KR100693357B1 - Positive photosensitive composition - Google Patents

Abstract

It can be burned and applied under conditions of 25 ~ 60% of humidity in the workroom to obtain the necessary sufficient adhesiveness, high sensitivity is maintained so that no residue can be produced, sharp outlines are cut, and the resist film is very hard, Provided is a positive photosensitive composition having improved scratch resistance in handling. Alkali-soluble organic polymer material having a phenolic hydroxyl group (A), a photothermal conversion material (B) for absorbing infrared light which is an image exposure light source and converting it into heat, (1) vinylpyrrolidone / vinyl acetate copolymer, etc. At least 1 sort (s) of resin (C) and dissolution inhibitor (D) were included.

Positive photosensitive composition, burning, developing, gravure plate making, photothermal conversion material

Description

Positive photosensitive composition

The present invention relates to an alkali-soluble positive photosensitive composition having an infrared wavelength laser sensitivity in which the sensitive portion is exposed to a laser light having a wavelength of 700 to 1,100 nm so as to be soluble in an alkali developer. The positive photosensitive composition of the present invention is particularly used in the field of photofabrication of printing plates, electronic parts, precision instrument parts and the like.

As a method of forming a positive image by increasing the solubility of a developer in an exposed part by a change other than chemical change, a method of printing a positive photosensitive composition with a laser beam having a wavelength of 700 to 1,100 nm has been noted. For example, refer patent documents 1-9.

The positive photosensitive composition which forms the coating film of the flat plate of each said patent document is a main component which absorbs infrared light, such as an infrared absorbing dye, and converts it into heat, and alkali-soluble resin, such as novolak resin. By the heat generated by the infrared laser light exposure, the main chain or side chain portion of the molecule is cleaved to cause a conformation change that results in a lower molecule with higher alkali solubility, and some of the physical changes such as the conformation change of the ablation resin. To increase the solubility in the developer.

On the other hand, as one of the methods for making a gravure printing roll, a so-called etching method in which a photosensitive film is coated on a copper sulfate plated surface of a plate making roll, the image is printed by a laser, then developed, etched, and the resist is peeled off and chromium plated. This is done. In the conventional etching method, a negative photosensitive film is applied to a toner plate roll, the coating film is dried at room temperature to form a negative photosensitive film, and is printed with an argon laser.

On the other hand, forming a positive photosensitive film | membrane and printing it with the laser beam of wavelength 700-1,100 nm was not performed in the engraving of a gravure printing roll. The high-resolution gravure plate making system using a positive photosensitive film using a semiconductor laser or a YAG laser capable of high output of laser light having a wavelength of 700 to 1,100 nm is not practical, and compared to the case of using an argon laser. The realization is strongly demanded in terms of miniaturization and environmental light during plate making.

If the beam diameter of the argon laser light and the beam diameter of the laser light having a wavelength of 700 to 1,100 nm are the same size, the resolution of the laser becomes higher in the positive type than the negative type, and the processing time can be greatly shortened. It is also preferable to print the positive type image by using the photosensitive film of the negative photosensitive composition with a laser of an infrared wavelength region, and the fineness of the pattern is better than printing the negative image by argon laser on the photosensitive film of the negative photosensitive composition. This is considered to be a difference in the fineness of the pattern due to the difference in composition between the positive photosensitive composition and the negative photosensitive composition.

Canada's high power semiconductor laser head from CreoTax Inc. emits an infrared wavelength laser and is mounted on an offset printing machine to irradiate the positive photosensitive composition to perform a good phenomenon and is used worldwide. .

Then, about the etching method as one of the methods for making a gravure printing roll, the stock solution of the positive photosensitive composition which mix | blended the novolak resin and the cyanine pigment | dye was made, and the positive photosensitive agent which thinned this stock solution with the solvent was used for the gravure roll. The test was performed on the copper sulfate plated surface of the copper sulfate plate and irradiated with a laser in the infrared wavelength region by a exposure apparatus (manufactured by Think Laboratories, Inc.) equipped with CreoTax's high-power semiconductor head to print a positive image and then develop it. As a result, the photosensitive film was detached from the entire surface, and no satisfactory resist image could be obtained.

On the other hand, for example, after rotating the 200 mm-thick platen roll at a low speed of 25 r.pm, the negative photosensitive film was applied in a spiral scan method, and a time (approximately 5 minutes) that no liquid flow occurred was completed. After 15 minutes have elapsed, the film is formed at the point where rotation is stopped, and developed after printing the image by a laser.

Therefore, it was thought that it is necessary to burn by heating a membrane surface at high temperature, and to provide adhesive force. The need for burning is considered to be due to the lack of adhesion to the copper-plated surface or copper alloy-plated surface of the positive photosensitive composition, resulting in a non-coated state. When burning after film formation, alkali solubility having a phenolic hydroxyl group is obtained. It is because it was thought that adhesiveness can be improved by strengthening the hydrogen bond of an organic high molecular material.

In the offset printing plate, a good photosensitive film is formed without burning, but it is necessary to burn the photosensitive film to the gravure plate roll, and in the offset printing plate, the substrate forming the photosensitive film is a thin aluminum plate and the adhesiveness is high. On the contrary, it was considered that the object of the gravure plate was made from copper sulfate plated surface, and the adhesion to copper sulfate plated surface was extremely poor.

By the way, the positive photosensitive composition which mix | blended the above-mentioned novolak resin and cyanine pigment | dye was apply | coated to a toner plate roll, and it burned for 30 minutes so that temperature might become 60 degreeC, and developed by laser exposure, and the image development became poor. As a result of repeating several tests, it was found that the solvent residual concentration of the sum total of MEK, IPA, PM and the like at the time of film formation was approximately 6% or more, and that the image could not be printed by laser.

Therefore, when the film was burned for 30 minutes so that the surface temperature was 130 ° C, the solvent concentration was 2%. However, a phenomenon in which the entire surface deviated from the non-fired part also occurred. Even if it burned, it was considered that the adhesiveness with respect to the copper sulfate plating surface of a positive photosensitive composition was too low as a cause of developing defect.

Therefore, when using a positive photosensitive composition, in order to make solvent residual concentration into 6% or less, preferably to 3% or less, and to give a sufficient adhesive force, it is necessary to burn after application of the photosensitive film. When the silane coupling agent was added as the adhesive agent to increase the adhesion of the photosensitive film, exposure and development were performed slightly satisfactorily. Specifically, a positive sensitizer is applied, for example, by rotating a 200 φ mm of the platen roll at a low speed of 25 r.pm, and continuing the rotation so as not to produce a liquid flow, and passing the liquid for 5 minutes under natural drying conditions. When the photosensitive film of the drying degree which the solvent vaporized in the state which disappeared was set, and burned at 130 degreeC for 30 minutes afterwards, the solvent residual density | concentration is less than 2%, the image by a laser can be printed and it can develop. there was.

However, the adhesion to the film cannot be said to be the best, and the exposure and development did not fall from the slightly good region. Moreover, when the film surface temperature was 130 degreeC, it turned out that time required for 100 minutes or more for burning and subsequent cooling requires a large amount of thermal energy, and the running cost becomes high and it lacks utility. Moreover, when the film surface temperature is 130 degreeC, the hydrogen bond of the alkali-soluble organic high molecular substance which has a phenolic hydroxyl group will become strong, it will become difficult to develop, and will bring about denaturation to a cyanine pigment | dye, and sensitivity will fall.

