the intensity of infrared laser light is caused by excess and deficiency of thermal decomposition of the organic polymer substance present in the exposed part. Since it is related, it is set to an appropriate amount. The content ratio of the photothermal conversion substance (B) in the positive photosensitive composition of the present invention is as follows: (A) component, (B) component, (C) component, (D) component, (E) component, and (F) component The total solid content is preferably 0.1 to 10% by weight, more preferably 1 to 4% by weight.

  The dissolution inhibitor (C) is blended for the purpose of increasing the difference in solubility between the exposed area and the non-exposed area in the alkaline developer, and forms a hydrogen bond with the polymeric substance (A) to form the polymer substance. Those having a function of lowering the solubility, hardly absorbing light in the infrared region, and not being decomposed by light in the infrared region are used.

  As the dissolution inhibitor (C), a compound represented by the following formula (2) (4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol ) Is preferably used.

  Moreover, a well-known dissolution inhibitor can also be used as a dissolution inhibitor (C). Specifically, sulfonic acid ester, phosphoric acid ester, aromatic carboxylic acid ester, aromatic disulfone, carboxylic acid anhydride, aromatic ketone, aromatic aldehyde, aromatic amine, aromatic ether, etc., lactone skeleton, thiolactone skeleton , N, N-diarylamide skeleton, or acid color-forming dye having a diarylmethylimino skeleton, base color-forming dye having a lactone skeleton, thiolactone skeleton, or sulfolactone skeleton, nonionic surfactant, etc. Among these, acid coloring dyes having a lactone skeleton are preferred.

  The content of the dissolution inhibitor (C) in the positive photosensitive composition of the present invention is as follows: (A) component, (B) component, (C) component, (D) component, (E) component, and (F) component The total solid content is preferably 0.5 to 8% by weight, more preferably 1 to 5% by weight. These dissolution inhibitors may be used alone or in combination of two or more.

  The photoacid generator (D) is a substance that generates an acid by light, and acts as a sensitizer. Examples of the photoacid generator (D) include diphenyliodonium salts, triphenylsulfonium salts, aromatic sulfonic acid esters, triazine compounds, diazodisulfone compounds, and the following general formulas (13) to (47). The compound shown by these is preferable, and the compound shown by following formula (5) is especially preferable.

In formula (13), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, an alkyl group or an alkoxyl group, preferably a hydrogen atom, a methyl group, a tert-butyl group, a methylpropyl group or a methoxy group. Z ⁻ represents a counter anion, and as Z, inorganic acid anions such as PF ₆ , CF ₃ SO ₃ , C ₄ F ₉ SO ₃ , SbF ₆ , BF ₄ , p-toluenesulfonic acid, camphor-β-sulfonic acid, etc. Organic acid anions, and the like.

In formula (14), R ²¹ represents a hydrogen atom, an alkyl group, an alkoxyl group, or a —SC ₆ H ₅ group, and preferably a hydrogen atom, a methyl group, a tert-butyl group, a methylpropyl group, or a methoxy group. Z ⁻ is the same as in formula (13).

In the formula (16), R ²² is a monovalent organic group, and includes a trichloromethyl group, a phenyl group, a p-methoxyphenyl group, a dimethoxyphenyl group, a p-CH ₃ SC ₆ H ₄ group, a p-chlorophenyl group, Examples include methoxystyryl group, dimethoxystyryl group, trimethoxystyryl group, propoxystyryl group, butoxystyryl group, pentyloxystyryl group, p-methoxy-m-chlorostyryl group, 4'-methoxy-1'-naphthyl group, and the like. .

In formula (21), R ²³ represents a hydrogen atom or a monovalent organic group, and examples thereof include a hydrogen atom and a tert-butyl group.

In formula (24), R ²⁴ and R ²⁵ are each independently a hydrogen atom or a monovalent organic group, and examples thereof include a hydrogen atom, a methyl group, and a tert-butyl group.

