DE60317337T2 - Positive-working photosensitive composition - Google Patents

Description

BACKGROUND OF THE INVENTION

1. Field of the invention

It becomes an alkali-soluble positive photosensitive composition with laser sensitive Property provided in the range of infrared wavelengths whose light-sensitive part of a laser beam with a wavelength of 700 to 1100 nm is exposed and in a developer liquid soluble is.

2. Description of the related technology

A conventional, the prior art positive photosensitive lithographic plate contains a composition of novolak resin and o-quinone diazide, a substance the opposite white light is sensitive to light. This plate becomes a keten structure by a Transformation of the Arndt-Eisten type by photolysis (chemical transformation) of o-quinone diazide, as in the following chemical Formula (1), wherein a five-membered cyclic carboxylic acid is formed. Keten in an upper part of the photosensitive layer in one exposed area reacts with naphthoquinone diazide in the lower Part of the photosensitive layer and forms a lactone; this becomes sodium carboxylate by opening the lactone ring, if a developing process with an alkaline aqueous solution takes place. The co-existing novolak resin will also washed out, since it is soluble with alkali, and the still unexposed The area of the photosensitive layer in turn generates a coupling reaction with the co-existing novolak resin becomes an alkali solution retarder and remains as a resist image. In this way, if an o-quinone diazide composition is a considerable one Development latitude are achieved.

In In this case, the development latitude can be defined as one in which a development process can be performed, wherein a There is a difference between a time in which the exposed area the developer solution is exposed and the exposed area completely removed is, and a time in which a sufficient amount of residual film guaranteed in the unexposed area is, even if it is exposed to the developer liquid.

On the other hand, in order to enable the production of a photogravure plate under a white light lamp, a positive photosensitive composition having another change than a chemical change was invented. A method has been developed for copying a positive image with laser light of infrared wavelength range, wherein the solubility of the exposed area increases compared to the developer liquid, so that a positive image is formed, and this was done in the manufacture of an offset plate or a flexographic printing plate. As technical documents are in the Japanese Official Gazette published documents no. 1998 (10) -268,512 ; 1999 (11) -194.504 ; 1999 (11) -223.936 ; 1999 (11) -84.657 ; 1999 (11) -174.681 ; 1999 (11) -231.515 ; WO97 / 39.894 ; WO98 / 42.507 ; the Japanese Patent Laid-Open Publication No. 2002-189293 ; and 2002 to 189.295 and the like are available.

The in each of the above documents described positive photosensitive Contains lithographic plate as the main one photosensitive component of a substance, the infrared rays absorbed to heat these up to convert, for. An IR-absorbing pigment, and an alkali-soluble one Resin such. Novolac resin and the like, and it becomes a physical change like a conformational change of the Resin and the like by heat caused by exposure to an infrared laser light, and then the solubility across from the developer fluid elevated.

However, in the positive type photosensitive lithographic plate containing no o-quinonediazide composition, copying a positive image with a laser beam in an infrared wavelength range, generating a physical change such as a conformational change of the resin and the like to increase its solubility requires a firing process. a warming operation) after applying a film. Such compositions are for example in WO 2003 001301 A1 and in US 6,489,078 B1 disclosed. Even when the firing process is performed, the difference in the dissolution speed between an exposed part and an unexposed part is small, the basic performance characteristics of a printing plate such as sensitivity and development latitude are poor, so that it is difficult to achieve constancy in the development process when the number of plates is increased during the development process.

With regard to the above situation, this situation is in the photo engraving plate manufacturing process very different. In Japan, where photogravure plate making and printing technology is widely used in the industry, there has not yet been any method of producing a photogravure plate in the prior art in which photogravure plate production can be performed by applying a positive thermal resist, which can be performed Development process without heating after forming a coating film, and there are no patent documents and trial documents.

Of the Photographic plate manufacturing process for a plate made Roller by means of a corrosive / laser beam plate manufacturing process consists of clamping → degreasing → washing → pickling → washing → ballast or roller processing → washing → ballad or roller copper plating → washing → grinding with a whetstone → wash → apply of a photosensitive agent → application of antioxidant → image copy with an infrared laser exposure device → development → washing → etching → washing → peeling off the Resists → washing → grinding Washing → Unclamping.

As technical documents disclosing the photogravure plate manufacturing method for a clad gravure roll by means of a corrosive / laser plate-making method, there can be cited some prior art documents, ie Japanese Patent Application No. 1998 (10) -193551 ; 1998 (10) -193552 ; the Japanese Patent Laid-Open Publication No. 2000-062342 ; 2000-062343 ; 2000-062344 ; 2001-179923 ; 2001-179924 ; 2001-187440 ; 2001-187441 ; 2001-191475 ; 2001-191476 ; 2001-260304 ; 2002-127369 ; 2002-187249 ; 2002-187250 ; 2002-200728 ; 2002-200729 ; 2002-307640 ; and 2002-307641 ,

All Photographic printing plate production process described in the above-mentioned documents be done that way that a photosensitive film consisting of a negative photosensitive Composition is applied, and no photosensitive Film is applied, which consists of a positive photosensitive Composition exists. During the etching process The prior art becomes the negative photosensitive film Applied to the plated gravure roll, the applied Film dried at room temperature and solidified to a negative photosensitive film is formed with an argon ion laser beam made a copy, and there is no more positive photosensitive in the prior art Film formed on the plated gravure roll, and there is none Copy image onto the positive photosensitive medium with a laser beam of infrared wavelength.

One High power semiconductor laser head manufactured by Creo-Scitex Corporation Canada, emits a laser beam of infrared wavelength range and this is attached to an offset press to to radiate against the positive photosensitive composition. It can be done a high quality development, and therefore finds this practically worldwide application.

at a same beam diameter of an argon ion laser beam and a laser beam having a wavelength of 700 to 1,100 nm the laser resolution higher than in the positive photosensitive composition those in the negative photosensitive composition, and the Processing time can be considerable be reduced.

moreover can through the photosensitive film of the photosensitive positive working composition, for copying a negative image is used with an argon ion laser, better, sharper structures can be achieved as through the photosensitive film of the negative photosensitive composition used to copy a negative image is used with an argon ion laser. This is at a difference Sharp in the structure according to one Difference in the positive photosensitive composition and the negative photosensitive composition.

One Reason why in the prior art, the positive photosensitive Composition for producing an offset plate or a flexographic printing plate is used, but not in the Photogravurplattenherstellung is used in the fact that the negative photosensitive Medium was used in the latter Photogravurplattenherstellung. The negative photosensitive agent is a material for use when irradiated with ultraviolet rays to such an extent of resin polymerization Adjust in the irradiated area that, no matter what material quality at the coated area chosen a necessary and sufficient development latitude can be guaranteed.

Again, there was no positive photosensitive composition with development latitude that could be satisfactory in terms of copper sulfate plating on the photogravure printing roll. In particular, there was no photosensitive composition without performing any firing after coating. Although the positive photosensitive composition used in the Production of an offset plate or flexographic printing plate is used, is applied to the plated gravure roll, there is hardly the prerequisite for the formation of a film. In many cases, the coating film of the positive photosensitive composition in the plated photogravure roll is thoroughly washed off by the alkaline developer. This also applies to the case that firing is carried out after coating.

One System for the production of photogravure plates with high resolution by means of of the positive photosensitive film using either a semiconductor laser or a YAG laser or the like, the is capable of producing a powerful laser beam of infrared Wavelength range is to be generated in terms of its realization a device of small dimensions, ambient light at the time plate making, resolving power and sharp structures and the like in comparison with the case in which an argon ion laser is used, highly desirable.

The present inventor et al. have begun to make a positive to develop photosensitive composition, in view of on the copper sulfate plating of a photogravure printing roll in Considering the above circumstances without performing any Burning process after coating a required and sufficient Has development latitude.

Then, the present inventors et al. as to the etching method used as one of the plate-making methods for a photo-engraved printing roller, an undiluted solution of the positive photosensitive composition mixed with novolak resin and cyanine dye is prepared, and the solvent-diluted positive photosensitive agent is applied to the copper sulfate plating surface of the plated photoengraving roller; to form this. In the case of applying the positive photosensitive agent, a photosensitive film coating apparatus according to the present invention was used Japanese Patent Publication No. 1995 (07) -109511 (manufactured by Think Laboratory Co., Ltd.). Then, an infrared wavelength laser beam was irradiated from an infrared laser exposure apparatus (manufactured by Think Laboratory Co., Ltd.) having a built-in high-power semiconductor laser head of Creo-Scitex Corporation to copy the positive image, and a development test was carried out As a result, the photosensitive film was completely removed and a satisfactory resist image could not be obtained.

The evaluation of a formed film formed by the photosensitive film coating apparatus of the present invention Japanese Patent Publication No. 1995 (7) -109511 This prior art apparatus has been shown to be a contact coating type spiral scanning system in which the coating roller is immersed in the photosensitive agent in the container. The photosensitive agent is applied several times on the coated surface, and it can be assumed that air mixes with the photosensitive film. The container is an open structure so that solvents in the photosensitive agent stored in the container are vaporized and latent heat of vaporization is dissipated. The coating roller is cooled so that a coating with equation phenomenon is produced. The concentration of the solvent becomes ever smaller, the viscosity gradually increases, and a coating film of uniform film thickness can not be obtained. Therefore, the present inventors have concluded that the positive photosensitive agent film is wholly unsuitable even if the negative-working photosensitive agent is properly applied and the photosensitive film coating apparatus according to the present invention Japanese Patent Publication No. 1995 (7) -109511 makes a movie.

In view of the above, the present inventors have the photosensitive film coating apparatus of the present invention Japanese Patent Publication No. 1995 (7) -109511 and to develop a photosensitive film coating apparatus in which the solvent in the photosensitive agent in the container is not evaporated in its sealed state, the material can be applied to the plated gravure roller without contact, and the coating with a toner can be prevented Equation phenomenon goes along.

The Apparatus for coating with photosensitive film is in the section which is the preferred embodiment of the present invention Invention treated in detail to be discribed.

Briefly, as a method for applying the positive photosensitive agent to a plated gravure roll, the upper end of the photosensitive agent discharge tube functioning as a vertical tube approximates a lower surface of one end of the plated gravure roll clamped at both ends in a horizontal state is and is rotated, the photosensitive agent is added so that it overflows slightly bulging at the upper end of the photosensitive agent outflow tube, the photosensitive agent outflow tube is moved from one end of the plated gravure roll to the other end thereof, the coating liquid is applied to the photosensitive member through a spiral scanning system plated gravure roll is applied and the rotation of the roll is continued until the applied film shows an automatic drying.

Regarding the above showed our continued investigation that no Condition of a tight, close contact of the positive photosensitive Achieved composition with the copper sulphate plated surface could be and the operation of their development led to that the positive photosensitive composition on all image lines and non-image lines was quickly removed with alkaline developer solution.

by virtue of This fact was unavoidable that a burning process for warming the film surface is performed at a high temperature after application of the film and a firm contact force is applied.

One Reason why it was necessary to perform the burning process existed in the fact that as a result of a pretty bad liability no positive photosensitive composition on the copper sulfate plating surface Film is formed and the firing process after film formation allows that a hydrogen bond the alkali-soluble organic high molecular weight substance containing a phenolic hydroxyl group has amplified and the liability is improved.