Gravure plate rolls are made of aluminum and iron, and the thickness of the gravure rolls is different when the roll diameters are different and the roll diameters are different. Even if heat is transferred to the roll base and the film surface temperature is not always heated to 130 ° C. but irregular distribution is generated at different temperatures, it was considered important to lower the temperature to eliminate the problem of specific heat capacity.

It was thought that burning for achieving a solvent concentration of 6% or less can be achieved even by making the film surface temperature much lower than 130 ° C by selecting a composition having good solvent separation. When the test was performed to shorten the heating time, and the film was burned for 50 minutes after the burning temperature was lowered to 80 ° C to 100 ° C, it was confirmed that the residual solvent concentration was 6% or less. As a cause, it was concluded that sufficient adhesive force could not be obtained with the silane coupling agent.

Next, although the imidazole which is a hardening accelerator was added instead of a silane coupling agent as an adhesive agent, it did not change in particular with the case of a silane coupling agent, The burning temperature of a film surface was also the same as that of a silane coupling agent.

Subsequently, various kinds of adhesives were changed and added to the stock solution of the positive photosensitive composition which consists of an alkali-soluble organic high molecular material which has a phenolic hydroxyl group, and the photothermal conversion material which absorbs infrared rays which are image exposure light sources, and converts it into heat, and it is copper sulfate at room temperature 25 degreeC. The test which formed and developed the photosensitive film in the plating roll showed that the burning temperature was remarkably reduced about the photosensitive film of the positive photosensitive composition which added the titanium organic compound (refer patent document 10).

In the case of the photosensitive film of the positive photosensitive composition which added the titanium organic compound, even if burning temperature is 46 degreeC, it could form into a film favorably, and the sensitivity became favorable and image development became easy. However, in the test without the burning process, good film formation was not possible and the development was poor.

Although it is possible to reduce the burning temperature to around 50 ° C, the need for burning means that cooling is required after burning, burning and subsequent cooling takes time and energy, and the device line is as long as the burning device. It is disadvantageous to lose weight, and to increase equipment cost and running cost. The burning is one of the causes of the thinning of the resist during development and the generation of pinholes. Therefore, development of a positive photosensitive film which does not require burning is strongly desired.

When the positive type photosensitive agent which added the above-mentioned titanium organic compound was apply | coated to the copper sulfate plating plate, and the solvent residual density | concentration when it passed for 15 minutes in the natural dry conditions which are not blown at room temperature 25 degreeC, when 11% and 25 hours passed, Solvent residual concentration was 9%. After the application of the positive photosensitive agent to the spinneret roll rotating at 45r.p.m and the elapse of 10 minutes, it was found that the residual solvent concentration was reduced to only 7%. In this way, even if the raw material of the positive photosensitive agent is included in the adhesive preparation to improve the properties, and even if the result is confirmed by the development, the solvent residual concentration cannot be significantly reduced by more than 6%, so that no positive type is required. Image printing by the laser of the photosensitive film was impossible.

Therefore, the present inventors have developed the theme of the practical use of the positive photoresist film which does not require burning, and the development of a positive photoresist film which can improve the adhesiveness of the positive photoresist film itself by addition of an adhesive without depending on the burning. In order to solve the two problems simultaneously, conceptually distinguishing the development of the film-forming drying technique which can reduce the solvent residual concentration by more than 6% in a short time and easily without resorting to burning.

Since the coating film dries from the surface in contact with air, it is considered that the diffusion becomes lower as the surface dries over time. On the other hand, after the coating film does not flow, it is considered that forcibly pressurizing the membrane surface to diffuse the residual solvent into the air can effectively reduce the residual solvent. Therefore, after the coating film was no longer flowed, the platen roll was rotated at a high speed. As a result, it was found that the solvent residual concentration could be lowered to 3% or less in a short time.

Based on this fact, it is possible to reduce the concentration of solvent to 6% or less in a very short time without burning, and to support the platen roll horizontally at both ends of the spiral scan type coating apparatus to rotate it at the required low speed. Position the pipe from which the photosensitive agent elutes to have a slight gap at one end of the platen roll, and allow the photosensitive agent to be eluted in an amount necessary for coating, and then move the pipe from one end of the platen roll to the other end to form a gap in the spiral scan method. Apply the test sensitizer uniformly so that it does not open and the overlap is small, and then proceed with rotation to set the dry photosensitive film vaporized by the solvent in the state that liquid flow does not occur, and then place it in the coating apparatus or laser Move to exposure equipment, etc., and rotate the platen roll to the required highway for the required time By friction to that leaving the residual solvent in the photosensitive layer by diffusion into the air and established a technique to obtain a film of a low residual solvent levels in the image flammability it can be expressed by the laser.

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

Nevertheless, we developed a technology that can reduce the solvent concentration to 6% or less in a very short time without burning, and the positive type photosensitive composition with respect to the positive type photosensitive agent having sufficient adhesion even without burning by adding various adhesive preparations. The improved properties were tested.

As a result, cellulose derivatives, titanium alkoxides, titanium acylates, and the like are prepared in the stock solution of a positive photosensitive composition composed of an alkali-soluble organic high molecular material having a phenolic hydroxyl group and a photothermal conversion material that absorbs infrared rays which are image exposure light sources and changes into heat. Alternatively, when the titanium chelate contained at least one of the titanium organic compounds was tested, the development was poor when the burning process was performed, and the development was excellent when the burning process was not performed, thereby obtaining the best resist pattern.

Patent Document 1: Japanese Patent Application Laid-Open No. 10-268512

Patent Document 2: Japanese Patent Application Laid-Open No. 11-194504

Patent Document 3: Japanese Patent Application Laid-Open No. 11-223936

Patent Document 4: Japanese Patent Application Laid-Open No. 11-84657

Patent Document 5: Japanese Patent Application Laid-Open No. 11-174681

Patent Document 6: Japanese Patent Application Laid-Open No. 11-231515

Patent Document 7: International Publication No. 97/39894

Patent Document 8: International Publication No. 98/42507

Patent Document 9: Japanese Patent Application Laid-Open No. 2002-189294

Patent Document 10: Japanese Patent Application Laid-Open No. 2004-133025

Patent Document 11: JP-A 47-25470

Patent Document 12: Korean Patent Application Publication No. 48-85679

Patent Document 13: Special Publication No. 51-21572

However, as a result of testing on a day when the humidity was extremely low, when the development was conducted, the photoresist film detached entirely. Positive type photosensitizers are known to have a humidity dependency that generally prevents film formation due to bleaching at a high humidity of 60% or higher, but it has been found that there is a humidity dependency that adhesion is lost even when the humidity is extremely low as 25%.

Therefore, as a result of testing by adding various adhesive aids, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, vinylpyrrolidone / Vinyl caprolactam / dimethylaminoethyl methacrylate copolymer, polyvinylbutylal, polyvinylformal, styrene / maleic acid resin, terpene phenolic resin, alkylphenolic resin, melamine / formaldehyde resin, polyvinyl acetate, or ketone resin In the case of the mixed addition, it is applied to a 200 φmm coated plate roll rotating at 25 r.pm under the conditions in which the temperature in the laboratory is changed to 25 ° C. and the humidity is 25%, 30%, 55%, 60%. After the rotation was continued for 5 minutes under natural drying conditions, the solution was stopped for 10 minutes at 100 r.pm. In this way, four test rolls which apply | coated and formed the extremely hard photosensitive film | membrane which have all the glossiness very strong adhesiveness with respect to the copper sulfate plating surface of a skin plate roll were obtained. The film thickness was 3.5-3.8 micrometers. As a result of measuring the solvent residual concentration, all test rolls were 2.3%. Thus, as a result of image development by laser printing in the infrared wavelength region, an extremely sharp and residue-free alkali-soluble resist pattern with almost no film reduction compared to the film thickness before development was obtained. And, it was confirmed that the naturally dry resist pattern was extremely hard, and completed the present invention.