In formula (25), R ²⁶ and R ²⁷ are each independently a hydrogen atom or a monovalent substituent, and examples thereof include a hydrogen atom, a chlorine atom, a methyl group, and a tert-butyl group. R ²⁸ and R ²⁹ are each independently a hydrogen atom or a methyl group.

In formula (31), Z ⁻ is the same as in formula (13).

In formula (32), Z ⁻ is the same as in formula (13). A is a hydrogen atom or a hydroxyl group.

In formula (33), Z ⁻ is the same as in formula (13).

In formula (34), R ³⁰ represents a hydrogen atom or a —SCH ₃ group.

In formula (36), R ^{31 to} R ³³ are each independently a monovalent organic group, and an alkyl group such as a methyl group or an ethyl group is preferable.

In the formula (37), R ³⁴ and R ³⁵ each independently represent a hydrogen atom or a NO ₂ group.

In the formula (38), R ³⁶ represents a hydrogen atom or a NO ₂ group.

In the formula (39), R ³⁷ represents a methyl group, a CF ₃ group, a phenyl group or a p-methylphenyl group.

In the formula (41), R ³⁷ is the same as in the formula (39).

In the formula (43), R ³⁷ is the same as in the formula (39).

In formula (47), Z ⁻ is the same as in formula (13).

  Specific examples of the photoacid generator include IRGACURE series of Ciba Specialty Chemicals Co., Ltd., and product names of Midori Chemical Co., Ltd .: BDE, Anisil, BBI-102, TAZ-101, TAZ-104, TAZ- Photoacid generators such as 106, TAZ-110, and BC can be widely used. Further, diazodisulfone and triphenylsulfonium photoacid generators from Wako Pure Chemical Industries, Ltd. can be used.

  The content ratio of the photoacid generator (D) in the positive photosensitive composition of the present invention is as follows: (A) component, (B) component, (C) component, (D) component, (E) component, and (F). It is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the total solid content of the components. These photoacid generators may be used alone or in combination of two or more. Moreover, you may use it in combination with another sensitizer.

  The resin (E) includes (1) vinyl pyrrolidone / vinyl acetate copolymer, (2) vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) vinyl pyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate copolymer, and (4) polyvinyl acetate. , (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenol resin, (8) alkylphenol resin, (9) melamine-formaldehyde resin, and (10) at least one selected from the group consisting of ketone resins It is an alkali-soluble resin and functions as an adhesion improver.

  The (1) vinyl pyrrolidone / vinyl acetate copolymer (hereinafter referred to as PVP / VA copolymer) is a thermoplastic resin obtained by copolymerizing vinyl pyrrolidone and vinyl acetate, and is represented by the following general formula (48). It has a structure.

  In formula (48), n and m are each an integer of 1 or more. The ratio of vinyl pyrrolidone and vinyl acetate in the PVP / VA copolymer is not particularly limited, but the ratio of vinyl pyrrolidone and vinyl acetate is preferably 70/30 to 30/70, more preferably 50/50.

  The method for producing the PVP / VA copolymer is not particularly limited, but a linear random copolymer obtained by free radical polymerization of vinylpyrrolidone and vinyl acetate is preferable. The molecular weight of the PVP / VA copolymer is not particularly limited, but is preferably 10,000 to 60,000, and more preferably 20,000 to 50,000.

  The (2) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer has a structure represented by the following general formula (49).

  In formula (49), n and m are each an integer of 1 or more.

  The (3) vinylpyrrolidone / vinylcaprolactam / dimethylaminoethyl methacrylate copolymer is a copolymer of vinylpyrrolidone, vinylcaprolactam and dimethylethyl methacrylate, and has a structure represented by the following general formula (50).

  In formula (50), n, m, and l are each an integer of 1 or more.

  The (4) polyvinyl acetate is a homopolymer of vinyl acetate or a copolymer containing vinyl acetate as a main component, and has a structure represented by the following general formula (51).

  In formula (51), n is an integer of 1 or more. As polyvinyl acetate, for example, Sacanol SN-09T (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd. is preferably used.