Our discontinued Investigation on the assumption that the firing process is currently being carried out, showed that when the positive photosensitive composition, in which the above mentioned prepared novolak resin and cyanine dye mixed together were applied to the plated gravure roll, the burning Run through for 30 minutes was to the film surface temperature to 60 ° C to bring, she was exposed with a laser and developed, an inferior developed condition has been achieved.

Therefore the firing was carried out for 30 minutes such that the film surface temperature was 130 ° C. Even under this condition a flawed appearance arose, where both the image lines and the non-image lines Completely were away.

The present inventors came to the conclusion that a reason for the emergence a poorly developed state even when performing the Burning in too low adhesion of the positive photosensitive Composition consists of copper sulfate plating.

Therefore could due to an increase the adhesion to the photosensitive film by adding Silane coupling agent as a promoter to increase the adhesive force to the positive Photosensitive composition both exposure and development done in a slightly better way become.

In practical terms, the plated craving roll having a diameter of, for example, ⌀ 200 mm was rotated at a low rotational speed of 0.42 s ^-1 (25 rpm), the positive photosensitive agent was applied thereto, and its rotation was continued to drip of liquid, the photosensitive film had a degree of drying after 5 minutes under natural drying conditions, at which the solvent had turned into gas so far that no dripping of liquid occurred, and after this operation, the residual concentration of solvent became 30 -minous firing at 130 ° C less than 2%, the image could be copied by means of a laser and the operation could be carried out to its development.

Even though the film liability could be described as excellent, went both Exposure as well as development does not have a marginally better Area beyond.

moreover became clear that upon heating the film surface up 130 ° C the Burning and the subsequent Cooling a longer one Time required as 100 minutes, a big heat was required, the running costs were high and bad Performance characteristics showed.

In addition, when the film surface temperature was brought to 130 ° C, the hydrogen bonding of the phenolic hydroxyl group-containing alkali-soluble organic high molecular substance was enhanced, which caused hardly any development, and at the same time was ge The sharpness of the structure suggests that the cyanine dye was denatured and its sensitivity lowered.

Then A closer look at the resist image made it clear that many pinholes had been generated. In the case of the negative resist image there were no such pinholes as above. Reasons for this Apparition consisted in the fact that mere washing with water after the precision grinding with a whetstone not completely wash away the at the clad gravure roll allowed adhering sanding dust; if the plate making room is not considered a high-grade clean room was designed, the grinding dust on the plated engraved roller while hanging from their transport; and the positive resist image was a lot more sensitive to the Film production conditions as the negative resist image.

consequently could occur in relation to our various investigations be limited by pinholes by before coating the plated gravure roller with photosensitive agent sufficient Wiping process was performed with a cloth.

When next the present inventors et al. for important, the film surface temperature to reduce the problem of specific heat capacity, as it is at There are two types of rollers to plated photogravure rollers, i. H. a roller with aluminum as base material and the other roller with Iron as base material. In addition, their roll diameters are different different, and cause different diameters of the rolls, that their thickness completely different is what causes that, even if they are from a heater just for the same Duration of time to be heated in terms of a difference in specific heat capacity, Heat to Roll base material is passed and the film surface temperature not always at 130 ° C heated and where the rolls are heated to different temperatures, a disorder arises.

The The present inventors believed that the burning process for significant reduction in solvent concentration can be accomplished, even if it is at a much lower level Temperature as 130 ° C carried out is chosen by choosing a composition that is better Solvent elimination shows.

It a test to reduce the heating time was performed Firing temperature for the film surface was at 80 ° C up to 100 ° C lowered, and the firing was carried out for 50 minutes. It confirmed itself, that the concentration of the solvent is 6% or less amounted to. However, led this process to a state of poor development. As a reason It was assumed that the above-mentioned silane coupling agent no required and sufficient liability.

Then was used in place of the silane coupling agent acting as a holding agent experimentally added imidazole, which acts as a curing accelerator. However, there was no specific change compared to the case of the silane coupling agent, and the firing temperature at the film surface was also the same as the silane coupling agent.

Then led the The present inventor carried out an experiment in which a neat solution of a positive photosensitive composition consisting of an alkali-soluble organic high molecular weight substance with phenolic hydroxyl group and a light in heat transforming substance for absorption of infrared rays one Image exposure light source and for conversion of infrared rays in heat existed, various types of adhesives were added. at a room temperature of 25 ° C was a photosensitive film on the copper sulphate plated roller formed by the above mentioned Infrared laser exposure apparatus (manufactured by Think Laboratory Co., Ltd.) became a test image exposed, and the film was developed, with the result that the firing temperature for the photosensitive film with an organo-organic compound Substituted positive photosensitive composition considerably could be reduced.

in the Case of the photosensitive film with an organo-organic Compound offset positive photosensitive composition the film could even in a first class at a firing temperature of 46 ° C. Be prepared, its sensitivity was excellent and the development process was easy to do.

however could do a test without implementation a burning process does not achieve any improved film formation, and there was a poor development.

Also when the firing temperature could be lowered to about 50 ° C, was with regard to the necessity of carrying out the firing process, the Necessity of implementation a cooling process after the burning process, where for the burning process and its subsequent cooling process time and energy needed that's about the length the firing device enlarged length of the Plant, of the raised Costs for the plant and the raised Operating costs at a disadvantage. Therefore, the present inventors were the view that the removal of the burning process is a problem is that solved should.

at the implementation a burning process shows that the roller has a high heat load which differs from that of a thin plate member; It takes 30 to 60 minutes to get to a required temperature heated is, it takes 50 to 100 minutes or more to cool down to room temperature, and moreover can not be unified control because these times in terms the size of the roller to become different. In addition, the execution of the burning process causes that the cyanine dye is denatured, its sensitivity decreases, sharp structures deteriorate, the thickness of the resist at the time the development process thinner becomes, its contour shrinks and a reason for the production of some pinholes arises.

consequently is a development of the positive photosensitive film without the need for a burning process is highly desirable.

When Result of a repetition of several tests carried out made a high Concentration of residual solvent such as MEK, IPA, PM and the like at the time of film production clearly that a picture can not be copied by a laser (It will either be a main chain or a side chain of molecules of the the photosensitive film-forming resin in the exposed one Area divides, causing them to become lower molecules, the one increased alkali show, and at the same time, in a state where the photosensitive Layer is sufficiently distributed, no latent image is formed).

When the positive photosensitive agent was applied to the copper sulfate coating, the residual concentration of solvent after 15 minutes under natural drying conditions at a room temperature of 25 ° C without air blowing was 11% and the residual concentration of solvent after the elapse of 25 Hours 9%. The result of a 10-minute measurement in which the positive photosensitive agent was applied to the plated photogravure roller at a rotational speed of 0.75 s ^-1 (45 rpm) showed that the residual concentration of the solvent dropped only to 7% was.

Around the quality by including a promoter that strengthens the adhesive force in the positive to change photosensitive agents, an undiluted one solution of the positive photosensitive film, which does not burn requires to recreate and the result of it by exposure and to confirm evolution, It has therefore proved necessary, in advance, a process engineering to develop, with which it is possible is the residual concentration of solvent to reduce the above accordingly considerably.

thereupon The present inventors et al. for the first time as a development topic a practical application of no burning process requiring positive photosensitive film, distinguished as technical Concept both developments, d. H. the development of a film production and drying technology, with which it is possible the residual concentration on solvent in a short span of time and easily through another Means that independent from a burning process after the film formation is to significantly reduce and the other development of the positive photosensitive film, a significant improvement in the adhesive properties of the positive photosensitive film even by adding an adhesion-enhancing Promotors enabled and a big one Development latitude, and then continue the investigation to solve the former problem first.

The Present inventors have considered the fact that solvents volatilized from the applied film. It has been considered the distribution of the solvent present on the inner layer decreases with increasing time and the surface dries increasingly, since the applied film touches air, leaving it from the surface it dries and its hardness rises and its structure is strengthened. Then again it was considered that the extent, in which the solvent volatilized from the applied film, is changed by the pressure of the surrounding atmosphere, the extent of evaporation, with the solvent volatilized from the applied film, at a negative pressure is high and the remaining solvent can be effectively reduced. It is not possible, however Roller with the film applied to it in one by a vacuum pump to arrange evacuated space.

In In view of the above, the present inventors et al. the plated photoengraving roller at a high speed after no liquid more of the enraged film, and found that the Residual concentration of the solvent within a short period of time down to 3% or below can be.

In view of the above, the plated photogravure roller was used in the photosensitive film coating apparatus of the present invention Japanese Patent Publication No. 1995 (07) -109511 supported at both ends in a horizontal state, rotated at a predetermined low speed, uniformly photosensitive test liquid was applied by a spiral scanning and non-contact coating system, rotation was continued after this operation, the photosensitive film solidified with such a degree of dryness as one, in which the solvent has evaporated, so that no dripping of liquid was effected.

Then have the present inventors as a process technology with which it is possible the concentration of solvent within a fairly short period of time without performing any Significantly reduce firing, a technique for obtaining a introduced shaped film, which has a lower residual concentration of solvent and with the laser beam, an image printing property can be realized can, with the remaining solvent in the film by rotating the plated photogravure roller for a predetermined one Time is distributed at a predetermined high speed and discharged into the air is, with a centrifugal force on the residual solvent exercised in the film and the film surface comes in frictional contact with air.

Uniformly photosensitive liquid was applied to a test roller of ⌀ 200 mm, and rotation was continued at 0.42 s ^-1 (25 rpm) for 5 minutes after completion of the coating operation, after which rotation was stopped, maintained for 5 minutes, and dropped Fluid considered. No dripping of liquid was confirmed with the naked eye. The test roller was rotated and stopped at a rotational speed of 1.67 s ^-1 (100 rpm) for 20 minutes, the residual concentration of solvent in the photosensitive film was measured, and its value was 2.3%.

Of another led the development of process engineering with which it is possible the concentration of solvent within a fairly short period of time without performing any To significantly reduce firing, to make a promoter to amplify various Types of adhesive force has been added. The positive photosensitive Funds were exposed and developed, and further investigation was whether the product had a development margin.

consequently was at least one organo-organic compound from the group Cellulose derivative, titanium alkoxide, titanium acrylate or titanium chelate in the undiluted solution the positive photosensitive composition consisting of a alkali-soluble organic high molecular weight substance with phenolic hydroxyl group and a substance capable of photothermal conversion for absorption of infrared rays of the image exposure light source was incorporated and tested, with the result that a burning process becomes deficient Development led the omission of a burning process to an excellent state of development led and an exquisite one Resist pattern could be achieved. At this time, the room temperature was 25 to 27 ° C and the humidity was about 50 to 55%.

however showed tests in one day with a maximum of 16 ° C and a fairly low humidity of 21 to 23%, the photosensitive film is completely removed by the development process has been.

It is well known in the industry that the positive photosensitive Means a moisture dependence having at a high humidity of 60% or more a bleaching phenomenon can arise and no film can be formed.

The However, the above results made it clear that even at low air temperature and quite low humidity none Adhesive force of the positive photosensitive agent occurs. moreover could be the cause why the bleaching phenomenon arises and no movie is formed, not clarified become.

Thus, in a housing of a photosensitive film coating apparatus according to the above Japanese Patent Publication No. 1995 (07) -109511 installed a dehumidifier and a humidifier to control the humidity. Subsequently, it was searched extensively for substances to enhance the adhesive force, added a small amount of substance to form a film, and successively, a test for exposure and development of the film was carried out, with the result that each of the positive photosensitive agents having one of the adhesion property-improving agents of claim 1 and an undiluted solution of an alkali-soluble organic high molecular substance as claimed in claim 1 and one For the photothermal conversion capable of absorbing infrared rays of an image exposure light source and its conversion into heat mixed and added thereto, showed a large development latitude.