The present invention relates to a positive photosensitive composition in which exposure is sensitive to a laser beam having a wavelength of 700 to 1,100 nm and the sensitive portion is soluble in an alkaline developer, and is applied when the humidity in the coating chamber is applied in a 25 to 60% range. Not only can be applied to the object and subsequent burning is required, and sufficient adhesion to aluminum can be obtained, but also sufficient adhesion to copper or copper sulfate plating, which requires much stronger adhesion than aluminum, can be obtained for 60 to 70 seconds. Good alkali development is performed in which no residue is generated at a time, and an extremely good phenomenon is obtained in which the edge of the resist image maintained with high sensitivity is cut into a sharp outline through the exposure pattern of exposure without burning. It is possible to produce a very good phenomenon due to less film reduction and less pinholes caused by film reduction. In addition, the resist image is glossy, and even if it is used as it is for printing, a very hard resist image can be obtained that can be printed thousands of times, and the scratch resistance is improved in handling before development after the formation of the photosensitive film, and image printing by laser And it aims at providing the positive photosensitive composition from which image development latitude was excellent.

In addition, in this specification, in the case of image development, it is a situation that there is no change (film decrease) little, the area | region of a halftone does not change in predetermined development time, and there is no residue (the rest) suddenly coming out, and it is stable. It is said that there is a lattice of phenomena that can be produced.

In order to solve the above problems, the positive photosensitive composition of the present invention is an alkali-soluble organic polymer material (A) having a phenolic hydroxyl group, a photothermal conversion material (B) for absorbing and converting infrared rays as an image exposure light source (B), (1) Vinylpypolydon / vinyl acetate copolymer, (2) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) vinylpyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate copolymer, (4 Polyvinyl acetate, (5) Polyvinyl butylal, (6) Polyvinylformal, (7) Styrene / maleic acid copolymer, (8) Terpene phenolic resin, (9) Alkylphenolic resin, (10) Melamine / At least one resin (C) selected from the group consisting of formaldehyde resin and (11) ketone resin, and a dissolution inhibiting agent (D).

It is preferable that the said dissolution inhibitor (D) is a compound represented by following General formula (1).

[Tue 1]

It is preferable that the said photothermal conversion material (B) is a compound represented by following General formula (2).

[Tue 2]

[Formula (2) of, R ¹ ~ R ⁶ are each independently, represent a hydrogen atom, a C 1 -C 3 alkyl group, or a carbon number of groups 1-3 alkoxy, X is a halogen atom, ClO _4, BF _4, TsO ( p-CH ₃ C ₆ H ₄ SO ₃ ), or PF ₆ ].

Moreover, it is preferable that the said photothermal conversion substance (B) is a compound represented by following General formula (3).

[Tue 3]

Equation (3) of, R ⁷ ~ R ¹⁰ are each independently, a hydrogen atom, a methoxy group, N (CH _{3) 2,} or N (C ₂ H _{5) 2,} Y is C ₄ H ₉ -B (C ₆ H ₅ ) ₃ , p-CH ₃ C ₆ H ₄ SO _3, CF ₃ SO _3. ]

 The photofabrication technique of the present invention is characterized by using the positive photosensitive composition of the present invention. Examples of photofabrication include printing plates, electronic components, and precision instrument components.

The plate making method of the present invention is characterized by using the positive photosensitive composition of the present invention. By the plate-making method of this invention, printing plates, such as a recessed plate (gravure), a flat plate, a convex board, and a stencil, can be produced.

The general engraving process of the gravure plate using the positive photosensitive composition of this invention as a photosensitive liquid is as follows.

1. Apply photoresist to the cylinder (Dry film thickness is 2-5μm is preferred. The thicker film is preferable to remove pinhole, but the thinner one is used less costly) → 2. Drying (15 minutes to touch dry → finish Up to 15 ~ 20 minutes) → 3. Exposure (light source: semiconductor laser 830nm, 220mJ / cm ² ) → 4. Developing (60 ~ 90sec / 25 ℃) → 5. Washing (Spray 30sec) → 6. Etching (depth) 10 ~ 30μm, corrosion cupric chloride solution, copper equivalent 60g / L) → 7. Resist stripping (alkali peeling) → 8. Water washing → 9. Chromium plating (chromic acid 250g / L, sulfuric acid 2.5g / L) → 10. Flush → 11. Print.

The general engraving process of the flat plate (PS plate) using the positive photosensitive composition of this invention as a photosensitive liquid is as follows.

1.CTP (PS plate) (aluminum polishing → photoresist coating → drying) → 2. Exposure (light source: semiconductor laser 830nm, 220mJ / cm ² ) → 3. Developing → 4. Printing.

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

(1) In addition to aluminum and copper, necessary adhesion can be obtained without burning even on a target to be coated with poor adhesion, such as glossy mirror-plated copper. Moreover, the photosensitive film | membrane with the gloss equivalent to the case where the conventional burning is performed without burning is obtained.

(2) Even if the humidity is 25 to 60%, sufficient adhesion can be obtained.

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

(4) Even when image exposure is performed at a lower exposure energy than the high exposure energy at which excess heat is generated by the photothermal conversion material in the photosensitive layer, the development lattice can be widened, and the degree of photosensitive layer scattering is suppressed low. Therefore, there is no problem that the photosensitive layer is scattered (ablation) and contaminates the optical system of the exposure apparatus.

(5) In the absence of the burning process, an extremely good phenomenon can be obtained in which the edge of the resist image having high sensitivity is cut into a sharp outline through the exposure pattern of exposure. Moreover, the cross-sectional part also has no irregular distribution of the heat capacity by burning, and can hold | maintain a uniform film thickness after image development.

(6) Gravure engraving can be performed so that the resist image has little film reduction, is glossy, and there is no pinhole even if it is corroded as it is. In addition, a resist image having a degree of printing resistance can be obtained by printing or the like to print thousands or more sheets, and the occurrence of pinholes can be avoided in handling before development after photosensitive film drying, or scratch resistance爪 傷 性) improves.

(7) The rate of change for the image printing by the laser is small, and the development latitude is excellent.

(8) Since the film reduction after development is small, there is little generation of pinholes.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the photosensitive liquid test pattern and measurement location used in Example 1, (a) is a test pattern, (b) is an enlarged view of the ring part of (a).

EMBODIMENT OF THE INVENTION Although embodiment of this invention is described below, these embodiment is shown as an illustration, and it cannot be overemphasized that a various deformation | transformation is possible, without deviating from the technical idea of this invention.

The positive photosensitive composition of this invention contains the following component (A)-(D), It is characterized by the above-mentioned.

(A) Alkali-soluble organic high molecular substance which has a phenolic hydroxyl group, (B) The photothermal conversion substance which absorbs infrared rays which are image exposure light sources, and converts into heat, (C) (1) Vinylpyrrolidone / vinylacetate copolymer, (2 ) Vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) Vinylpyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate copolymer, (4) Polyvinyl acetate, (5) Polyvinyl butylal , (6) polyvinylformal, (7) styrene / maleic acid resin, (8) terpene phenol resin, (9) alkylphenol resin, (10) melamine / formaldehyde resin, and (11) ketone resin At least one resin selected, and (D) a dissolution inhibitor.