  The (5) polyvinyl butyral (abbreviated as PVB) is a resin obtained by butyralization in which polyvinyl alcohol is reacted with butyraldehyde, and has a structure represented by the following general formula (52).

  In formula (52), n, m, and l are each an integer of 1 or more. Specifically, as polyvinyl butyral, products from Denki Kagaku Kogyo Co., Ltd., Denkabutyral 5000A and 6000EP, products from Sekisui Chemical Co., Ltd., low polymerization types BL-1, BL-2, BL-2, BL -S, BX-L, medium polymerization type BM-1, BM-2, BM-5, BM-S, high polymerization type BH-3, BH-S, BX-1, BX-2, BX -5, BX-55, and the like are preferable examples, and BL-S, BM-S, and BH-S, which are soluble in various types of solvents, are particularly preferable.

  Said (6) polyvinyl formal (PVFM) is resin with favorable electrical insulation which has a structure shown by the following general formula (53).

  In formula (53), n, m, and l are each an integer of 1 or more. The method for producing polyvinyl formal is not particularly limited. For example, polyvinyl acetate is dissolved in acetic acid, and formaldehyde and sulfuric acid are added to perform a saponification reaction and a formalization reaction at the same time. The product is obtained through precipitation of formal and solvent recovery, washing, and drying steps.

  As said (7) terpene phenol resin, a conventionally well-known thing can be used widely. Specifically, Tamanol 803L and 901 (trade names manufactured by Arakawa Chemical Industries, Ltd.) are preferable examples.

  As said (8) alkylphenol resin, a conventionally well-known thing can be used widely. Specifically, Tamanol 520S, 521, 526, 586, and 572S (trade names manufactured by Arakawa Chemical Industries, Ltd.) are preferable examples.

  The (9) melamine-formaldehyde resin is a resin obtained by an addition condensation reaction between melamine and formaldehyde, and known melamine-formaldehyde resins can be widely used. Specifically, for example, it is preferable to use Vanserin SM-960 (trade name) manufactured by Harima Chemicals Co., Ltd.

  As said (10) ketone resin, a well-known ketone resin can be used and it is not specifically limited. For example, it can be obtained by reacting ketones with formaldehyde by a known method. Examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, and methylcyclohexanone, and cyclohexanone and acetophenone are particularly preferable. As the ketone resin, a cyclohexanone-based ketone resin represented by the following formula (54) and an acetophenone-based ketone resin having a structure represented by the following formula (55) are preferable.

  In Formula (54) and Formula (55), m and n are each an integer of 1 or more.

  The content ratio of the resin (E) in the positive photosensitive composition of the present invention is the solid content of the component (A), the component (B), the component (C), the component (D), the component (E), and the component (F). It is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the total amount of the components.

  As the (F) triarylmethane-based dye, conventionally known triarylmethane-based colored dyes can be widely used. Specifically, methyl violet, crystal violet, Victoria blue B, oil blue 613 (Orient Chemical Industries) (Trade name) manufactured by KK and their derivatives are preferred. These triarylmethane dyes can be used alone or in combination of two or more.

  By using a colored dye, there is an effect that when a pattern is formed by development, pinholes, dust and the like on the surface of the photosensitive film can be clearly recognized and the coating operation can be easily performed with a correction solution (opaque). The higher the concentration of the dye, the better it is easy to see. Since the semiconductor industry cannot make corrections, manufacturing is performed in a clean room. However, in the printing industry and electronic parts, corrections are made to regenerate failed products.

  The content ratio of the dye (F) in the positive photosensitive composition of the present invention is the solid content of the component (A), the component (B), the component (C), the component (D), the component (E), and the component (F). The amount is preferably 0.1 to 10% by weight, more preferably 1 to 4% by weight based on the total amount of the components.

Po di photosensitive composition of the present invention, in addition to the aforementioned components, as necessary, a coloring agent such as other pigments or dyes, sensitizers, development accelerators, adhesion modifiers, coating properties Various additives such as an improving agent may be blended. As the development accelerator, for example, it is preferable to add a small amount of dicarboxylic acid or amines or glycols.