In detail, the ⌀ 200 mm plated photogravure roller clad with copper sulfate was clamped at both ends to a photosensitive film coating apparatus and rotated at a rotational speed of 0.42 s ^-1 (25 rpm) under conditions of wherein the room temperature in a test room was 25 ° C and the humidity in the housing of the photosensitive film coating apparatus was changed to 25%, 30%, 55% and 60%, respectively. The roller was wiped with a wiper, the positive photosensitive agent was applied appropriately, and rotation was continued even after completion of the coating operation to prevent dripping of liquid. The film was formed after lapse of 5 minutes under natural drying conditions, and the roller was then rotated at a rotation speed of 1.67 s ^-1 (100 rpm) for 10 minutes, the residual solvent was reduced, and its rotation was stopped.

All plated photogravure rollers, the coating device were taken with photosensitive film could as test rolls to be obtained with a gloss that is quite hard-sensitive Film coated and formed, which showed gloss and one pretty high adhesion.

The Film thickness of the resist was about 3.5 to 3.8 microns. The measurement of the remaining Solvent concentration showed that all test rolls had about 2.3%.

Then was determined by the above-mentioned infrared laser exposure apparatus (manufactured by Think Laboratory Co., Ltd.) with a laser of infrared wavelength range exposed the test image (the image lines were exposed), then it was developed with alkali, with the result being that in the non-image area by dissolving a movie reduction was created. However, in all cases, after 60- to 70-second Dipping into the alkali developer liquid is quite a tart Resist pattern achieved without residues. Then it could be proved that in a natural way dried resist pattern after a certain time after the Development process is quite tough. The film thickness of the resist film After the development process was 1.8 to 2.5 microns. There were no pinholes as a result of the film reduction.

With From the above, the present invention was developed.

SUMMARY OF THE INVENTION

This invention relates to a positive photosensitive composition in which the photosensitive member is exposed by means of a laser beam having a wavelength of 700 to 1100 nm. It can be dissolved in an alkaline developing solution and has the objective of providing a positive photosensitive composition with the following results:
after firing, no firing is necessary, and sufficient and sufficient adhesion to aluminum can be achieved when coating is carried out at a humidity of 25 to 60% in a working space;
moreover, it has, in particular, the property that a required and sufficient state of adhesion can be attained not only on aluminum but also on copper or copper sulfate plating, which requires much more adhesion than aluminum;
it can be in an appropriate time, about 60 to 70 seconds, an excellent alkaline development without generating any residues;
non-burning processing makes it possible to carry out a very excellent development in which high sensitivity can be preserved and an edge of the resist image is cut in sharp outline in strict accordance with an exposure pattern;
a very excellent development can be carried out while only a small film reduction takes place. It is possible to avoid the occurrence of pinholes caused by film reduction;
the resist image has a gloss, it can be achieved a fairly hard resist image, with which during the print proper printing several thousand copies, and there are better scratch-resistant properties after forming the photosensitive film in handling before the development process; and
the copy of the image by laser and the development latitude are excellent.

The The above objects are achieved by the positive photosensitive composition solved according to claim 1 of the invention.

• (1) Ein Brennen nach dem Beschichten eines plattierten Photogravurgegenstands ist nicht zweckmäßig, und es besteht die Eigenschaft, dass ein erforderlicher und ausreichender Haftungszustand erzielt werden kann, auch wenn das Brennen nicht durchgeführt wird. Es kann ein lichtempfindlicher Film mit Glanz und einem recht harten Zustand gewonnen werden.
• (2) Es kann eine erforderliche und ausreichende Haftung erzielt werden, wenn das Beschichten an einem schönen Tag bei einer Feuchtigkeit von 25 bis 60% in einem Arbeitsraum durchgeführt wird oder das Beschichten bei einer Feuchtigkeit von 25 bis 60% in dem Arbeitsraum unter Einsatz einer Entfeuchtungsvorrichtung und einer Befeuchtungsvorrichtung durchgeführt wird.
• (3) Es kann in einer angemessenen Zeit eine ausgezeichnete alkalische Entwicklung ohne Erzeugung irgendwelcher Rückstände durchgeführt werden. Ungeachtet der Tatsache, dass die Komponente in der lichtempfindlichen Schicht durch Belichtung im wesentlichen keinerlei chemische Veränderung erzeugt, können alle grundlegenden Leistungsanforderungen an eine Druckplatte wie z. B. eine Plattenverschleißeigenschaft, Empfindlichkeit und Entwicklungsspielraum (Differenz zwischen der Zeit, in welcher der belichtete Bereich bei der Entwicklung vollständig entfernt wird und der restliche Filmanteil des unbelichteten Bereichs bei der Entwicklung vollständig gewährleistet ist) erfüllt werden.
• (4) Auch wenn die Bildbelichtung statt mit einer höheren Belichtungsenergie, bei der von der zur photothermischen Umwandlung fähigen Substanz in der lichtempfindlichen Schicht übermäßige Wärme erzeugt wird, mit einer geringeren Belichtungsenergie durchgeführt wird, kann der Entwicklungsspielraum breit angesetzt werden, so dass der an der lichtempfindlichen Schicht erzeugte Verteilungsgrad deutlich niedrig begrenzt ist und kein Problem auftritt, dass die lichtempfindliche Schicht auseinanderläuft und das optische System in der Belichtungsvorrichtung kontaminiert wird.
• (5) Eine Verarbeitung ohne Brennen ermöglicht die Durchführung einer ganz ausgezeichneten Entwicklung, bei der eine hohe Empfindlichkeit bewahrt werden kann und eine Kante des Resistbildes in genauer Übereinstimmung mit einem Belichtungsmuster in einer scharfen Kontur geschnitten wird.
• (6) Es kann eine ganz ausgezeichnete Entwicklung durchgeführt werden, während kaum eine Filmreduktion erfolgt. Es ist möglich, das Auftreten von Nadelstichporen zu vermeiden, die durch Filmreduktion verursacht werden;
• (7) Das Resistbild hat einen Glanz, es kann ein recht hartes Resistbild erzielt werden, mit dem sich während des eigentlichen Drucks mehrere tausend Kopien drucken lassen, und es bestehen nach dem Bilden des lichtempfindlichen Films bei der Handhabung vor dem Entwicklungsvorgang bessere Kratzschutzeigenschaften.
• (8) Die Kopie des Bildes mittels Laser und der Entwicklungsspielraum sind ausgezeichnet.

The positive photosensitive member of this invention having the photosensitive member is exposed by means of a laser beam having an infrared wavelength and can be dissolved in an alkaline developing liquid. And the following excellent results are obtained with the positive photosensitive composition:

• (1) Burning after the coating of a clad photogravure article is not appropriate, and there is a characteristic that a required and sufficient state of adhesion can be obtained even if the burning is not performed. A photosensitive film with gloss and a fairly hard state can be obtained.
• (2) A required and sufficient adhesion can be obtained when the coating is carried out on a nice day at a humidity of 25 to 60% in a working space or the coating at a humidity of 25 to 60% in the working space using a Dehumidifying device and a moistening device is performed.
• (3) Excellent alkaline development can be performed in a timely manner without producing any residue. Notwithstanding the fact that the component in the photosensitive layer produces substantially no chemical change by exposure, all basic performance requirements can be met by a printing plate such as a printing plate. A plate wear property, sensitivity and development margin (difference between the time in which the exposed area is completely removed in the development and the residual film portion of the unexposed area is completely ensured in the development) are satisfied.
• (4) Although the image exposure is performed at a lower exposure energy, rather than a higher exposure energy, which generates excessive heat in the photosensitive layer from the photo-thermal conversion substance, the development latitude can be set broadly, so that the light output at the light-sensitive layer generated is significantly low limited and there is no problem that the photosensitive layer diverge and the optical system is contaminated in the exposure device.
• (5) Processing without burning makes it possible to carry out a very excellent development in which high sensitivity can be preserved and an edge of the resist image is cut in a sharp contour in strict accordance with an exposure pattern.
• (6) Very excellent development can be made while hardly reducing the film. It is possible to avoid the occurrence of pinholes caused by film reduction;
• (7) The resist image has a gloss, a rather hard resist image capable of printing several thousand copies during the actual printing, and better scratch-resistant properties after forming the photosensitive film in handling before the development process.
• (8) The laser copy of the image and the development latitude are excellent.

Even though the positive photosensitive composition according to the present invention Invention for forming a positive photosensitive film a copper sulfate-plated surface of a plated photogravure roller preferably for a copper light pressure is used, this composition not limited to this application, and even if this composition is on a plate of metals such as aluminum, zinc and steel or the like, a metallic one Plate made with aluminum, copper, chrome and nickel or the like clad or vaporized, resin coated paper, paper is connected to a metal foil such as aluminum and the like, a plastic film, a hydrophilized plastic film and a glass plate is applied, it shows an excellent Adhesion at a low temperature, and it can be a high sensitivity be achieved.

consequently she can preferably for a printing plate of a photosensitive lithograph, a template for a convenient proof, a printed circuit board or a photogravure copper etch resist, a color filter resist, as used in the manufacture of a flat panel display unit and a photoresist for making an LSI or the like be used.

BRIEF DESCRIPTION OF THE DRAWINGS

1 Fig. 12 is a schematic plan view illustrating an apparatus for producing photo-engraving plates for carrying out a photo-engraving plate manufacturing method.

2 Fig. 10 is an elevational view illustrating an apparatus for applying a photosensitive film.

3 is an elevational view illustrating an NC lathe.

4 is a display screen that displays input values or measurements or calculated values such as Cutting depth and the like for use in performing high-precision machining of rolls by an NC lathe.

5 is a view based on a roller cross-sectional area, the relationship between input values or measured values or calculated values such. Cutting depth and the like for use in performing high-precision machining of rolls by an NC lathe.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The The above objects are achieved by the positive photosensitive composition solved according to claim 1 of the invention.

Possibly For example, the positive photosensitive composition may also be a development accelerator or contain a solution retarder.

Of the Solids content of alkali-soluble organic polymeric substance having hydroxyl group in the positive The photosensitive composition is preferably 80 to 96% by weight. and it is further preferable that this value is 90 to 94% by weight. is.

Of the Solids content of substance capable of photothermal conversion in the positive photosensitive composition is preferably 1 to 10 wt .-%, and it is further preferable that this value 2 to 4 wt .-% is.

Of the Solids content of vinylpyrrolidone / vinyl acetate copolymers or the like as an alkali-soluble resin is Preferably 1 to 10 wt .-%, and it is further preferable that this value is 2 to 4% by weight.

The positive photosensitive composition of the present invention becomes in its diluted state in solvent used. The amount of solvent used is in this Fall normally in a range between 1 to 20 times in terms of the total amount of photosensitive composition (Weight ratio).