As an alkali-soluble organic high molecular substance (A) which has the said phenolic hydroxyl group, For example, the copolymer of the acrylic acid derivative which has a novolak resin, a resol resin, polyvinyl phenol resin, a phenolic hydroxyl group, an epoxy resin which has a phenolic hydroxyl group (For example, epoxy / phenolic), and the like, and particularly, as disclosed in Patent Document 6 and the like, a novolak resin, a resol resin, or a polyvinyl phenol resin is preferable. These alkali-soluble organic polymer substances (A) may be used independently and may be used together 2 or more types.

Novolak resin is resin which polycondensed at least 1 sort (s) of phenols with at least 1 sort (s) of aldehyde or ketone under an acidic catalyst, and resol resin uses an alkali catalyst instead of an acid catalyst in polycondensation of novolak resin. Other than that, it is the same and polycondensed resin. In the novolak resin and the resol resin, phenol, o-cresol, m-cresol, p-cresol, 2,5-quisylenol, 3,5-quisylenol, resorcinol or mixed phenols thereof and formaldehyde Preference is given to polycondensates with acetaldehyde or propionaldehyde. It is preferable that the novolak resin and the resol resin each have a polystyrene reduced weight average molecular weight (MW) of 1,500 to 150,000 by gel permeation chromatography measurement.

Examples of the polyvinylphenol resin include resins obtained by polymerization of hydroxystyrenes alone or in combination of two or more thereof in the presence of a radical polymerization initiator or a cationic polymerization initiator. The polymer of the hydroxy styrene which has a C1-C4 alkyl group as a substituent in the benzene ring, and the polymer of the hydroxy styrene of an unsubstituted benzene ring are preferable. In addition, polyvinyl phenol derivatives (e.g., derivatives obtained by tert-butylation or styrene of polyvinyl phenol), and copolymers of vinyl phenol and other vinyl monomers (e.g., vinyl phenol-methyl methacrylate) Copolymers, vinylphenol-styrene copolymers, vinylphenol-methacrylic acid-2-hydroxyethyl copolymers, vinylphenol-phenylmaleimide copolymers, and the like).

Although the content rate of alkali-soluble organic high molecular substance (A) in the positive photosensitive composition of this invention is not specifically limited, It is based on the solid content total amount of (A) component, (B) component, (C) component, and (D) component. It is preferable that it is 80 to 95 weight% with respect to it, and it is more preferable that it is 90 to 94 weight%.

The photothermal conversion material (B) is not particularly limited as long as it is a compound capable of converting absorbed light into heat, but an organic or inorganic pigment, dye or organic pigment having an absorption band in part or all of the infrared region having a wavelength of 700 to 1,100 nm. , Metals, metal oxides, metal carbides, metal borides, and the like, and efficiently absorb light in the wavelength region, and light absorbing pigments that hardly absorb or substantially do not absorb light in the ultraviolet region. Is preferable, and the compound represented by following General formula (2) or (3) and its derivative are especially preferable.

[Tue 4]

[In formula (2), R <^1> -R <^6> respectively independently represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, X <^-> is a relative anion, X is a halogen atom, ClO ₄ , BF ₄ , p-CH ₃ C ₆ H ₄ SO ₃ or PF ₆ and the like.

[Tue 5]

Equation (3) of, R ⁷ ~ R ¹⁰ are each independently, a hydrogen atom, a methoxy group, N (CH _{3) 2,} or _{N (C 2 H 5) 2} , Y - is a counter anion, Y Examples of the compound include C ₄ H ₉ -B (C ₆ H ₅ ) ₃ , p-CH ₃ C ₆ H ₄ SO _3, CF ₃ SO ₃ , and the like.]

As a compound represented by the said General formula (3), the near-infrared region absorption pigment | dye represented by following formula (4)-(7) whose maximum absorption wavelength is a near-infrared region is more preferable.

[Tue 6]

[Tue 7]

[Tue 8]

[Tue 9]

Moreover, as another light-absorbing dye, for example, as described in Patent Document 6, a heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or the like is broadly bonded with polymethine (-CH =) n. Examples of so-called cyanine-based pigments may be cited. Specifically, for example, quinoline-based (so-called cyanine-based), indole-based (so-called indocyanine-based), benzothiazole-based (so-called thiocyanine-based), Iminocyclohexadiene-based (so-called polymethine-based), pyryllium-based, thiapyryllium-based, squarylium-based, croconium-based, azrenium-based and the like, among which, quinoline-based, indole-based and benzothiazole-based , Iminocyclohexadiene-based, pyryllium-based or thiapyryllium-based are preferable. In particular, phthalocyanine and cyanine are preferable.

The photothermal conversion material (B) has a property of absorbing and thermally decomposing laser light in an infrared wavelength region having an absorption band in a part or all of the infrared wavelength region having a wavelength of 700 to 1,100 nm, and having an alkali-soluble organic polymer having the phenolic hydroxyl group. It is involved in alkali-soluble low molecular weight ablation by thermal cleavage of molecules of substances.

Some of the addition amount of the photothermal conversion material is related to the excessive and insufficient heat generated by the exposure, and the intensity of the infrared laser light is related to the excessive and insufficient thermal decomposition of the alkali-soluble organic polymer material present in the exposed part. Is set. In the positive photosensitive composition of the present invention, the content ratio of the photothermal conversion material (B) is 0.1 to 10% by weight relative to the total solids of the components (A), (B), (C) and (D). It is preferable and 1-4 weight% is more preferable.

The resin (C) comprises (1) vinylpyrrolidone / vinyl acetate copolymer, (2) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) vinylpyrrolidone / vinyl caprolactam / dimethylamino Ethyl methacrylate copolymer, (4) polyvinyl acetate, (5) polyvinyl butylal, (6) polyvinylformal, (7) styrene / maleic acid resin, (8) terpene phenolic resin, (9) alkylphenol It is at least 1 sort (s) of alkali-soluble resin chosen from the group which consists of resin, (10) melamine / formaldehyde resin, and (11) ketone resin, and functions as an adhesive improving agent.

Said (1) vinylpyrrolidone / vinyl acetate copolymer (henceforth a PVP / VA copolymer) is a thermoreversible resin obtained by copolymerizing vinylpyrrolidone and vinyl acetate, and is represented by following General formula (8) Has a structure.

[Tue 10]

In formula (8), n and m are each an integer of 1 or more. Although the ratio of vinylpyrrolidone and vinyl acetate of a PVP / VA copolymer is not specifically limited, It is preferable that the ratio of vinylpyrrolidone and vinyl acetate is 70/30 to 30/70, and 50/50 is more preferable. Do.

Although the manufacturing method of PVP / VA copolymer is not specifically limited, The linear random copolymer obtained by free-radically polymerizing vinylpyrrolidone and vinyl acetate is preferable. Although the molecular weight of PVP / VA copolymer is not specifically limited, 10,000-60,000 are preferable and 20,000-50,000 are more preferable.

The (2) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer has a structure represented by the following general formula (9).

[Tue 11]

In formula (9), n and m are each an integer of 1 or more.

Said (3) vinylpyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate copolymer is a copolymer of vinylpyrrolidone, vinyl caprolactam, and dimethylethyl methacrylate, and is represented by following General formula (10) Has a structure.

[Tue 12]

In formula (10), n and m are each an integer of 1 or more.

The polyvinyl acetate (4) is a homopolymer of vinyl acetate or a copolymer containing vinyl acetate as a main component, and has a structure represented by the following general formula (11).

[Tue 13]

In formula (11), n is an integer of 1 or more. As polyvinyl acetate, for example, Saxol SN-09T (trade name) of Electrochemical Industry Co., Ltd. is preferably used.