  The positive photosensitive composition of the present invention is usually used as a solution dissolved in a solvent. The ratio of the solvent used is usually in the range of about 1 to 20 times by weight with respect to the total solid content of the photosensitive composition.

  The solvent is not particularly limited as long as it has sufficient solubility with respect to the components used and gives good coating properties. Cellosolve solvent, propylene glycol solvent, ester solvent, alcohol solvent, ketone solvent Solvents and highly polar solvents can be used. Examples of the cellosolve solvent include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate. Examples of the propylene glycol solvent 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, dipropylene glycol dimethyl ether and the like. . As ester solvents, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate Etc. Examples of the alcohol solvent include heptanol, hexanol, diacetone alcohol, furfuryl alcohol and the like. Examples of the highly polar solvent include ketone solvents such as cyclohexanone and methyl amyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. In addition, acetic acid or a mixed solvent thereof, and those obtained by adding aromatic hydrocarbons to these may be used.

  The positive photosensitive composition of the present invention is usually a copper-plated surface of a plate-making roll for gravure printing which is a support surface as a solution obtained by dissolving the above components in a solvent such as a cellosolve solvent or a propylene glycol solvent. After coating on the copper sulfate plating surface and air-drying, it rotates at high speed and blows off the surface of the plate-making roll. Is reduced to 6% or less to obtain a positive photosensitive film in which a photosensitive composition layer is formed on the support surface.

  As a coating method, meniscus coating, fountain coating, dip coating, spin coating, roll coating, wire bar coating, air knife coating, blade coating, curtain coating, and the like can be used. The thickness of the coating film is preferably in the range of 1 to 6 μm, more preferably 3 to 5 μm.

As a light source for image exposure of the positive photosensitive composition layer, a semiconductor laser or a YAG laser that generates an infrared laser beam having a wavelength of 700 to 1,100 mm is preferable. In addition, a solid laser such as a ruby laser or an LED can be used. The light intensity of the laser light source is preferably 2.0 × 10 ⁶ mJ / s · cm ² or more, and more preferably 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 the present invention, an inorganic alkali (for example, a salt of Na or K) or an organic alkali (for example, TMAH (Tetra Methyl Ammonium Hydroxide) is used. ) Or choline or the like, and a developer made of an inorganic or organic alkali is preferable.

  Development is usually performed at a temperature of about 15 to 45 ° C., preferably 22 to 32 ° C., by immersion development, spray development, brush development, ultrasonic development and the like.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

Example 1
A positive photosensitive composition was prepared with the compounding substances and blending ratios shown in Table 1, and used as a test photosensitive solution.

Each component in Table 1 is as follows.
Resin A1: SMA 1440 (manufactured by SARTOMER, partially esterified product of styrene / maleic anhydride copolymer with butyl cellosolve).
Infrared absorbing dye B1: Infrared absorbing dye represented by the above formula (3) Dissolution inhibitor 1: TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd., compound represented by the above formula (2)).
Photoacid generator 1: IRGACURE 250 (Ciba Specialty Chemicals Co., Ltd., compound represented by formula (5))
Resin E1: PVP / VA copolymer (copolymer of vinylpyrrolidone and vinyl acetate having a molecular weight of 46,000 and a glass transition point of 96 ° C., vinylpyrrolidone / vinyl acetate 50/50)
Coloring dye F1: Oil blue 613 (Orient Chemical Co., Ltd., Color Index (CI) No. 42595)
PM: Propylene glycol monomethyl ether IPA: Isopropyl alcohol MEK: Methyl ethyl ketone

  The following experiment was conducted using the obtained test photosensitive solution. The experiment was conducted at 25 ° C. under the humidity conditions shown in Table 2. A roll made of iron, copper sulfate-plated, and mirror-polished 200 mm mm plate-making roll is chucked at both ends with a fountain coating device (a device that can control humidity as desired by a dehumidifying device and a humidifying device). . p. Rotate at m and wipe thoroughly with a wiping cloth. In addition, this fountain coating apparatus avoids that the solvent in a positive photosensitive composition evaporates during coating and the ratio of a solvent changes.