As the alkali-soluble organic polymer substance having phenolic hydroxyl group, novolak resin, resole resin, polyvinyl phenol resin, copolymers of acrylic acid derivatives having phenolic hydroxyl group, alkali-soluble epoxy resin in which the epoxy resin has been reacted with phenolic hydroxyl groups or the like, and further those described in U.S.Pat Japanese Patent Laid-Open Publication No. 1999-231515 As described, the above-described alkali-soluble organic polymer substance having phenolic hydroxyl group can be used, and it is preferable to use, in particular, novolak resin or polyvinylphenol resin.

novolak is a resin in which at least one of the phenols is present an acidic catalyst with at least one aldehyde or ketone was polycondensed. It is in particular a polycondensation material from mixed phenols consisting of m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and resorcinol, or mixed phenols that are composed of phenol, m-cresol and p-cresol, and formaldehyde, and that by means of a gel permeation chromatography measurement by polystyrene reduced weight average molecular weight (MW) is preferably 1,500 to 10,000.

resole is a resin that is polycondensed in the same way with Exception of using an alkaline catalyst instead of the acid catalyst in a polycondensation of novolac resin.

polyvinyl is a resin in which, for example, one or more than two types of hydroxystyrene in the presence of a radical polymerization initiator or cationic polymerization initiator. Preferably, a polymer of hydroxystyrenes which is an alkyl group having 1 to 4 carbon atoms as a substituent on the benzene ring, or a polymer of hydroxystyrenes which has a bezol ring without any Substitution have used.

The substance capable of photothermal conversion has one absorbing area in a part or the whole of an infrared Wavelength range with one wavelength from 700 to 1,100 nm, the property possesses a laser beam in the infrared wavelength range to absorb to perform a thermolysis, and contributes to the erosion and formation of alkali-soluble lower molecules by thermal decomposition of molecules of the alkali-soluble organic polymer substances having the above phenolic hydroxyl group at. A larger or lower amount of added photothermal conversion volume enabled Substances are related to an excessive or small amount of heat generated by exposure, strong or weak Infrared laser beam is related to excessive or deficient thermolysis the alkali-soluble organic polymer substance present in the exposed area, so that a suitable content is set.

As a substance capable of photothermal conversion, there may be mentioned organic or inorganic pigments or dyes, organic pigment, metal, metal oxide, metal carbide, metal boride or the like, and those described in U.S. Pat Japanese Patent Laid-Open No. 1999 (11) -231515 described photothermal conversion substance having an absorbing region in a part or in the entire infrared region having a wavelength of 700 to 1100 nm are used entirely as such. Heterocycles or the like containing a nitrogen atom, oxygen atom or sulfur atom and the like are linked by polymethine (-CH =) n; the broadly defined so-called cyanine dye can be more typically used, and, for example, quinoline type dyes (so-called "cyanine"), indole type (so-called "indocyanine"), benzothiazole type (so-called "thiocyanine"), iminocyclohexadiene type (so-called "polymethine"), Pyrylium type, thiapyrylium type, squarylium type, chloronium type, azulenium type or the like, and in particular, quinoline type, indole type, benzothiazole type, iminocyclohexadiene type, pyrylium type or thiapyrylium type dyes are particularly preferred. Specifically, phthalocyanine or cyanine is preferred.

What the solvent no specific restriction is required if the Solvent substance a sufficient solubility for the used component and a very good film coating property guaranteed. It can solvent Cellosolve type, propylene glycol type, ester type, alcoholic type, Ketone type and strongly polar solvents be used.

When solvent Cellosolvetyp can Methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate and the like can be used.

When solvent of the propylene glycol type 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 can be used.

When solvent butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, Diethyl oxolate, ethyl acetylformate, 2-hydroxybutanoate, Ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate or the like can be used.

When alcoholic solvent may heptanol, hexanol, diacetone alcohol, furfuryl alcohol or the like be used.

When strongly polar solvent can solvent ketone type such as cyclohexanone, methylamyl ketone, dimethylformamide, Dimethylacetamide, N-methylpyrrolidone or the like become.

Of Further can acetic acid or a solvent mixture these components and solvents, to which an aromatic hydrocarbon has been added become.

Possibly For example, the positive photosensitive composition may also be a development accelerator or contain a solution retarder.

Preferably For example, the development accelerator becomes a small amount Dicarboxylic acid or Added amines or glycols.

When Solution Delay is an acidic color pigment having a lactone structure is preferable. This solution retarder works such that it forms a hydrogen bond with alkali-soluble forms organic polymer substance and the solubility of the polymer substance degrades, so the solubility with respect to the alkaline developer liquid in the exposed area and stronger in the unexposed area delayed is, and also acts so that it has little light in the infrared range absorbed and not dissolved with light in the infrared range.

When other dissolution inhibitors can be acidic Color pigments with thiolactone structure, N, N-diarylamide structure and diarylmethylimine structure, basic color pigments with sulfolactone structure, non-ionic surfactants or the like, such as sulfonate, phosphate, aromatic carboxylate, aromatic disulfonic acid, carboxylic anhydride, aromatic ketone, aromatic aldehyde, aromatic amine, aromatic Ethers and the like can be used.

The positive photosensitive composition of the present invention is normally applied as a positive photosensitive film formed with a photosensitive composition layer on a surface of a support member by a method in which a solution in which each of the above-mentioned components is dissolved in solvents such as Cellosolve ^™ type solvent or a propylene glycol type solvent is applied to either a copper plating surface or a copper sulfate plating surface of the plated photogravure roller for a copper light pressure serving as a surface of the support member, dried naturally, and then the roller at a high speed is rotated, air is blown onto the surface of the plated photogravure roller, a mass action is caused in the photosensitive film by a centrifugal force and a slight under pressure kzustand near the surface causes the residual concentration of solvent to be reduced to 6% or less.

Although, as the coating method, the photosensitive film applying device 6 which is an in-plane photosensitive film device 6 is preferably used 1 This sprayer is not limited to this process. It is also possible to apply a meniscus coating or a dip coating obtained by a vertical dip coating apparatus. The thickness of the coated film may be set in a range of 1 to 6 μm, and is preferably set in a range of 3 to 5 μm.

When Light source for use in the exposure of an image becomes a layer of positive photosensitive composition preferably using either a semiconductor laser or a YAG laser, which generates an infrared laser beam with a wavelength of 700 to 1100 nm. Furthermore, it is also possible a solid-state laser how to use a ruby laser and an LED or the like.

The beam intensity of the laser light source is preferably 2.0 × 10 ⁶ mJ / s · cm ² or more, and it is particularly preferable that its value is 1.0 × 10 mJ / s · cm ² or more.

When developer liquid for one photosensitive film using the positive photosensitive Composition of the present invention is formed, is preferably a developer composed of either an inorganic or an organic alkali such as inorganic alkali, salts of Na, K or organic alkali, TMAH or choline and the like consists. In the case of an experiment was used as a developer liquid Original developer liquid used, the (a) sodium orthosilicate (b) trisodium phosphate, etc. (c) containing surfactant and the like.

Of the Development process is usually done by a dipping development, spray development, Brush development and ultrasound development or the like a temperature of 15 to 45 ° C and preferably at a temperature of 27 to 32 ° C.

[Development latitude of the positive photosensitive Composition]

• (1) der Kupplungsgrad von Filmen zweckentsprechend ist, entweder die Hauptkette oder die Seitenkette von Molekülen im belichteten Bereich durch Belichtung mit dem Infrarotlaserstrahl zertrennt wird, eine physikalische Veränderung wie eine Konformationsänderung, die bewirkt, dass die Moleküle zu niederen Molekülen werden, die eine größere Alkalilöslichkeit zeigen, sowie eine geeignete Ablösbarkeit der lichtempfindlichen Schicht erzeugt wird, um einen dünnen Film zu erzielen, und das Molekül so verändert wird, dass es sich in der alkalischen Entwicklerflüssigkeit innerhalb einer kurzen Zeitspanne löst; und
• (2) der unbelichtete Bereich für einen verhältnismäßig längeren Zeitraum als der belichtete Bereich nicht aufgelöst wird, bis er mit alkalischer Entwicklerlösung aufgelöst wird, auch wenn eine leichte Abweichung in Temperatur und Feuchtigkeit auftritt, und stark und eng an der beschichteten Oberfläche haftet.

The development latitude of the positive photosensitive composition is achieved by the phenomenon that

• (1) the degree of coupling of films is appropriate, either the main chain or the side chain of molecules in the exposed region is disrupted by exposure to the infrared laser beam, a physical change such as a conformational change that causes the molecules to become low Mo molecules which exhibit greater alkali solubility as well as suitable releasability of the photosensitive layer are formed to obtain a thin film, and the molecule is changed so as to dissolve in the alkaline developing liquid in a short period of time; and
• (2) the unexposed area is not dissolved for a relatively longer period of time than the exposed area until it is dissolved with alkaline developing solution, even if a slight deviation in temperature and humidity occurs, and strongly and closely adheres to the coated surface.

Of the Development latitude can not be achieved according to the fact that if the adhesion of the material that reinforces the adhesion, strong is a weak adhesion of the alkali-soluble organic polymer substances can be reinforced with phenolic hydroxyl group. The achievement of adhesion by the adhesion-enhancing material in the positive Photosensitive composition is relatively fixed in relation on both the type and the added amount of haftkraftverstärkendem Material.

in the Case of the positive photosensitive composition becomes, for example when choosing titanium alkoxide as an adhesion-enhancing material and additive a big one Amount of titanium alkoxide the strength, stability and adhesion of the whole Films after a burning process too strong, which leads to a physical change like a conformational change by exposure to the infrared laser beam or a resolution the photosensitive layer is not generated, and even if the development process performed becomes, the exposed area hardly in the developer liquid resolved and the entire movie is not reduced. That is, the Development latitude can not be achieved under any circumstances.

at increasing the amount added reduces the film and it slowly creates an area in which a development latitude can be achieved, a slight difference in room temperature or moisture, however, causes the development latitude not reached immediately.

On the other hand can, even if the alkali-soluble organic polymeric substance having phenolic hydroxyl group Silane coupling agent is added, no strong adhesion achieved become. There is no difference between the time in which the layer of positive photosensitive composition in exposed area in the alkaline developer liquid disbanded becomes, and the other time, in which the layer of positive photosensitive composition in the unexposed area in the alkaline developer liquid disbanded and this happens at the same time, and it can not be a development process be achieved.

in the Further, the following positive photosensitive composition under the condition of a room temperature of 25 ° C and a humidity of 25 to 60% made. The composition is applied to a copper surface or a copper sulfate-plated surface applied, the concentration of residual solvent is 6% or less, it can be an excellent development process be performed, in which in about 60 to 70 seconds sharp structures without generation any residues received can be.

Of the best development latitude is achieved when vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers and the like are contained at a solid content of 3%.

[Positive Photosensitive Composition of the present invention]

[Chemische Formel 3]

The positive photosensitive composition of the present invention contains an alkali-soluble organic polymer substance as claimed in claim 1 and a photothermal conversion substance for absorbing infrared rays of an image exposure light source and converting them to heat, and is further subjected to any of the respective ones claimed in claim 1 Substances as an adhesive property improving agent may be mixed and offset. [Chemical formula 2]

[Chemical Formula 3]

[Chemical formula 4]

[Chemical formula 5]

[Chemische Formel 7]

[Chemische Formel 8]

[Chemische Formel 9]

[Chemische Formel 10]

[Chemische Formel 11]

[Chemische Formel 12]

[In formula (5), R 1 denotes either a hydrogen atom or a methyl group, R 2 denotes a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group, R 3 denotes either a hydrogen atom or a hydroxyalkyl group, R 4 and R 5 independently denote a hydrogen atom, a lower alkyl group or a group with reactive double bond, m and n denote integers above 1 and is m ≥ n.] [Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

The [Chemical formula 2] represents a vinylpyrrolidone / vinyl acetate copolymer dar. PVP / VA copolymers (vinylpyrrolidone / vinyl acetate copolymers) are transparent thermoplastic linear random copolymers in which Vinylpyrrolidone and vinyl acetate in a ratio of 70/30 to 30/70 free have been radically polymerized, the molecular weight of 20,000 up to 50,000 and their hydrophilicity increases with increasing proportion of vinylpyrrolidone.