Said (5) polyvinyl butyl alcohol (abbreviated PVB) is resin obtained by the butyl aldehyde which makes butyl aldehyde react with polyvinyl alcohol, and has a structure represented by following General formula (12).

[Tue 14]

In formula (12), n, m, and l are each an integer of 1 or more. Specific examples of the polyvinyl butyl al include the products of Electrochemical Industry Co., Ltd., Denkabutyl Al 5000A and 6000EP, the product of Integra Chemical Co., Ltd., BL-1, BL-2, BL-S, BX-L, Polymerization type BM-1, BM-2, BM-5, BM-S, high polymerization type BH-3, BH-S, BX-1, BX-2, BX-5, BX-55 and the like are preferred. As an example, the use of BL-S, BM-S, and BH-S which has solubility in many kinds of solvents is especially preferable.

Said (6) polyvinyl formal (PVFM) is resin with favorable electrical insulation which has a structure represented by following General formula (13).

[Tue 15]

In formula (13), n, m, and l are each an integer of 1 or more. Although the manufacturing method of polyvinyl formal is not specifically limited, For example, polyvinyl acetate is melt | dissolved in acetic acid, formaldehyde and sulfuric acid are added, and a kneading reaction and a formalization reaction are performed simultaneously, and dilute sulfuric acid is added to this reaction liquid. The polyvinylformal is added to precipitate, and the product is obtained through solvent recovery, washing and drying.

The (7) styrene / maleic acid resin is a copolymer obtained by copolymerizing a styrene monomer and a maleic acid monomer, a derivative of the copolymer, or a modified product thereof. It is preferable that the said (7) styrene / maleic-acid resin contains a carboxyl group so that it may become an acid value of 30-200, especially 50-170. As a weight average molecular weight, 1,500-100,000 are preferable.

The styrene-based monomer is a styrene or a derivative thereof, for example, styrene, α-methylstyrene, m or p-methoxy styrene, p-methyl styrene, p-hydroxy styrene, 3-hydroxymethyl-4- Hydroxy-styrene etc. are mentioned as a preferable example.

Maleic acid monomers are maleic acid or derivatives thereof, maleic anhydride, maleic acid, or monomethyl maleate, monoethyl maleate, mono-maleic acid maleate, monoisopropyl maleate, mono-n-butyl maleate, monoisobutyl maleate and monomaleic acid maleate Maleic acid esters, such as -tert- butyl, are preferable.

It is preferable that the said (7) styrene / maleic acid-type resin is a copolymer (henceforth a copolymer (a)) of the styrene-type monomer which has a structure represented by following General formula (14), and a maleic acid-type monomer. In addition, other copolymers, for example, those obtained by further copolymerizing vinyl monomers such as acrylic monomers (eg, alkyl methacrylates such as methyl methacrylate and t-butyl methacrylate, alkyl acrylates, etc.) are used. It is also possible.

[Tue 16]

In formula (14), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group, R ¹³ represents a hydrogen atom or a hydroxyl group, and R ¹⁴ and R ¹⁵ are each Independently, the group which has a hydrogen atom, a lower alkyl group, or a reactive double bond is represented, m and n are each an integer of 1 or more, and m≥n is preferable.

As the (7) styrene / maleic acid-based resin, a modified product of the copolymer (a) with a compound having a reactive double bond (hereinafter referred to as copolymer (b)) may be used. In this case, m and n are integers of 1 or more in formula (14), m≥n is preferable, and m / n = 1-1.1 are more preferable. Specifically as said copolymer (b), it can manufacture by making the compound which has a reactive double bond react with the acid anhydride group or carboxy group in copolymer (a). In this case, in order to improve adhesiveness, it is preferable that a carboxyl group remains in the copolymer.

As the compound having a reactive double bond, a compound having a carbon-carbon double bond is preferable, and specifically, an unsaturated alcohol (for example, aryl alcohol, 2-butene-1-2-ol, perfuryl alcohol, oleic acid) Monoalcohol, cinnamil alcohol, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, etc.), alkyl (meth) acrylate (e.g., methyl methacrylate, t-butyl) Methacrylate, an oxirane ring, and an epoxy compound each having one reactive double bond (for example, glycidyl acrylate, glycidyl methacrylate, arylglycidyl ether, α-ethylglycidyl) Acrylate, clotonylglycidyl ether, itaconic acid monoalkyl monoglycidyl ester, etc.) etc. are mentioned as a preferable example.

In addition, the copolymer (b) is reacted with an epoxy compound having one of the above-described oxirane ring and one reactive double bond in order to increase the concentration of the reactive double bond by introducing a reactive double bond with an unsaturated alcohol. It may be used to increase the reactive double bond concentration.

The manufacturing method of the said copolymer (a) and (b) is not specifically limited, It can carry out according to a well-known method (for example, refer patent documents 11-13 etc.). The provision of the reactive double bond to the copolymer is preferable in terms of degree of curing and chain resistance.

As said (8) terpene phenol resin, a conventionally well-known thing can be used widely. Specifically, tamanol 803L and 901 (trade name of a sulfur chemical company) are mentioned as a preferable example.

As said (9) alkylphenol resin, a conventionally well-known thing can be used widely. Specifically, tamanol 520S, 521, 526, 586, and 572S (The brand name of a sulfur chemical company make) are mentioned as a preferable example.

The (10) melamine-formaldehyde resin is a resin obtained by the addition condensation reaction of melamine and formaldehyde, and a known melamine-formaldehyde resin can be widely used. Specifically, it is preferable to use Banserin SM-960 (brand name) of Harima Chemical Co., Ltd., for example.

As said (11) ketone resin, a well-known ketone resin can be used and it is not specifically limited. For example, it can obtain by making ketones and formaldehyde react by a well-known method. As ketones, methyl ethyl ketone, methyl isopropyl ketone, acetophenone, cyclohexanone, methylcyclohexanone, etc. are mentioned, for example, Cyclohexanone and acetophenone are preferable. As ketone resin, the cyclohexane ketone resin represented by following formula (15), and the acetophenone ketone resin which has a structure represented by following formula (16) are preferable.

[Tue 17]

[Tue 18]

In Formulas (15) and (16), m and n are each an integer of 1 or more.

In the positive photosensitive composition of the present invention, the content ratio of the resin (C) is preferably 1 to 40% by weight based on the total amount of solids of the component (A), (B), (C) and (D) , 5 to 30% by weight is more preferable.

The dissolution inhibiting agent (D) is blended for the purpose of increasing the time difference of solubility in the alkaline developer of the exposed portion and the non-exposed portion, and has a function of forming a hydrogen bond with the alkali-soluble organic polymer material to reduce the solubility of the polymer material. Moreover, the thing which hardly absorbs the light of an infrared region and does not decompose into the light of an infrared region can be used.

As said dissolution inhibitor (D), the compound represented by following formula (1) (4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethyldene] Bisphenol).

[Tue 19]

Moreover, a well-known dissolution inhibitor can be used as a dissolution inhibitor (D). Specifically, sulfonic acid ester, phosphate ester, aromatic carboxylic acid ester, aromatic disulfone, carboxylic anhydride, aromatic ketone, aromatic aldehyde, aromatic amine, aromatic ether, etc., lactone skeleton, thiolactone skeleton, N, N-diaryl Acid-chromic dyes having an amide skeleton, or a diarylmethylimino skeleton, a lactone skeleton, a thiolactone skeleton, a base-chromic pigment having a sulfolactone skeleton, a nonionic surfactant, and the like, among which are mentioned. Acid-chromic pigments having

In the positive photosensitive composition of the present invention, the content ratio of the dissolution inhibiting agent (D) is 0.5 to 8% by weight based on the total solid content of the components (A), (B), (C) and (D). It is preferable, and 1 to 5 weight% is more preferable. These dissolution inhibitors may be used alone or in combination of two or more thereof.