  After that, the pipe from which the test photosensitive solution is sprinkled from the upper end is positioned so as to have a gap of about 500 μm at one end of the plate making roll, and the test photosensitive solution is swelled by an amount necessary for coating, and the pipe is made to plate making. Move from one end of the roll to the other end and apply the test sensitizing solution uniformly by a spiral scan method. p. After continuing the rotation at m, the rotation stopped.

  After waiting for 5 minutes and observing the dripping, it was not possible to observe that dripping occurred with the naked eye. When the film thickness was measured, there was no difference between the lower surface portion and the upper surface portion of the roll. Thus, it was confirmed that the dried photosensitive film could be set in a state without dripping.

  Subsequently, the test roll was set to 100 r. p. After rotating at m for 20 minutes and stopping, the residual solvent concentration in the photosensitive film was measured and found to be 2.9%.

  Subsequently, the test roll is attached to an exposure apparatus (manufactured by Sink Laboratories, Inc.) equipped with a high-power semiconductor laser head of Creositex, and a positive image is printed by irradiating the test roll with a laser in the infrared wavelength region. Then, the test roll was attached to the developing device and rotated to raise the developing tank, and development was performed until there was no residue, followed by washing with water. The developing solution used was 4.2% KOH (25 ° C.). The obtained resist images were evaluated with a microscope. The results are shown in Table 2.

The evaluation methods in Table 2 are as follows.
1) Edge Resolution Using the resolving power test pattern shown in FIG. 1, it was measured whether the edge of a 7.9 μm line of a checkered pattern or a grating was sharp. In the table, “◎” indicates a good result and the resolution is acceptable, and “×” indicates that the plate cannot be made without an image and the resolution is unacceptable.
2) Development latitude The measurement was carried out using a cell warehouse manufactured by Dai Nippon Printing Co., Ltd. (an apparatus capable of automatically measuring the aperture ratio of halftone dots). According to the test with a large number of developments (three times in this embodiment), if the cell area calculation is within 60-75 μm ² due to exposure of 7.9 μm × 7.9 μm, the print density is within the allowable range. Therefore, it is good and indicated by ◎ in the table. The case outside the allowable printing range is indicated by x in the table.
3) Adhesiveness tesa test: DIN EN ISO 2409 ◎ when 100 squares remain in the cross-cut adhesion test with tesa tape, ○ when peeled in a range of less than 20%, × when peeled 20% or more It was.
4) Sensitivity The exposure is determined and the sensitivity is determined by the reproducibility close to the image pattern. The exposure machine was a Creo thermal imaging head.
5) Development The development time until no residue was found was measured.
6) Remaining film ratio Using FILMETRICS Thin Film Analyzer F20 (manufactured by Filmmetrics Co), which is an apparatus for measuring the thickness of the coating film, the film thickness before development and the film thickness after development were measured, and the remaining film ratio was calculated. .
7) Image It was evaluated whether the reproducibility was close to the original image. A: Very good, X: Very bad,-: Image disappears in development.

  The photosensitive solution test pattern and measurement points are shown in FIG. Table 3 shows the check items and measurement methods for the measurement points in FIG.

  As shown in Table 2, the positive photosensitive composition of Example 1 has a good development that gives a sharp pattern with no residue in about 70 seconds under conditions of room temperature of 25 ° C. and humidity of 35 to 55%. Could do. The development latitude was also good.

  In addition, although the experiment was also performed when a copper surface or an aluminum surface was used instead of the copper sulfate plating surface, good results were obtained as in Example 1. In the case of the aluminum surface, a particularly wide development latitude was obtained.

(Examples 2 to 6)
The experiment was performed in the same manner as in Example 1-2 except that the components (B) and (F) in the composition were changed as shown in Table 4. The measurement conditions were those under a humidity of 45%. The results are also shown in Table 4.