The PVP / VA copolymers are preferably such that vinyl pyrrolidone and vinyl acetate are present in a ratio of 60/40, in which case the molecular weight is 45 x 10 ³ and T g is 110 ° C.

The [Chemical Formula 3] represents polyvinyl butyral. Polyvinyl butyral:
The existing chemical substance No. 6-708 is a substance obtained by butyral formation when butylaldehyde is reacted with polyvinyl alcohol. There remains a considerable amount of hydroxyl groups and acetyl groups, and this is indicated by a structure represented by the above general formula.

As PVB many products are available, eg. Denka ^™ Butyral 5000A, 6000EP, manufactured by Denki Kagaku Kogyo Kabushiki Kaisha; the products of Sekisui Kagaku Kogyo Co., Ltd. BL-1, BL-2, BL-S, BX-L of low degree of polymerization; BM-1, BM-2, BM-5, BM-S of medium degree of polymerization; BH-3, BH-S, BX-1, BX-2, BX-5, BX-55 of high degree of polymerization, and as to an experimental result, the use of BL-S, BM-S and BH-S, which in different Types of solvents are soluble, preferably.

The [Chemical formula 4] and [Chemical formula 5] represent styrene / maleic acid copolymers.

Styrene / maleic acid copolymers are copolymers of styrene and maleic acid.

The styrene / maleic acid copolymers represented in formula (4) bear the product name Oxilack ^™ SH-101, copolymers of styrene and maleic acid half-ester. Preferably, a product is used wherein maleic acid half ester is adjusted in styrene solution having an acid value of 60 to 90 under an alcoholic reaction.

As styrene / maleic acid copolymers represented by formula (5), there may be copolymers in which styrenes such as styrene, alphamethylstyrene, m- or p-methoxystyrene, p-methylstyrene, p-hydroxystyrene, 3-hydroxymethyl-4-hydroxy styrene or derivatives thereof (styrene type monomer) and maleic acid derivatives such as maleic anhydride, maleic acid, monomethylmaleic acid, monoethylmaleic acid, mono-n-propylmaleic acid, monoisopropylmaleic acid, mono-n-butylmaleic acid, monoisobutylmaleic acid, mono-tert-butylmaleic acid and the like are copolymerized (hereinafter referred to as " Copolymer (a) "designated). As the copolymer (a), though not shown in the above structural formula, methyl methacrylate, alkyl methacrylate such as methyl methacrylate, etc., may be used. T-butyl methacrylate, alkyl acrylate, or the above copolymer (a) has been denatured by a compound having a reactive double bond (hereinafter referred to as copolymer (b)). In this case, m and n are integers greater than 1 and are in a ratio of m ≥ n, and preferably m / n = 1 to 1.1. As the weight-average molecular weight, a value of 1,500 to 100,000 be vorzugt.

The The above-mentioned copolymer (b) can be produced by a method in which either the acid anhydride group or the carboxyl group in the copolymer (a) with unsaturated Alcohols, for example allyl alcohol, but-2-ene-1,2-diol, furfuryl alcohol, Oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, N-methylolacrylamide; and an epoxy compound, each having a Oxiranring and having a reactive double bond, such as. Glycidyl acrylate, Glycidyl methacrylate, allyl glycidyl acrylate, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, Itaconsäuremonoalkylmonoglycidylester or the like is reacted. In this case is it is necessary for the carboxyl group to carry out a alkaline development process is necessary in the copolymer remains.

The Epoxy compound, each having the above-mentioned oxirane ring and a reactive Has double bond, is reacted with material, which has a reactive double bond, which is characterized by the unsaturated Alcohol of the copolymer (b) obtained as described above was introduced, to increase the concentration of reactive double bond, and then a copolymer with an increased concentration of reactive Double bond (hereinafter referred to as "copolymer (c) "designates) getting produced.

Other polymers having carboxyl groups as styrene / maleic acid copolymers can also be given a reactive double bond in the same manner as described above. The addition of the reactive double bond to the copolymer is preferable in terms of photosensitivity. The synthesis of these copolymers (copolymer (a), copolymer (b), copolymer (c) and the like) can be carried out according to the methods described in patent publication numbers , 1972 (47) -25 470 . 1973 (48) -85 679 and 1976 (51) -21 572 of the Japanese Official Journal.

The [Chemical formula 6] represents vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers.

The [Chemical formula 7] represents vinylpyrrolidone / vinylcaprolactam / dimethylaminoethyl methacrylate terpolymers represents.

The [Chemical formula 8] represents polyvinyl formal. Polyvinyl formal resin can be recovered as a product by a process in which vinyl acetate monomer is polymerized by means of a catalyst to polyvinyl acetate then polyvinyl acetate is dissolved in acetic acid, then formaldehyde and sulfuric acid be added to both a saponification (alkaline Hydrolysis) as well as a reaction with formaldehyde, dilute sulfuric acid added is to precipitate polyvinyl formal resin, its further processing by solvent recovery, Washing and drying steps takes place.

polyvinyl is composed of polyvinyl formal groups, polyvinyl alcohol groups and Polyvinyl acetate groups together and has excellent electrical Insulating properties.

[Terpene phenol resin and alkylphenol resin are not shown in a chemical formula.]

Terpene-phenolic resin and alkylphenol resin are products manufactured by Arakawa Chemical Industry Ltd. getting produced. As the terpene phenolic resin, the products named Tamanor ^™ 803L, 901 can be used, and as the alkylphenol resin, the products named Tamanor ^™ 520S, 521, 526, 586 and 572S can be used.

The [Chemical formula 9] represents melamine / formaldehyde resin.

Melamine / formaldehyde resin is prepared by reaction of melamine (C ₃ H ₆ N ₆ ) and formaldehyde. This synthetic reaction is incomplete and unreacted formaldehyde is left behind.

The [Chemical formula 10] represents polyvinyl acetate.

Polyvinyl acetate is a polymer compound prepared by polymerizing vinyl acetate, and for example, Sacnor ^™ SN-09T (product name) manufactured by Denki Kagaku Kogyo Kabushiki Kaisha can be used. Polyvinyl acetate has the structure shown in the following chemical formula which is solid, has a white to light yellow color, is insoluble in water, but is soluble in alcohol type, acetic type and aromatic type solvents.

[Chemical Formula 11] and [Chemical Formula 12] represent ketone resin.

When Ketone resin may be any of methyl ethyl ketone, methyl isobutyl ketone, Acetophenone, cyclohexanone, methylcyclohexanone find use. In this case, the use of cyclohexanone is shown in the chemical formula 11, and acetophenone, presented in the chemical formula 12, preferred.

[Embodiments and comparative examples]

[Development latitude of the positive photosensitive Composition of the present invention]

In Table 1 through Table 10 are some results of embodiments in which the Photogravurplattenherstellung according to the described Plate-making process using these positive photosensitive Compositions performed has been.

The the following four kinds of a positive photosensitive composition, in the embodiments in Table 1 to Table 10 and in the Comparative Example in Table 11 were used, asl undiluted solutions were produced. The values in Table 1 to Table 11 are% by weight of solid.

(a) undiluted solution A:

These consists of novolak resin and phthalocyanine dye, which is an absorption band in a part or the entire infrared range with a wavelength of 700 to 1100 nm, laser beams absorbed and a thermolysis achieved.

When Novolak resin in this case became a polycondensation substance used, which consists of a phenol mixture of m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and resorcinol and formaldehyde.

(b) undiluted solution B:

These is a solution which consists of resole resin and the above-mentioned phthalocyanine dye.

(c) undiluted solution C:

These is an undiluted Solution, that of polyvinylphenol resin and the above-mentioned phthalocyanine dye consists.

(d) undiluted solution D:

These is an undiluted Solution, from a copolymer of acrylic acid derivatives with phenolic Hydroxyl group and phthalocyanine dye.

The embodiments and comparative examples were performed such that the roll stock in all of these examples is iron, a plated photo-engraved roll having a diameter of 200 mm, which is copper sulfate-plated and mirror-ground is clamped at both ends in a spray coater (there being a dehumidifier and a moistening device are installed to control the moisture as desired), where during the coating process solvent in the positive photosensitive composition is vaporized and the proportion of solvent therein is prevented from changing, the roller rotates at a rate of 0.42 seconds ^-1 (25 rpm), the roll is wiped off sufficiently with a wiping cloth, then a tube for squirting photosensitive test liquid, wherein the positive photosensitive composition at its upper end by solvent el (MEK) is diluted to a predetermined concentration so as to be disposed at one end of the plated photogravure roll so as to have a gap of 500 μm, the photosensitive test liquid is ejected only in an amount as required for the coating process, the tube from one end of the plated photogravure roll to the other end to form a uniform coating of photosensitive test liquid by means of a spiral scanning system, with its rotation continued for 5 minutes at a rate of 0.42 s ^-1 (25 rpm) after completion of the coating process and then the rotation is stopped. Thereafter, it was waited 5 minutes and the liquid dripping condition was considered, and it could with the naked eye no dripping of liquid can be detected. Subsequently, when measuring the film thickness, it was found that there was no difference between the upper surface of the roller and the lower surface of the roller. Thus, it was confirmed that the photosensitive film had dried sufficiently that no dripping of liquid took place.

Subsequently, the test roll was rotated at a rotational speed of 1.67 s ^-1 (100 rpm) for 10 minutes, stopped, and the residual solvent concentration in the photosensitive film was measured to be 2.9%.

Subsequently was the test roller on an infrared laser exposure device 7 (manufactured from Think Laboratory Co., Ltd.), which has a powerful Semiconductor laser head manufactured by Creo-Scitex Corporation, a laser beam of infrared wavelength was irradiated against the test roller which Development tank was raised, the development process became for about 60 to 70 seconds, until the residues are removed and then the roller was washed with water.

By doing a cut was made on an edge of the resist image, were residues, surface condition of the resist and its hardness viewed through a microscope, the pressure sensitivity, the better or poor state of development and development latitude to judge.

What relates to these positive photosensitive compositions, so The film was formed on the plated photoengraving roller Roller was under unheated conditions on the developing device fastened, the roller was turned, the development tank was raised, the development process was for carried out for about 60 to 70 seconds, until the residues are removed were, then the roller was washed with water. By a cut was carried out on an edge of the resist image, residues, surface condition of the resist and its hardness viewed through a microscope to determine the pressure sensitivity, the better or poorer state of development, the film reduction and to assess the development latitude.