In addition to the above-mentioned components, the positive photosensitive composition of this invention may mix | blend various additives, such as a coloring agent, a sensitizer, a development promoter, and a coating property improving agent, such as a pigment or dye as needed. As a sensitizer, the compound (photoacid generator) which generate | occur | produces an acid by light is preferable. It is preferable to add a trace amount of dicarboxylic acid or amines or glycols, for example.

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

There is no restriction | limiting in particular as long as it has sufficient solubility with respect to a used component, and can provide favorable coating-film property, A vertical solvent solvent, a propylene glycol solvent, ester solvent, alcohol solvent, ketone solvent, high polarity Solvents may be used. Examples of the vertical solver solvent include methyl vertical solver, ethyl vertical solver, methyl vertical solver acetate, ethyl vertical solver acetate, and the like. As the propylene glycol solvent, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, etc. Can be mentioned. Examples of the ester solvent include butyl acetate, amyl acetate, ethyl lactate, butyl lactate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutylate, ethyl acetoacetate, methyl lactate, ethyl lactate, and 3-methoxypropionic acid Methyl etc. are mentioned. Heptanol, hexanol, diacetone alcohol, perfuryl alcohol, etc. are mentioned as alcohol solvent. In addition, nitric acid, these mixed solvents, or the like which added aromatic hydrocarbon to these is mentioned.

The positive photosensitive composition of the present invention is usually a solution in which each component is dissolved in a solvent such as a vertical solvent solvent, a propylene glycol solvent, or the like, and then applied to the copper plated surface or copper sulfate plated surface of the gravure printing surface coating roll on the support surface and then dried naturally. The surface of the photosensitive composition is reduced on the surface of the support by reducing the solvent residual concentration to 6% or less by rotating at a high speed and cutting off the wind from the surface of the platen roll to cause mass action by the centrifugal force in the photosensitive film and a slight vicinity of the surface. It becomes a positive photosensitive film in which a layer was formed.

As a coating method, a meniscus coat, a fountain coat, a dip coat, a rotary coating, a roll coating, a wire bar coating, an air knife coating, a blade coating, a caten coating and the like can be used. It is preferable to set it as the range of 1-6 micrometers, and, as for the thickness of a coating film, it is more preferable to set it as 3-5 micrometers.

As a light source which image-exposes a positive photosensitive composition, a semiconductor laser and a YAG laser which generate the infrared laser beam of wavelength 700-1,100 nm are preferable. In addition, solid lasers, such as a ruby laser and LED, can be used. As light intensity of a laser light source, it is preferable to set it as 2.0 * 10 <^6> mJ / s * cm <^2> or more, and it is especially preferable to set it as 1.0 * 10 <^7> mJ / s * cm <^2> or more.

As a developer used for the photosensitive film formed using the positive photosensitive composition of this invention, inorganic alkali (for example, salt of Na, K, etc.), or organic alkali (for example, TMAH (Tetra Methyl Ammonium Hydroxide)) Or a developer made of an inorganic or organic alkali such as choline).

The development is usually carried out at a temperature of about 15 to 45 ° C., preferably at 22 to 32 ° C., by immersion, spray or ultrasonic development.

Although an Example is given to the following and this invention is demonstrated to it further more concretely, it is a matter of course that these Examples are shown as an illustration and should not be interpreted limitedly.

(Example 1)

The positive photosensitive composition (5% of solid content) by the compounding material and compounding ratio shown in Table 1 was prepared, and it was set as the test photosensitive liquid.

TABLE 1

Compound Compounding amount (part by weight) Ingredient (A)  Novolak Resin 100 Ingredient (B)  Near infrared ray absorption pigment 1  One Ingredient (C)  PVP / VA Copolymer  5 Ingredient (D)  Dissolution inhibitor 1  5 menstruum  PM IPA MEK 800 800 600

Each component of Table 1 is as follows.

Novolak resin: PR-NMD-100 (manufactured by Juw backlight)

Light Absorption Pigment 1: Cyanine Dye PVP / VA Copolymer: Copolymer of vinyl pyrrolidone and vinyl acetate having a molecular weight of 46,000 and a glass transition point of 96 ° C. (vinylpyrrolidone / vinyl acetate 50/50)

Dissolution inhibitor 1: Honshu Chemical Co., Ltd. make, brand name: TrisP-PA (compound represented by Formula (1))

PM: propylene glycol monoether

IPA: Isopropyl Glycol

MEK: methyl ethyl ketone

The following experiment was done using the obtained test photosensitive liquid. In addition, the experiment was performed in 25 degreeC and the humidity conditions shown in Table 2. The copper plated roll of 200φmm coated with copper sulfate and mirror-polished with iron iron is rotated at 25r.pm by both ends with a fountain coating device (a device that can control the humidity as desired by installing a dehumidifying device and a humidifying device). Wipe clean enough by wiping cloth. In addition, the fountain coating apparatus avoids that the solvent in a positive photosensitive composition evaporates during coating, and the ratio of a solvent changes.

Thereafter, the pipe from which the test photosensitive solution elutes is positioned at one end of the platelet roll to have a gap of about 500 μm, and the test photosensitive solution is eluted by the amount necessary for coating, so that the pipe from one end to the other end of the platelet roll is removed. The test photosensitive liquid was uniformly coated by the spiral scanning method, and the rotation was stopped after continuing the rotation at 25 r.pm for 5 minutes from the end of the coating.

After waiting for 5 minutes to observe the flow, it was not possible to observe the appearance of the liquid. And as a result of measuring the film thickness, there was no difference in the lower surface part and the upper surface part of a roll. In addition, it was confirmed that the dry photosensitive film could be set in a state where no liquid flow occurred.

Subsequently, the test roll was rotated and stopped at 100 r · p · m for 20 minutes, and the solvent residual concentration in the photosensitive film was measured, and the result was 2.9%.

Subsequently, a test roll was installed in an exposure apparatus (manufactured by Think Laboratories Co., Ltd.) equipped with CreoTax's high-power semiconductor laser head, and the test roll was irradiated with an infrared wavelength laser to print a positive image. The test roll was installed in a developing apparatus, rotated to raise the developing tank, and developed until there was no residue, followed by washing with water. In addition, KOH 4.2% (25 degreeC) was used for the developing solution. The obtained resist image was evaluated under a microscope. The results are shown in Table 2.

TABLE 2

Humidity (%) Adhesion Sensitivity (mJ / cm ² ) Symptoms (seconds) Residual Rate (%) burn Edge resolution Phenomenon Latter Example 1-1 35 ◎ 220 75 75 ◎ ◎ ◎ Example 1-2 45 ◎ 220 75 74 ◎ ◎ ◎ Example 1-3 55 ◎ 220 75 73 ◎ ◎ ◎

The evaluation method in Table 2 is as follows.

1) Resolution of the edges

Using the resolution test pattern shown in FIG. 1, it was measured whether the edge of the line shape and grazing 7.9 micrometers line was sharp. In the table,? Indicates that the resolution is acceptable, and x does not have an image and cannot be plated, and the resolution fails.