In Table 4, the dyes B2 to B6 and the dyes F2 to F4 are as follows. In addition, the compounding quantity of a component (B) and (F) shows the weight part when the compounding quantity of a component (A) is 100 weight part, respectively.
Dye B2: IR-B (manufactured by Showa Denko KK, infrared absorbing dye represented by the above formula (9))
Dye B3: IR-T (manufactured by Showa Denko KK, infrared absorbing dye represented by the formula (10))
Dye B4: IR-2MF (manufactured by Showa Denko KK, infrared absorbing dye represented by the formula (11))
Dye B5: IR-13F (manufactured by Showa Denko KK, infrared absorbing dye represented by the formula (12))
Dye B6: NK-2014 (produced by Hayashibara Biochemical Laboratories, Inc., infrared absorbing dye represented by the following formula (56))

Dye F2: Eisenmethyl Violet BB Special (Hodogaya Chemical Co., Ltd., CI Basic Violet 1, No. 42535)
Dye F3: Eisen Crystal Violet (Hodogaya Chemical Co., Ltd., CI Basic Violet 3, No. 42555)
Dye F4: Eisen Victoria Blue BH (manufactured by Hodogaya Chemical Co., Ltd., CI Basic Blue 26, No. 44045)

(Examples 7 to 15)
An experiment was conducted in the same manner as in Example 1-2 except that the component (A) in the composition was changed as shown in Table 5. The results are also shown in Table 5.

In Table 5, the compounding quantity of a component (A) is the same as that of Example 1, and resin A2-A10 is as follows.
Resin A2: SMA 17352 (manufactured by SARTOMER, partially esterified product of styrene / maleic anhydride copolymer with isopropanol / cyclohexanol).
Resin A3: SMA 2624 (manufactured by SARTOMER, partially esterified product of styrene / maleic anhydride copolymer with n-propanol).
Resin A4: SMA 3840 (manufactured by SARTOMER, partially esterified product of styrene / maleic anhydride copolymer with isooctanol).
Resin A5: Oxylac SH-101 (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., styrene / maleic acid half ester copolymer).
Resin A6: A copolymer of acrylic acid, methyl methacrylate, and styrene (acid value 98, weight average molecular weight 21000, base monomer ratio acrylic acid: methyl methacrylate: styrene = 1: 1: 1).
Resin A7: Maleic acid polymer (acid value 300, weight average molecular weight 10,000)
Resin A8: Acrylic acid polymer (acid value 100, weight average molecular weight 25000)
Resin A9: Oxylac SH-101 derivative (styrene / maleic acid copolymer added with glycidyl methacrylate, acid value 80)
Resin A10: Resin A6 added with glycidyl methacrylate

(Examples 16 to 25)
An experiment was conducted in the same manner as in Example 1-2 except that each resin shown in Table 6 was used as the component (E) instead of the resin E1. The results are also shown in Table 6.

In Table 6, resins E2 to E11 are as follows.
Resin E2: GAFQUAT 734 (manufactured by ISP, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer)
Resin E3: GAFFIX VC-713 (manufactured by ISP, vinylpyrrolidone / vinylcaprolactam / dimethylaminoethyl methacrylate terpolymer)
Resin E4: Sacnol SN-09T (Electrochemical Industry Co., Ltd., polyvinyl acetate)
Resin E5: Denka butyral # 3000 (manufactured by Denki Kagaku Kogyo Co., Ltd., polyvinyl butyral)
Resin E6: Vinylec-K type (manufactured by Chisso Corporation, polyvinyl formal)
Resin E7: Tamanoru 803L (Arakawa Chemical Industries, Ltd., terpene phenol resin)
Resin E8: Tamanoru 520S (Arakawa Chemical Industries, Ltd., alkylphenol resin)
Resin E9: Vanserin SM-960 (Halima Kasei Co., Ltd., melamine / formaldehyde resin)
Resin E10: Hilac 111 (Hitachi Chemical Co., Ltd., cyclohexane resin)
Resin E11: Hilac 110H (Hitachi Chemical Co., Ltd., acetophenone resin)

(Example 26)
The experiment was performed in the same manner as in Example 1-2 except that the component (C) was not blended. The results are shown in Table 7.