• * Vergleichsbeispiel

Tabelle 2 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Hafteigenschaft verbessern-den Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 13 unverdünnte Lösung A Polyvinyl-butyral 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 14 unverdünnte Lösung A Polyvinyl-butyral 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 15 unverdünnte Lösung A Polyvinyl-butyral 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 16 unverdü nnte Lösung A Polyvinyl-butyral 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 17 unverdü nnte Lösung B Polyvinyl-butyral 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 18 unverdünnte Lösung B Polyvinyl-butyral 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 19 unverdünnte Lösung B Polyvinyl-butyral 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 20 unverdünnte Lösung B Polyvinyl-butyral 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 21 unverdünnte Lösung C Polyvinyl-butyral 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 22 unverdünnte Lösung C Polyvinyl-butyral 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 23 unverdünnte Lösung C Polyvinyl-butyral 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 24 unverdünnte Lösung C Polyvinyl-butyral 4% kein 25°C kein Brennen 60% ausgezeichnet Tabelle 3 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Hafteigenschaft verbessern-den Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 25 unverdünnte Lösung A SM-Copolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 26 unverdünnte Lösung A SM-Copolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 27 unverdünnte Lösung A SM-Copolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 28 unverdünnte Lösung A SM-Copolymer 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 29 unverdünnte Lösung B SM-Copolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 30 unverdünnte Lösung B SM-Copolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 31 unverdünnte Lösung B SM-Copolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 32 unverdünnte Lösung B SM-Copolymer 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 33 unverdünnte Lösung C SM-Copolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 34 unverdünnte Lösung C SM-Copolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 35 unverdünnte Lösung C SM-Copolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 36 unverdünnte Lösung C SM-Copolymer 4% kein 25°C kein Brennen 60% ausgezeichnet

• Anmerkung: SM-Copolymer bedeutet Styrol/Maleinsäure-Copolymer

Tabelle 4 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Haft-eigenschaft verbessernden Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 37 unverdünnte Lösung A Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 38 unverdünnte Lösung A Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 39 unverdünnte Lösung A Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 40 unverdünnte Lösung A Vinylpyrrolidon/Dimethylamino kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 41 unverdünnte Lösung B ethylmethacry-lat-Copolymer 4% Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 42 unverdünnte Lösung B Vinylpyrrolidon/ Dimethylaminoethylmethacry-lat-Copolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 43 unverdünnte Lösung B Vinylpyrrolidon/ Dimethylaminoethylmethacry-lat-Copolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 44 unverdünnte Lösung B Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 45 unverdünnte Lösung C Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 46 unverdünnte Lösung C Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 47 unverdünnte Lösung C Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 48 unverdünnte Lösung C Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Copolymer 4% kein 25°C kein Brennen 60% ausgezeichnet Tabelle 5 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Haft-eigenschaft verbessernden Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 49 unverdünnte Lösung A Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 50 unverdünnte Lösung A Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 51 unverdünnte Lösung A Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 52 unverdünnte Lösung A Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 53 unverdünnte Lösung B Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 54 unverdünnte Lösung B Vinyipyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 55 unverdünnte Lösung B Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 56 unverdünnte Lösung B Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 57 unverdünnte Lösung C Vinylpyrrolidon/dimethylaminoethylmethacry-lat-Terpolymer 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 58 unverdünnte Lösung C Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 59 unverdünnte Lösung C Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 60 unverdünnte Lösung C Vinylpyrrolidon/Dimethylaminoethylmethacry-lat-Terpolymer 4% kein 25°C kein Brennen 60% ausgezeichnet Tabelle 6 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Hafteigenschaft verbessern-den Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 61 unverdünnte Lösung A Polyvinyl-formal 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 62 unverdünnte Lösung A Polyvinyl-formal 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 63 unverdünnte Lösung A Polyvinyl-formal 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 64 unverdünnte Lösung A Polyvinyl-formal 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 65 unverdünnte Lösung B Polyvinyl-formal 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 66 unverdünnte Lösung B Polyvinyl-formal 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 67 unverdünnte Lösung B Polyvinyl-formal 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 68 unverdünnte Lösung B Polyvinyl-formal 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 69 unverdünnte Lösung C Polyvinyl-formal 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 70 unverdünnte Lösung C Polyvinyl-formal 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 71 unverdünnte Lösung C Polyvinyl-formal 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 72 unverdünnte Lösung C Polyvinyl-formal 4% kein 25°C kein Brennen 60% ausgezeichnet Tabelle 7 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Hafteigenschaft verbessern-den Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 73 unverdünnte Lösung A TAMANOR^TM 803L 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 74 unverdünnte Lösung A TAMANOR^TM 803L 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 75 unverdünnte Lösung A TAMANOR^TM 803L 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 76 unverdünnte Lösung A TAMANOR^TM 803L 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 77 unverdünnte Lösung B TAMANOR^TM 803L 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 78 unverdünnte Lösung B TAMANOR^TM 803L 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 79 unverdünnte Lösung B TAMANOR^TM 803L 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 80 unverdünnte Lösung B TAMANOR^TM 803L 4% kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 81 unverdünnte Lösung C TAMANOR^TM 803L 2% kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 82 unverdünnte Lösung C TAMANOR^TM 803L 2,5% kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 83 unverdünnte Lösung C TAMANOR^TM 803L 3% kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 84 unverdünnte Lösung C TAMANOR^TM 803L 4% kein 25°C kein Brennen 60% ausgezeichnet

• Anmerkung: TAMANOR^TM 8031 ist ein Warenname von Terpenphenolharz, das von Arakawa Chemical Industry Ltd. hergestellt wird.

Tabelle 8 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Hafteigenschaft verbessern-den Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 85 unverdünnte Lösung A TAMANOR^TM 520S 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 86 unverdünnte Lösung A TAMANOR^TM 520S 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 87 unverdünnte Lösung A TAMANOR^TM 520S 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 88 unverdünnte Lösung A TAMANOR^TM 520S 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 89 unverdünnte Lösung B TAMANOR^TM 520S 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 90 unverdünnte Lösung B TAMANOR^TM 520S 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 91 unverdünnte Lösung B TAMANOR^TM 520S 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 92 unverdünnte Lösung B TAMANOR^TM 520S 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 93 unverdünnte Lösung C TAMANOR ^TM 520S 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 94 unverdünnte Lösung C TAMANOR^TM 520S 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 95 unverdünnte Lösung C TAMANOR^TM 520S 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 96 unverdünnte Lösung C TAMANOR^TM 520S 4% Kein 25°C kein Brennen 60% ausgezeichnet

• Anmerkung: TAMANOR^TM 526 und TAMANOR^TM 572S sind Alkylphenolharze, die von Arakawa Chemical Industry Ltd. hergestellt werden.

Tabelle 9 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Hafteigenschaft verbessern-den Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 97 * unverdünnte Lösung A Polyvinyl-acetat 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 98 * unverdünnte Lösung A Polyvinyl-acetat 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 99 * unverdünnte Lösung A Polyvinyl-acetat 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 100 * unverdünnte Lösung A Polyvinyl-acetat 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 101 * unverdünnte Lösung B Polyvinyl-acetat 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 102 * unverdünnte Lösung B Polyvinyl-acetat 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 103 * unverdünnte Lösung B Polyvinyl-acetat 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 104 * unverdünnte Lösung B Polyvinyl-acetat 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 105 * unverdünnte Lösung C Polyvinyl-acetat 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 106 * unverdünnte Lösung C Polyvinyl-acetat 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 107 * unverdünnte Lösung C Polyvinyl-acetat 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 108 * unverdünnte Lösung C Polyvinyl-acetat 4% Kein 25°C kein Brennen 60% ausgezeichnet

• * Vergleichsbeispiel

Tabelle 10 Art der unverdünnten Lösung der positiven lichtempfindlichen Zusammensetzung Art und Anteil des Hafteigenschaft verbessern-den Mittels Feststoff-gehalt an Entwicklungsbeschleu-niger Brenntemperatur kein Brennen Feuchtigkeit Haftung Ausführungsform 109 unverdünnte Lösung A Cyclohexan-harz 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 110 unverdünnte Lösung A Cyclohexan-harz 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 111 unverdünnte Lösung A Cyclohexan-harz 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 112 unverdünnte Lösung A Cyclohexan-harz 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 113 unverdünnte Lösung B Cyclohexan-harz 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 114 unverdünnte Lösung B Cyclohexan-harz 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 115 unverdünnte Lösung B Cyclohexan-harz 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 116 unverdünnte Lösung B Cyclohexan-harz 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 117 unverdünnte Lösung C Cyclohexan-harz 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 118 unverdünnte Lösung C Cyclohexan-harz 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 119 unverdünnte Lösung C Cyclohexan-harz 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 120 unverdünnte Lösung C Cyclohexan-harz 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 121 unverdünnte Lösung A Cyclohexan-harz 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 122 unverdünnte Lösung A Cyclohexan-harz 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 123 unverdünnte Lösung A Cyclohexan-harz 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 124 unverdünnte Lösung A Cyclohexan-harz 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 125 unverdünnte Lösung B Cyclohexan-harz 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 126 unverdünnte Lösung B Cyclohexan-harz 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 127 unverdünnte Lösung B Cyclohexan-harz 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 128 unverdünnte Lösung B Cyclohexan-harz 4% Kein 25°C kein Brennen 60% ausgezeichnet Ausführungsform 129 unverdünnte Lösung C Cyclohexan-harz 2% Kein 25°C kein Brennen 25% ausgezeichnet Ausführungsform 130 unverdünnte Lösung C Cyclohexan-harz 2,5% Kein 25°C kein Brennen 30% ausgezeichnet Ausführungsform 131 unverdünnte Lösung C Cyclohexan-harz 3% Kein 25°C kein Brennen 55% ausgezeichnet Ausführungsform 132 unverdünnte Lösung C Cyclohexan-harz 4% Kein 25°C kein Brennen 60% ausgezeichnet Although the image line area exposed to the alkaline developer liquid was washed away and the non-image line area which was not exposed to the alkaline developer liquid produced film reduction, the attempt to develop the roller with development latitude confirmed sharp structures stay behind and not be washed away. Table 1 Type of undiluted solution of the positive photosensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 1 * undiluted solution A PVPNA copolymer 2% no 25 ° C no burning 25% excellent Embodiment 2 undiluted PVPNA copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 3 * undiluted solution A PVPNA copolymer 3% no 25 ° C no burning 55% excellent Embodiment 4 * undiluted solution A PVPNA copolymer 4% no 25 ° C no burning 60% excellent Embodiment 5 * undiluted solution B PVPNA copolymer 2% no 25 ° C no burning 25% excellent Embodiment 6 * undiluted solution B PVPNA copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 7 * undiluted solution B PVPNA copolymer 3% no 25 ° C no burning 55% excellent Embodiment 8 * undiluted solution B PVPNA copolymer 4% no 25 ° C no burning 60% excellent Embodiment 9 * undiluted solution C PVPNA copolymer 2% no 25 ° C no burning 25% excellent Embodiment 10 * undiluted solution C PVPNA copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 11 * undiluted solution C PVP / VA copolymer 3% no 25 ° C no burning 55% excellent Embodiment 12 * undiluted solution C PVPNA copolymer 4% no 25 ° C no burning 60% excellent