2) Developing Latitude

The measurement was carried out using a cell warehouse (a device capable of automatically measuring the porosity of the dots) of Dae Nippon Printing Co., Ltd. According to the test that increased the number of times of development (three times in this example), when the exposure is 7.9 μm × 7.9 μm, and the cell area calculation is within 60-75 μm ² , it is within the allowable range of the print density. In the table,? Is indicated. In the table, cases outside the printing allowable range are indicated by x.

3) Adhesion

tesa test; (Circle) and the case where it peeled in less than 20% of the case where 100 masses remain | survived by the checkerboard scale test by DIN EN ISO 2409 tesa tape were made into x.

4) Sensitivity

Sensitivity is determined by the exposure amount being close to the reproducibility of the reference image pattern. The exposure machine used Creo's thermal imaging head.

5) phenomenon

The developing time until there was no residue was measured.

6) Residual rate

The film thickness before image development and the film thickness after image development were measured using FILMETRICS Thin Film Analyzer F20 (made by Filmetrics Co.) which is an apparatus which measures the thickness of a coating film, and the residual film ratio was computed.

7) burns

We evaluated whether reproducibility was close to the original image. (Double-circle): Very good, x: Very bad,-: No image by image development.

The photosensitive liquid test pattern and measurement point were shown in FIG. Table 3 shows check items and measurement methods for the measurement points in FIG. 1.

TABLE 3

Measurement point Check item Photo shoot Area measurement (cell warehouse) ① Status of present residue - - ② 1 pixel feed ○ - ③ 1 pixel highlight ○ ○ ④ 7μm grazing ○ ○

As shown in Table 2, the positive photosensitive composition of Example 1 became a favorable phenomenon that the sharp pattern without a residue was obtained in about 70 second on 25 degreeC room temperature and 35-55% of conditions. Developing latitude was also good.

Moreover, although the case where the copper surface or the aluminum surface was used instead of the copper sulfate plating surface, experiment was carried out, but all were the same as Example 1, and the favorable result was obtained. In the case of the aluminum plane, a particularly wide development latencies have been obtained.

(Examples 2-6)

As shown in Table 4, experiment was carried out similarly to Example 1 except having changed the component (B) in a composition. In addition, measurement conditions were performed on the conditions of 45% of humidity. The results are shown in Table 4 together.

TABLE 4

Ingredient (B) Adhesion Sensitivity (mJ / cm ² ) Symptoms (seconds) Residual Rate (%) burn Edge resolution Phenomenon Latter Example 2 Pigment 2 ◎ 220 75 76 ◎ ◎ ◎ Example 3 Coloring 3 ◎ 220 75 73 ◎ ◎ ◎ Example 4 Coloring 4 ◎ 220 75 72 ◎ ◎ ◎ Example 5 Pigment 5 ◎ 220 75 73 ◎ ◎ ◎ Example 6 Pigment 6 ◎ 220 75 75 ◎ ◎ ◎

In Table 4, the compounding quantity of a component (B) is the same as that of Example 1, and the pigment | dye 2-the pigment | dye 6 are compounds represented by said formula (2), (4)-(7), respectively.

(Examples 7-9)

As shown in Table 5, experiment was carried out similarly to Example 1 except having changed the component (A) in a composition. Moreover, it performed on the conditions of 45% of measurement conditions. The result was combined with Table 5 and shown.

TABLE 5

Ingredient (A) Adhesion Sensitivity (mJ / cm ² ) Symptoms (seconds) Residual Rate (%) burn Edge resolution Phenomenon Latter Example 7 Resin 1 ◎ 220 75 72 ◎ ◎ ◎ Example 8 Resin 2 ◎ 220 75 74 ◎ ◎ ◎ Example 9 Resin 3 ◎ 220 75 75 ◎ ◎ ◎

In Table 5, the compounding quantity of a component (A) is the same as that of Example 1, and resin 1-3 is as follows.

Resin 1: Alkylphenol resin (trade name Hitanol 2181, manufactured by Ellipse Co., Ltd.)

Resin 2: p-vinylphenol butyl acrylate copolymer (brand name Maru Carerca CBA, circulating oil company)

Resin 3: polyvinyl phenol resin (brand name Maru Caring Car M, circulating oil company)

(Examples 10-20)

The experiment was carried out in the same manner as in Example 1, except that each polymer shown in Table 6 was used instead of the PVP / VA copolymer as the component (C). In addition, measurement conditions were performed on the conditions of 45% of humidity. The result was combined with Table 6 and shown.

TABLE 6

Example number Ingredient (C) Adhesion Sensitivity (mJ / cm ² ) Symptoms (seconds) Residual Rate (%) burn Edge resolution Phenomenon Latter 10 Polymer 1 ◎ 180 75 75 ◎ ◎ ◎ 11 Polymer 2 ◎ 180 70 69 ◎ ◎ ◎ 12 Polymer 3 ◎ 180 75 74 ◎ ◎ ◎ 13 Polymer 4 ◎ 180 75 69 ◎ ◎ ◎ 14 Polymer 5 ◎ 180 72 73 ◎ ◎ ◎ 15 Polymer 6 ◎ 180 75 75 ◎ ◎ ◎ 16 Polymer 7 ◎ 180 72 72 ◎ ◎ ◎ 17 Polymer 8 ◎ 180 73 73 ◎ ◎ ◎ 18 Polymer 9 ◎ 180 70 70 ◎ ◎ ◎ 19 Polymer 10 ◎ 180 69 69 ◎ ◎ ◎ 20 Polymer 11 ◎ 180 68 68 ◎ ◎ ◎

In Table 6, the compounding quantity of a component (C) is the same as that of Example 1, and polymers 1-11 are as follows.

Polymer 1: GAFQUAT 734 (manufactured by ISP, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer)

Polymer 2: GAFFIX VC-713 (manufactured by ISP, vinylpyrrolidone / vinylcaprolactam / dimethylaminoethyl methacrylate tapolymer)

Polymer 3: Saxol SN-09T (manufactured by Electrochemical Industry Co., Ltd., polyvinyl acetate)

Polymer 4: Dencabutylal # 3000 (manufactured by Electrochemical Industry Co., Ltd., polyvinylbutylal)

Polymer 5: Vinyl Rec-K type (Chick Sosa, polyvinyl formal)

Polymer 6: Oxylac SH-101 derivative (glycidyl methacrylate-added styrene / maleic acid copolymer, acid value 80)

Polymer 7: tamanol 803L (manufactured by Hwangcheon Chemical Co., Ltd., terpene phenol resin)

Polymer 8: Tamanol 520S (manufactured by Hwangcheon Chemical Co., Ltd., alkylphenol resin)

Polymer 9: Banserine SM-960 (manufactured by Harima Chemical Co., Ltd., melamine / formaldehyde resin)

Polymer 10: Hylock 111 (manufactured by Iso Chemical Co., Ltd., cyclohexane resin)

Polymer 11: Hylock 110H (manufactured by Iso Chemical Co., Ltd., acetphenol resin)

(Examples 21 to 42)

Experiments were carried out in the same manner as in Example 1, except that the resins and polymers shown in Tables 7 or 8 were used for the component (A) and the component (C). Measurement conditions were performed under the conditions of 45% humidity. The results are shown in Tables 7 and 8. In addition, in Table 7 and Table 8, the compounding quantity of a component (A) and a component (C) is the same as that of Example 1, resins 2 and 3 are the same as Table 5, and polymers 1-11 are the same as Table 6.