(Example 27)
The experiment was performed in the same manner as in Example 1-2 except that the component (D) was not blended. The results are shown in Table 7.

(Experimental Example 1)
The experiment was performed in the same manner as in Example 1-2 except that the component (E) was not blended. The results are shown in Table 7.

(Experimental Example 2)
The experiment was performed in the same manner as in Example 1-2 except that the components (C), (D), and (E) were not blended. The results are shown in Table 7.

(Comparative Examples 1-3)
The experiment was conducted in the same manner as in Example 1-2 except that the composition of the positive photosensitive composition was changed as shown in Table 8. The results are shown in Table 9.

In Table 8, the infrared absorbing dye B1 and the solvent are the same as in Table 1, and the other components are as follows.
Novolac resin: PR-NMD-100 (manufactured by Sumitomo Bakelite)
Titanium organic compound: ORGATICS TA-10 (Titanium alkoxide) manufactured by Matsumoto Kogyo Seiyaku Co., Ltd.
Imidazolesilane: A silane coupling agent having the structure of the following formula (57). In the formula ^(57), each of R 41 ^{to R 44} alkyl radical, n is an integer of 1-3.

  As shown in Table 9, in Comparative Examples 1 to 3, the image disappeared after development, and no development latitude was obtained.

  The positive photosensitive composition of the present invention is preferable for forming a positive photosensitive film on a copper sulfate plated surface of a plate-making roll for gravure printing, but is not limited to this, and aluminum, zinc, steel Metal plates such as aluminum, zinc, copper, iron, chrome, nickel, etc., paper coated with resin, paper coated with a metal foil such as aluminum, plastic film, hydrophilic plastic Even if it is applied to a film, a glass plate, etc., the adhesiveness at low temperature is good and high sensitivity is obtained.

  Therefore, it can be suitably used for photosensitive lithographic printing plates, simple proof printing proofs, copper etching resists for wiring boards and gravure, color filter resists used in flat display manufacturing, LSI manufacturing photoresists, and the like.

It is drawing which shows the photosensitive solution test pattern and measurement location which were used in Example 1, (a) is a test pattern, (b) is an enlarged view of the circled part of (a).

Claims (17)

(A) a polymer substance having at least one carboxyl group in the molecule;
(B) a photothermal conversion substance that absorbs infrared rays from an image exposure light source and converts it into heat, and (E) (6) polyvinyl formal, and (10) at least one resin selected from the group consisting of ketone resins. Contains ,
Wherein (6) polyvinyl formal to a positive photosensitive composition, characterized in that have a structure represented by the following general formula (53).
[In the formula (53), n, m and l are each an integer of 1 or more. ] (A) a polymer substance having at least one carboxyl group in the molecule;
(B) a photothermal conversion material that absorbs infrared rays from an image exposure light source and converts it into heat, and (E) (1) vinylpyrrolidone / vinyl acetate copolymer, (2) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) vinyl Pyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate copolymer, (4) polyvinyl acetate, (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenol resin, (8) alkylphenol resin, (9) melamine / formaldehyde resin And (10) at least one resin selected from the group consisting of ketone resins,
The high molecular substance (A), Ri polymer der represented by the following general formula (1),
The (4) polyvinyl acetate is a homopolymer of vinyl acetate,
The (5) polyvinyl butyral has a structure represented by the following general formula (52):
Wherein (6) polyvinyl formals, positive photosensitive composition characterized Rukoto that having a structure represented by the following general formula (53).