• * Comparative Example

Table 2 Type of undiluted solution of the positive photosensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 13 undiluted solution A Polyvinyl butyral 2% no 25 ° C no burning 25% excellent Embodiment 14 undiluted solution A Polyvinyl butyral 2.5% no 25 ° C no burning 30% excellent Embodiment 15 undiluted solution A Polyvinyl butyral 3% no 25 ° C no burning 55% excellent Embodiment 16 undiluted solution A Polyvinyl butyral 4% no 25 ° C no burning 60% excellent Embodiment 17 undiluted solution B Polyvinyl butyral 2% no 25 ° C no burning 25% excellent Embodiment 18 undiluted solution B Polyvinyl butyral 2.5% no 25 ° C no burning 30% excellent Embodiment 19 undiluted solution B Polyvinyl butyral 3% no 25 ° C no burning 55% excellent Embodiment 20 undiluted solution B Polyvinyl butyral 4% no 25 ° C no burning 60% excellent Embodiment 21 undiluted solution C Polyvinyl butyral 2% no 25 ° C no burning 25% excellent Embodiment 22 undiluted solution C Polyvinyl butyral 2.5% no 25 ° C no burning 30% excellent Embodiment 23 undiluted solution C Polyvinyl butyral 3% no 25 ° C no burning 55% excellent Embodiment 24 undiluted solution C Polyvinyl butyral 4% no 25 ° C no burning 60% excellent Table 3 Type of undiluted solution of the positive photosensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 25 undiluted solution A SM copolymer 2% no 25 ° C no burning 25% excellent Embodiment 26 undiluted solution A SM copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 27 undiluted solution A SM copolymer 3% no 25 ° C no burning 55% excellent Embodiment 28 undiluted solution A SM copolymer 4% no 25 ° C no burning 60% excellent Embodiment 29 undiluted solution B SM copolymer 2% no 25 ° C no burning 25% excellent Embodiment 30 undiluted solution B SM copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 31 undiluted solution B SM copolymer 3% no 25 ° C no burning 55% excellent Embodiment 32 undiluted solution B SM copolymer 4% no 25 ° C no burning 60% excellent Embodiment 33 undiluted solution C SM copolymer 2% no 25 ° C no burning 25% excellent Embodiment 34 undiluted solution C SM copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 35 undiluted solution C SM copolymer 3% no 25 ° C no burning 55% excellent Embodiment 36 undiluted solution C SM copolymer 4% no 25 ° C no burning 60% excellent

• Note: SM copolymer means styrene / maleic acid copolymer

Table 4 Type of undiluted solution of the positive photosensitive composition Type and proportion of detention-improving agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 37 undiluted solution A Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 2% no 25 ° C no burning 25% excellent Embodiment 38 undiluted solution A Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 39 undiluted solution A Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 3% no 25 ° C no burning 55% excellent Embodiment 40 undiluted solution A Vinylpyrrolidone / dimethylamino no 25 ° C no burning 60% excellent Embodiment 41 undiluted solution B ethyl methacrylate-lat copolymer 4% vinylpyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 2% no 25 ° C no burning 25% excellent Embodiment 42 undiluted solution B Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 43 undiluted solution B Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 3% no 25 ° C no burning 55% excellent Embodiment 44 undiluted solution B Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 4% no 25 ° C no burning 60% excellent Embodiment 45 undiluted solution C Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 2% no 25 ° C no burning 25% excellent Embodiment 46 undiluted solution C Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 47 undiluted solution C Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 3% no 25 ° C no burning 55% excellent Embodiment 48 undiluted solution C Vinyl pyrrolidone / dimethylaminoethyl methacrylate-lat copolymer 4% no 25 ° C no burning 60% excellent Table 5 Type of undiluted solution of the positive photosensitive composition Type and proportion of detention-improving agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 49 undiluted solution A Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 2% no 25 ° C no burning 25% excellent Embodiment 50 undiluted solution A Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 51 undiluted solution A Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 3% no 25 ° C no burning 55% excellent Embodiment 52 undiluted solution A Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 4% no 25 ° C no burning 60% excellent Embodiment 53 undiluted solution B Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 2% no 25 ° C no burning 25% excellent Embodiment 54 undiluted solution B Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 55 undiluted solution B Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 3% no 25 ° C no burning 55% excellent Embodiment 56 undiluted solution B Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 4% no 25 ° C no burning 60% excellent Embodiment 57 undiluted solution C Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 2% no 25 ° C no burning 25% excellent Embodiment 58 undiluted solution C Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 2.5% no 25 ° C no burning 30% excellent Embodiment 59 undiluted solution C Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 3% no 25 ° C no burning 55% excellent Embodiment 60 undiluted solution C Vinyl pyrrolidone / dimethylaminoethyl methacrylate lat terpolymer 4% no 25 ° C no burning 60% excellent Table 6 Type of undiluted solution of the positive photosensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 61 undiluted solution A Polyvinyl-formal 2% no 25 ° C no burning 25% excellent Embodiment 62 undiluted solution A Polyvinyl-formal 2.5% no 25 ° C no burning 30% excellent Embodiment 63 undiluted solution A Polyvinyl-formal 3% no 25 ° C no burning 55% excellent Embodiment 64 undiluted solution A Polyvinyl-formal 4% no 25 ° C no burning 60% excellent Embodiment 65 undiluted solution B Polyvinyl-formal 2% no 25 ° C no burning 25% excellent Embodiment 66 undiluted solution B Polyvinyl-formal 2.5% no 25 ° C no burning 30% excellent Embodiment 67 undiluted solution B Polyvinyl-formal 3% no 25 ° C no burning 55% excellent Embodiment 68 undiluted solution B Polyvinyl-formal 4% no 25 ° C no burning 60% excellent Embodiment 69 undiluted solution C Polyvinyl-formal 2% no 25 ° C no burning 25% excellent Embodiment 70 undiluted solution C Polyvinyl-formal 2.5% no 25 ° C no burning 30% excellent Embodiment 71 undiluted solution C Polyvinyl-formal 3% no 25 ° C no burning 55% excellent Embodiment 72 undiluted solution C Polyvinyl-formal 4% no 25 ° C no burning 60% excellent Table 7 Type of undiluted solution of the positive photosensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 73 undiluted solution A TAMANOR ^TM 803L 2% no 25 ° C no burning 25% excellent Embodiment 74 undiluted solution A TAMANOR ^TM 803L 2.5% no 25 ° C no burning 30% excellent Embodiment 75 undiluted solution A TAMANOR ^TM 803L 3% no 25 ° C no burning 55% excellent Embodiment 76 undiluted solution A TAMANOR ^TM 803L 4% no 25 ° C no burning 60% excellent Embodiment 77 undiluted solution B TAMANOR ^TM 803L 2% no 25 ° C no burning 25% excellent Embodiment 78 undiluted solution B TAMANOR ^TM 803L 2.5% no 25 ° C no burning 30% excellent Embodiment 79 undiluted solution B TAMANOR ^TM 803L 3% no 25 ° C no burning 55% excellent Embodiment 80 undiluted solution B TAMANOR ^TM 803L 4% no 25 ° C no burning 60% excellent Embodiment 81 undiluted solution C TAMANOR ^TM 803L 2% no 25 ° C no burning 25% excellent Embodiment 82 undiluted solution C TAMANOR ^TM 803L 2.5% no 25 ° C no burning 30% excellent Embodiment 83 undiluted solution C TAMANOR ^TM 803L 3% no 25 ° C no burning 55% excellent Embodiment 84 undiluted solution C TAMANOR ^TM 803L 4% no 25 ° C no burning 60% excellent

• Note: TAMANOR ^™ 8031 is a trade name of terpene phenolic resin sold by Arakawa Chemical Industry Ltd. will be produced.

Table 8 Type of undiluted solution of the positive photosensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 85 undiluted solution A TAMANOR ^TM 520S 2% No 25 ° C no burning 25% excellent Embodiment 86 undiluted solution A TAMANOR ^TM 520S 2.5% No 25 ° C no burning 30% excellent Embodiment 87 undiluted solution A TAMANOR ^TM 520S 3% No 25 ° C no burning 55% excellent Embodiment 88 undiluted solution A TAMANOR ^TM 520S 4% No 25 ° C no burning 60% excellent Embodiment 89 undiluted solution B TAMANOR ^TM 520S 2% No 25 ° C no burning 25% excellent Embodiment 90 undiluted solution B TAMANOR ^TM 520S 2.5% No 25 ° C no burning 30% excellent Embodiment 91 undiluted solution B TAMANOR ^TM 520S 3% No 25 ° C no burning 55% excellent Embodiment 92 undiluted solution B TAMANOR ^TM 520S 4% No 25 ° C no burning 60% excellent Embodiment 93 undiluted solution C TAMANOR ^TM 520S 2% No 25 ° C no burning 25% excellent Embodiment 94 undiluted solution C TAMANOR ^TM 520S 2.5% No 25 ° C no burning 30% excellent Embodiment 95 undiluted solution C TAMANOR ^TM 520S 3% No 25 ° C no burning 55% excellent Embodiment 96 undiluted solution C TAMANOR ^TM 520S 4% No 25 ° C no burning 60% excellent

• Note: TAMANOR ^™ 526 and TAMANOR ^™ 572S are alkylphenol resins marketed by Arakawa Chemical Industry Ltd. getting produced.

Table 9 Type of undiluted solution of the positive photosensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 97 * undiluted solution A Polyvinyl acetate 2% No 25 ° C no burning 25% excellent Embodiment 98 * undiluted solution A Polyvinyl acetate 2.5% No 25 ° C no burning 30% excellent Embodiment 99 * undiluted solution A Polyvinyl acetate 3% No 25 ° C no burning 55% excellent Embodiment 100 * undiluted solution A Polyvinyl acetate 4% No 25 ° C no burning 60% excellent Embodiment 101 * undiluted solution B Polyvinyl acetate 2% No 25 ° C no burning 25% excellent Embodiment 102 * undiluted solution B Polyvinyl acetate 2.5% No 25 ° C no burning 30% excellent Embodiment 103 * undiluted solution B Polyvinyl acetate 3% No 25 ° C no burning 55% excellent Embodiment 104 * undiluted solution B Polyvinyl acetate 4% No 25 ° C no burning 60% excellent Embodiment 105 * undiluted solution C Polyvinyl acetate 2% No 25 ° C no burning 25% excellent Embodiment 106 * undiluted solution C Polyvinyl acetate 2.5% No 25 ° C no burning 30% excellent Embodiment 107 * undiluted solution C Polyvinyl acetate 3% No 25 ° C no burning 55% excellent Embodiment 108 * undiluted solution C Polyvinyl acetate 4% No 25 ° C no burning 60% excellent