TABLE 7

Example number Ingredient (A) Ingredient (C) Adhesion Sensitivity (mJ / cm ² ) Symptoms (seconds) Residual Rate (%) burn Edge resolution Phenomenon Latter 21 Resin 2 Polymer 1 ◎ 180 75 75 ◎ ◎ ◎ 22 Resin 2 Polymer 2 ◎ 180 70 69 ◎ ◎ ◎ 23 Resin 2 Polymer 3 ◎ 180 75 74 ◎ ◎ ◎ 24 Resin 2 Polymer 4 ◎ 180 75 69 ◎ ◎ ◎ 25 Resin 2 Polymer 5 ◎ 180 72 73 ◎ ◎ ◎ 26 Resin 2 Polymer 6 ◎ 180 75 75 ◎ ◎ ◎ 27 Resin 2 Polymer 7 ◎ 180 72 72 ◎ ◎ ◎ 28 Resin 2 Polymer 8 ◎ 180 73 73 ◎ ◎ ◎ 29 Resin 2 Polymer 9 ◎ 180 70 70 ◎ ◎ ◎ 30 Resin 2 Polymer 10 ◎ 180 69 69 ◎ ◎ ◎ 31 Resin 2 Polymer 11 ◎ 180 68 68 ◎ ◎ ◎

TABLE 8

Example number Ingredient (A) Ingredient (C) Adhesion Sensitivity (mJ / cm ² ) Symptoms (seconds) Residual Rate (%) burn Edge resolution Phenomenon Latter 32 Resin 3 Polymer 1 ◎ 180 75 75 ◎ ◎ ◎ 33 Resin 3 Polymer 2 ◎ 180 70 69 ◎ ◎ ◎ 34 Resin 3 Polymer 3 ◎ 180 75 74 ◎ ◎ ◎ 35 Resin 3 Polymer 4 ◎ 180 75 69 ◎ ◎ ◎ 36 Resin 3 Polymer 5 ◎ 180 72 73 ◎ ◎ ◎ 37 Resin 3 Polymer 6 ◎ 180 75 75 ◎ ◎ ◎ 38 Resin 3 Polymer 7 ◎ 180 72 72 ◎ ◎ ◎ 39 Resin 3 Polymer 8 ◎ 180 73 73 ◎ ◎ ◎ 40 Resin 3 Polymer 9 ◎ 180 70 70 ◎ ◎ ◎ 41 Resin 3 Polymer 10 ◎ 180 69 69 ◎ ◎ ◎ 42 Resin 3 Polymer 11 ◎ 180 68 68 ◎ ◎ ◎

(Comparative Examples 1 to 3)

As shown in Table 9, the experiment was carried out in the same manner as in Example 1 except that the formulation of the positive photosensitive composition was changed. In addition, measurement conditions were performed on the conditions of 45% of humidity. The results are shown in Table 10.

TABLE 9

Comparative Example 1 Comparative Example 2 Comparative Example 3  Ingredient (A) Novolak Resin 100 100 100  Component (B) Light Absorption Pigment 1 One One One            Titanium Organic Compound ­ 2 ­            Imidazolesilane ­ ­ 2  Solvent PM IPA MEK 800 800 600 800 800 600 800 800 600

In Table 9, a novolak resin, the light absorption pigment | dye 1, and a solvent are the same as Table 1, and the other components are as follows.

Titanium Organic Compound: Organics TA-10 (titanium alkoxide) manufactured by Song-Bon Pharmaceutical Co., Ltd.

Imidazole silane: The silane coupling agent which has a structure of following formula (17). However, in Formula 17, R <^1> -R <^4> is an alkyl group and n is an integer of 1-3 respectively.

[Tue 20]

TABLE 10

Adhesion Sensitivity (mJ / cm ² ) Symptoms (seconds) Residual Rate (%) burn Edge resolution Phenomenon Latter Comparative Example 1 ○ 180-250 60 0 - × × Comparative Example 2 ○ 180-250 60 0 - × × Comparative Example 3 ○ 180-250 60 0 - × ×

As shown in Table 10, all of Comparative Examples 1-3 had no image after development, and no current lattice was obtained.

(Comparative Examples 4-15)

Except having mix | blended the dissolution inhibitor 1, it implemented similarly to Example 1 and Examples 10-20. The results are shown in Table 11.

TABLE 11

Adhesion Sensitivity (mJ / cm ² ) Symptoms (seconds) Residual Rate (%) burn Edge resolution Phenomenon Latter Comparative Example 4 ○ 180-250 60 0 - × × Comparative Example 5 ○ 180-250 60 12 × × × Comparative Example 6 ○ 180-250 60 0 - × × Comparative Example 7 ○ 180-250 60 0 - × × Comparative Example 8 ○ 180-250 60 0 - × × Comparative Example 9 ○ 180-250 60 0 - × × Comparative Example 10 ○ 180-250 60 0 - × × Comparative Example 11 ○ 180-250 60 10 × × × Comparative Example 12 ○ 180-250 60 5 × × × Comparative Example 13 ○ 180-250 60 0 - × × Comparative Example 14 ○ 180-250 60 0 - × × Comparative Example 15 ○ 180-250 60 0 - × ×

The positive photosensitive composition of the present invention is preferable for forming a positive photosensitive film on the copper sulfate plated surface of the gravure printing coated plate roll, but is not limited thereto. Metal plates such as aluminum, zinc, copper, aluminum, zinc, copper, Adhesiveness at low temperatures is good even when applied to metal plates plated or deposited with iron, chromium or nickel, paper coated with resin, paper with metal foil such as aluminum, plastic film, plastic film subjected to hydrophilization treatment, and glass plate, High sensitivity can be obtained.

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

Claims (7)

Alkali-soluble organic polymer material (A) which has a phenolic hydroxyl group, the photothermal conversion material (B) which absorbs infrared rays which are image exposure light sources, and converts it into heat, (1) vinylpyrrolidone / vinyl acetate copolymer, (2) vinylpi Ralidone / dimethylaminoethylmethacrylate copolymer, (3) vinylpyrrolidone / vinylcaprolactam / dimethylaminoethylmethacrylate copolymer, (4) polyvinyl acetate, (5) polyvinylbutylal, (6 Polyvinylformal, (7) styrene / maleic acid copolymer, (8) terpenephenol resin, (9) alkylphenol resin, (10) melamine / formaldehyde resin, and (11) ketone resin Positive type photosensitive composition containing at least 1 sort (s) of resin (C) and dissolution inhibiting agent (D), and the said dissolving inhibitor (D) is a compound represented by following General formula (1). [Tue 21]

delete The positive photosensitive composition as claimed in claim 1, wherein the photothermal conversion material (B) is a compound represented by the following general formula (2). [Tue 22]

[Formula (2) of, R ¹ ~ R ⁶ are each independently, represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group having a carbon number of 1 to 3 alkoxy, X is a halogen atom, ClO _4, BF _4, p- CH ₃ C ₆ H ₄ SO ₃ , or PF _6. ] The positive photosensitive composition as claimed in claim 1, wherein the photothermal conversion material (B) is a compound represented by the following general formula (3). [Tue 23]

Equation (3) of, R ⁷ ~ R ¹⁰ are each independently, a hydrogen atom, a methoxy group, N (CH _{3) 2,} or N (C ₂ H _{5) 2,} Y is C ₄ H ₉ -B (C ₆ H ₅ ) ₃ , p-CH ₃ C ₆ H ₄ SO _3, CF ₃ SO _3. ] The positive photosensitive composition of Claim 1 is used, The photofabrication characterized by the above-mentioned. The photofabrication according to claim 5, wherein the photofabrication is a printing plate, an electronic component or a precision instrument component. The positive type photosensitive composition of Claim 1 is used, The making method characterized by the above-mentioned.

Images