[In Formula (1), R < ¹ > and R < ² > show a hydrogen atom or a substituted or unsubstituted alkyl group each independently, a is an integer of 1-3, b is an integer of 6-8. ]


[In the formula (52), n, m, and l are each an integer of 1 or more. ]
[In the formula (53), n, m and l are each an integer of 1 or more. ] (A) a polymer substance having at least one carboxyl group in the molecule;
(B) a photothermal conversion substance that absorbs infrared rays from an image exposure light source and converts it into heat,
(D) a photoacid generator, and (E) (1) a vinylpyrrolidone / vinyl acetate copolymer, (2) a vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) a vinylpyrrolidone / vinylcaprolactam / dimethylaminoethyl methacrylate copolymer, 4) selected from the group consisting of polyvinyl acetate, (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenol resin, (8) alkylphenol resin, (9) melamine / formaldehyde resin, and (10) ketone resin. Containing at least one resin,
The photoacid generator (D) is, Ri compound der represented by the following formula (5),
The (4) polyvinyl acetate is a homopolymer of vinyl acetate,
The (5) polyvinyl butyral has a structure represented by the following general formula (52):
Wherein (6) polyvinyl formals, positive photosensitive composition characterized Rukoto that having a structure represented by the following general formula (53).

[In the formula (52), n, m, and l are each an integer of 1 or more. ]
[In the formula (53), n, m and l are each an integer of 1 or more. ]   A polymer obtained from the unsaturated compound (a1) having at least one carboxyl group and / or carboxylic anhydride group, and the unsaturated compound (a1) and the unsaturated compound; 4. The positive photosensitive composition according to claim 1, wherein the positive photosensitive composition is at least one polymer compound selected from the group consisting of copolymers obtained from the copolymerizable compound (a2).   The positive photosensitive composition according to claim 4, wherein the unsaturated compound (a1) is at least one compound selected from the group consisting of maleic acid, (meth) acrylic acid, and derivatives thereof. object.   The polymer substance (A) is at least one polymer selected from the group consisting of a maleic acid polymer, a (meth) acrylic acid polymer, a styrene / maleic acid copolymer, and derivatives thereof. The positive photosensitive composition according to any one of claims 1 and 3 to 5.   7. The positive material according to claim 6, wherein the polymer substance (A) is a styrene / maleic acid copolymer obtained by reacting a styrene / maleic anhydride copolymer with a compound having a hydroxyl group. Type photosensitive composition.   The positive photosensitive composition according to claim 7, wherein the compound having a hydroxyl group is an alcohol. The positive photosensitive composition according to any one of claims 1 and 3 to 8, wherein the polymer substance (A) is a polymer represented by the following general formula (1).

[In Formula (1), R < ¹ > and R < ² > show a hydrogen atom or a substituted or unsubstituted alkyl group each independently, a is an integer of 1-3, b is an integer of 6-8. ]   The positive photosensitive composition according to claim 1 or 2, further comprising (D) a photoacid generator.   (C) The positive photosensitive composition of any one of Claims 1-10 which further contains a dissolution inhibitor. The positive photosensitive composition according to claim 1, wherein the photothermal conversion substance (B) is a compound represented by the following general formula (3).

Wherein ^(3), R 3 ~R ⁸ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 3 carbon atoms having 1 to 3 carbon atoms, X a halogen atom, _ClO 4, _{BF 4, p-CH 3 C} 6 H 4 SO 3, or an PF _6. ] The positive photosensitive composition according to claim 1, wherein the photothermal conversion substance (B) is a compound represented by the following general formula (4).


Wherein ^{(4), R} 9 ~R ¹² independently represents a hydrogen atom, a methoxy group, -N _{(CH 3) 2,} or indicates _{-N (C 2 H 5) 2} , Y is _C 4 H _{9 -B (C 6 H 5)} 3, p-CH 3 C 6 H 4 SO 3, or an _CF 3 SO _3. ]   (F) The positive photosensitive composition according to any one of claims 1 to 13, further comprising a triarylmethane dye.   A photofabrication method using the positive photosensitive composition according to claim 1.   16. The photofabrication method according to claim 15, wherein the photofabrication method is applied to manufacture a printing plate, an electronic component, a precision instrument component, or an anti-counterfeit related member.   A plate making method using the positive photosensitive composition according to claim 1.