• * Comparative Example

Table 10 Type of undiluted solution of the positive photosensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning humidity liability Embodiment 109 undiluted solution A Cyclohexane resin 2% No 25 ° C no burning 25% excellent Embodiment 110 undiluted solution A Cyclohexane resin 2.5% No 25 ° C no burning 30% excellent Embodiment 111 undiluted solution A Cyclohexane resin 3% No 25 ° C no burning 55% excellent Embodiment 112 undiluted solution A Cyclohexane resin 4% No 25 ° C no burning 60% excellent Embodiment 113 undiluted solution B Cyclohexane resin 2% No 25 ° C no burning 25% excellent Embodiment 114 undiluted solution B Cyclohexane resin 2.5% No 25 ° C no burning 30% excellent Embodiment 115 undiluted solution B Cyclohexane resin 3% No 25 ° C no burning 55% excellent Embodiment 116 undiluted solution B Cyclohexane resin 4% No 25 ° C no burning 60% excellent Embodiment 117 undiluted solution C Cyclohexane resin 2% No 25 ° C no burning 25% excellent Embodiment 118 undiluted solution C Cyclohexane resin 2.5% No 25 ° C no burning 30% excellent Embodiment 119 undiluted solution C Cyclohexane resin 3% No 25 ° C no burning 55% excellent Embodiment 120 undiluted solution C Cyclohexane resin 4% No 25 ° C no burning 60% excellent Embodiment 121 undiluted solution A Cyclohexane resin 2% No 25 ° C no burning 25% excellent Embodiment 122 undiluted solution A Cyclohexane resin 2.5% No 25 ° C no burning 30% excellent Embodiment 123 undiluted solution A Cyclohexane resin 3% No 25 ° C no burning 55% excellent Embodiment 124 undiluted solution A Cyclohexane resin 4% No 25 ° C no burning 60% excellent Embodiment 125 undiluted solution B Cyclohexane resin 2% No 25 ° C no burning 25% excellent Embodiment 126 undiluted solution B Cyclohexane resin 2.5% No 25 ° C no burning 30% excellent Embodiment 127 undiluted solution B Cyclohexane resin 3% No 25 ° C no burning 55% excellent Embodiment 128 undiluted solution B Cyclohexane resin 4% No 25 ° C no burning 60% excellent Embodiment 129 undiluted solution C Cyclohexane resin 2% No 25 ° C no burning 25% excellent Embodiment 130 undiluted solution C Cyclohexane resin 2.5% No 25 ° C no burning 30% excellent Embodiment 131 undiluted solution C Cyclohexane resin 3% No 25 ° C no burning 55% excellent Embodiment 132 undiluted solution C Cyclohexane resin 4% No 25 ° C no burning 60% excellent

As described above, shows the fact that the positive photosensitive Composition that does not contain vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers or polyvinyl butyral and the like, has no development latitude but the positive photosensitive composition, the vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers or polyvinyl butyral and the like, a development margin that provides a strong adhesion of vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers or Polyvinyl butyral and the like, the weak adhesiveness of alkali-soluble organic Polymer substance having phenolic hydroxyl group in a suitable manner reinforced and causes a development latitude.

Development latitude of Comparative examples

As shown in Table 11, the firing temperature at the photosensitive Film of the positive photosensitive composition remarkably be lowered by the undiluted solution the positive photosensitive composition consisting of a alkali-soluble organic polymeric substance having phenolic hydroxyl group and Phthalocyanine dye was an organo-organic compound was added.

in the Case of the photosensitive film with an organo-organic Compound offset positive photosensitive composition The film was well formed even at a firing temperature of 46 ° C. its sensitivity has been excellent, and the development process could easily done become.

• Anmerkung: Orgatex^TM ist der Produktname titanorganischer Verbindungen, die von Arakawa Chemical Industry Ltd. hergestellt werden. Orgatex^TM TA-10 ist Tetraisopropyltitanat. Orgatex^TM TA-25 ist Tetranormaltitanat. Orgatex^TM TA-100 ist Titanacetylacetonat. Orgatex^TM TPHS ist Polyhydroxytitanstearat.

However, the test could not produce any high-quality film without performing a burning process, and the development became poor. Table 11 Type of undiluted solution of the positive light-sensitive composition Type and proportion of adhesive property improve-agent Solid content of development accelerator Firing temperature no burning liability Comparative Example 1 undiluted solution A Orgatex ^TM TA-10 1% no 46 ° C excellent Comparative Example 2 undiluted solution A Orgatex ^TM TA-25 1% no 46 ° C excellent Comparative Example 3 undiluted solution A Orgatex ^TM TA-22 1% no 46 ° C excellent Comparative Example 4 undiluted solution A Orgatex ^TM TPHS 1% no 46 ° C excellent Comparative Example 5 undiluted solution A Orgatex ^TM TA-100 1% no 46 ° C excellent Comparative Example 6 undiluted solution B Orgatex ^TM TA-10 1% no 46 ° C excellent Comparative Example 7 undiluted solution B Orgatex ^TM TA-25 1% no 46 ° C excellent Comparative Example 8 undiluted solution B Orgatex ^TM TA-100 1% no 46 ° C excellent Comparative Example 9 undiluted solution C Orgatex ^TM TA-10 1% no 46 ° C excellent Comparative Example 10 undiluted solution C Orgatex ^TM TA-25 1% no 46 ° C excellent Comparative Example 11 undiluted solution C Orgatex ^TM TA-100 1% no 46 ° C excellent Comparative Example 12 undiluted solution D Orgatex ^TM TA-10 1% no 46 ° C excellent Comparative Example 13 undiluted solution D Orgatex ^TM TA-25 1% no 46 ° C excellent Comparative Example 14 undiluted solution D Orgatex ^TM TA-100 1% no 46 ° C excellent Comparative Example 15 undiluted solution A Orgatex ^TM TA-10 1% no 25 ° C no burning bad Comparative Example 16 undiluted solution A Orgatex ^TM TA-25 1% no 25 ° C no burning bad Comparative Example 17 undiluted solution B Orgatex ^TM TA-10 1% no 25 ° C no burning bad Comparative Example 18 undiluted solution B Orgatex ^TM TA-25 1% no 25 ° C no burning bad Comparative Example 19 undiluted solution C Orgatex ^TM TA-10 1% no 25 ° C no burning bad Comparative Example 20 undiluted solution C Orgatex ^TM TA-25 1% no 25 ° C no burning bad Comparative Example 22 undiluted solution D Orgatex ^TM TA-25 1% no 25 ° C no burning bad

• Note: Orgatex ^™ is the product name of organoanorganic compounds marketed by Arakawa Chemical Industry Ltd. getting produced. Orgatex ^™ TA-10 is tetraisopropyl titanate. Orgatex ^™ TA-25 is tetranormaltitanate. Orgatex ^™ TA-100 is titanium acetylacetonate. Orgatex ^TM TPHS is polyhydroxytitanium stearate.

• (1) Ein Brennen nach dem Beschichten eines plattierten Photogravurgegenstands ist nicht zweckmäßig, und es besteht die Eigenschaft, dass ein erforderlicher und ausreichender Haftungszustand erzielt werden kann, auch wenn das Brennen nicht durchgeführt wird. Es kann ein lichtempfindlicher Film mit Glanz und einem recht harten Zustand gewonnen werden.
• (2) Es kann eine erforderliche und ausreichende Haftung erzielt werden, wenn das Beschichten an einem schönen Tag bei einer Feuchtigkeit von etwa 25 bis 60% in einem Arbeitsraum durchgeführt wird oder das Beschichten bei einer Feuchtigkeit von etwa 25 bis 60% in dem Arbeitsraum unter Einsatz einer Entfeuchtungsvorrichtung und einer Befeuchtungsvorrichtung durchgeführt wird.
• (3) Es kann in einer angemessenen Zeit eine ausgezeichnete alkalische Entwicklung ohne Erzeugung irgendwelcher Rückstände durchgeführt werden. Ungeachtet der Tatsache, dass die Komponente in der lichtempfindlichen Schicht durch Belichtung im wesentlichen keinerlei chemische Veränderung erzeugt, können alle grundlegenden Leistungsanforderungen an eine Druckplatte wie z. B. eine Plattenverschleißeigenschaft, Empfindlichkeit und Entwicklungsspielraum oder dergleichen erfüllt werden.
• (4) Auch wenn die Bildbelichtung statt mit einer höheren Belichtungsenergie, bei der von der zur photothermischen Umwandlung fähigen Substanz in der lichtempfindlichen Schicht übermäßige Wärme erzeugt wird, mit einer geringeren Belichtungsenergie durchgeführt wird, kann der Entwicklungsspielraum breit angesetzt werden, so dass der an der lichtempfindlichen Schicht erzeugte Verteilungsgrad deutlich niedrig begrenzt ist und kein Problem auftritt, dass die lichtempfindliche Schicht zerläuft und das optische System in der Belichtungsvorrichtung kontaminiert wird.
• (5) Eine Verarbeitung ohne Brennen ermöglicht die Durchführung einer ganz ausgezeichneten Entwicklung, bei der eine hohe Empfindlichkeit bewahrt werden kann und eine Kante des Resistbildes in genauer Übereinstimmung mit einem Belichtungsmuster in einer scharfen Kontur geschnitten wird.
• (6) Es kann eine ganz ausgezeichnete Entwicklung durchgeführt werden, während kaum eine Filmreduktion erfolgt. Es ist möglich, das Auftreten von Nadelstichporen zu vermeiden, die durch Filmreduktion verursacht werden;
• (7) Das Resistbild hat einen Glanz, es kann ein recht hartes Resistbild erzielt werden, mit dem sich während des eigentlichen Drucks mehrere tausend Kopien drucken lassen, und es bestehen nach dem Bilden des lichtempfindlichen Films bei der Handhabung vor dem Entwicklungsvorgang bessere Kratzschutzeigenschaften.
• (8) Die Kopie des Bildes mittels Laser und der Entwicklungsspielraum sind ausgezeichnet.

In view of the above results, in the photogravure plate manufacturing method, the following effects can be obtained when the positive photosensitive composition which does not require any firing after coating is used:

• (1) Burning after the coating of a clad photogravure article is not appropriate, and there is a characteristic that a required and sufficient state of adhesion can be obtained even if the burning is not performed. A photosensitive film with gloss and a fairly hard state can be obtained.
• (2) A required and sufficient adhesion can be obtained when the coating is carried out on a nice day at a humidity of about 25 to 60% in a working space or the coating at a humidity of about 25 to 60% in the working space Use of a dehumidifier and a humidifier is performed.
• (3) Excellent alkaline development can be performed in a timely manner without producing any residue. Notwithstanding the fact that the component in the photosensitive layer produces substantially no chemical change by exposure, all basic performance requirements can be met by a printing plate such as a printing plate. A disk wear property, sensitivity and development latitude or the like can be satisfied.
• (4) Although the image exposure is performed at a lower exposure energy, rather than a higher exposure energy, which generates excessive heat in the photosensitive layer from the photo-thermal conversion substance, the development latitude can be set broadly, so that the light output at the light-sensitive layer generated is significantly low limited and there is no problem that the photosensitive layer is tearing and the optical system is contaminated in the exposure device.
• (5) Processing without burning makes it possible to carry out a very excellent development in which high sensitivity can be preserved and an edge of the resist image is cut in a sharp contour in strict accordance with an exposure pattern.
• (6) Very excellent development can be made while hardly reducing the film. It is possible to avoid the occurrence of pinholes caused by film reduction;
• (7) The resist image has a gloss, a rather hard resist image capable of printing several thousand copies during the actual printing, and better scratch-resistant properties after forming the photosensitive film in handling before the development process.
• (8) The laser copy of the image and the development latitude are excellent.

Claims (1)

A positive photosensitive composition comprising: a photothermal conversion-capable substance for absorbing infrared rays of an image exposure light source and converting them to heat; and a) an alkali-soluble organic high molecular weight substance having phenolic hydroxyl groups and an adhesion-promoting agent, any of the following: (1) polyvinyl butyral; (2) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers, (3) vinylpyrrolidone / vinylcaprolactam / dimethylaminoethylmethacrylate terpolymers, (4) terpene-phenolic resin, (5) polyvinylformal resin, and (6) ketone resin, or b) an alkali-soluble organic high molecular substance comprising an epoxy resin with phenolic hydroxyl groups, and, as an adhesion-promoting agent, any of the following: (1) vinylpyrrolidone / vinyl acetate copolymers, (2) polyvinyl butyral, (3) vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymers, (4) vinyl pyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate terpolymers, (5) terpene phenolic resin, (6) polyvinyl formal resin, (7) polyvinyl acetate, and (8) ketone resin.