JPWO2008126722A1 - Positive photosensitive composition - Google Patents

Abstract

Provided is a positive photosensitive composition which has no adhesion before exposure and has excellent adhesion and high sensitivity. (A) a polymer substance having at least one carboxyl group in the molecule, (B) a photothermal conversion substance that absorbs infrared rays from an image exposure light source and converts it into heat, and (M) a thermal acid generator. I did it. The thermal acid generator (M) is preferably one or more selected from the group consisting of p-toluenesulfonic acid ester, p-toluenesulfonic acid anhydride, and diphenylsulfone.

Description

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

  Conventionally, it relates to a positive photosensitive composition in which the sensitive part becomes soluble in an alkaline developer by exposure to a semiconductor laser beam having a wavelength of 700 to 1,100 nm. 1) The humidity in the coating work chamber is 25 to 60%. When applying in a range, it is not necessary to apply to the object to be coated, and subsequent burning is not required, so that necessary and sufficient adhesion to aluminum is obtained. In particular, much stronger adhesion than aluminum is required. Necessary and sufficient adhesion to copper or copper sulfate plating can be obtained. 2) Even if the alkali strength of the developer is low, good alkali development can be performed without generating a residue in an appropriate time of about 60 to 70 seconds. Because development is possible, work during development and waste liquid processing are easy. 3) High sensitivity is maintained by not performing the burning process, and the edge of the resist image follows the exposure irradiation pattern. 4) Very good development that can be cut with sharp outlines 4) Less film loss after development and very good development with less pinholes due to film reduction 5) Glossy resist image, A resist image having printing durability enough to print several thousand sheets is obtained even if it is used for printing as it is, and scratch resistance in handling before development after formation of a photosensitive film is improved. 6) Latage of image printing and development by a semiconductor laser. In order to provide an excellent positive photosensitive composition, the applicant of the present application absorbs infrared rays from (A) a polymer substance having at least one carboxyl group in the molecule, and (B) an image exposure light source. Thus, a positive photosensitive composition containing a photothermal conversion substance that converts it into heat has been proposed and has been well received (Patent Document 1).

However, the conventional positive photosensitive composition as described above does not require burning before exposure and has excellent adhesion, but further improvement in sensitivity has been demanded.
WO2005 / 001576A1

  An object of the present invention is to provide a positive photosensitive composition that has excellent adhesion and does not require burning before exposure and has high sensitivity.

  In order to solve the above problems, the positive photosensitive composition of the present invention comprises (A) a polymer substance having at least one carboxyl group in the molecule, and (B) absorbing infrared rays from an image exposure light source to heat. It comprises a photothermal conversion substance to be converted and (M) a thermal acid generator.

  The thermal acid generator (M) is preferably one or more selected from the group consisting of p-toluenesulfonic acid ester, p-toluenesulfonic acid anhydride, and diphenylsulfone.

  The photothermal conversion substance (B) is preferably an infrared absorbing dye.

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

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

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

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

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

[In Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, a is an integer of 1 to 3, and b is an integer of 1 or more. ]

  The thermal acid generator (M) is preferably one or more selected from the group consisting of p-toluenesulfonic acid ester, p-toluenesulfonic acid anhydride, and diphenylsulfone.

It is preferable that the positive photosensitive composition of the present invention further contains (C) a dissolution inhibitor.
It is preferable that the positive photosensitive composition of the present invention further contains (D) a photoacid generator.
The positive photosensitive composition of the present invention comprises (E) (1) vinyl pyrrolidone / vinyl acetate copolymer, (2) vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) vinyl pyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate copolymer. , (4) polyvinyl acetate, (5) polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenol resin, (8) alkylphenol resin, (9) melamine / formaldehyde resin, and (10) ketone resin It is preferable to further contain at least one resin selected from the group consisting of:
It is preferable that the positive photosensitive composition of the present invention further contains (F) a triarylmethane dye.

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

The plate-making method of the present invention is characterized by using the positive photosensitive composition of the present invention.
The plate-making method of the present invention preferably includes a step of applying the positive photosensitive composition to an application target and a step of exposing the applied coating film without performing a heat treatment.
By the plate making method of the present invention, printing plates such as intaglio plates (gravure), planographic plates, letterpress plates and stencil plates can be prepared, and in particular, gravure plate making is suitable.

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

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

  According to the present invention, there is a remarkable effect that it is possible to provide a novel positive photosensitive composition that has excellent adhesion without burning before exposure and has high sensitivity.

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

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

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

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

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

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

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

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

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

  Examples of the polymer substance (A) include a polymer of the maleic monomer, a copolymer having a maleic monomer as a main component, a polymer of the (meth) acrylic monomer, and ( A copolymer based on a (meth) acrylic monomer, a maleic acid monomer, and a copolymer of a (meth) acrylic monomer and another monomer such as a styrene monomer, Styrene / maleic acid copolymer (hereinafter referred to as copolymer (b1)) obtained by copolymerizing maleic monomer and styrene monomer, acrylic monomer and styrene A copolymer with a monomer, a derivative of these polymers, or a modified product thereof is preferable. A maleic acid polymer, a (meth) acrylic acid polymer, represented by the following general formulas (2) and / or (3) A copolymer having a structure represented by the following general formula (4), or (meth) acrylic More preferably a copolymer of the Le acid (meth) acrylic acid ester and the styrene monomer, and more preferably a copolymer represented by the following general formula (1).

[In Formula (2), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent, preferably a hydrogen atom, a lower alkyl group or a group having a reactive double bond. ]

[In Formula (4), R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a monovalent substituent, A hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group is preferable. R ⁸ represents a hydrogen atom or a monovalent substituent, and a hydrogen atom or a hydroxyalkyl group is preferable. ]

[In Formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a substituted or unsubstituted alkyl group, a hydrogen atom, a lower alkyl group or When there are a plurality of R ¹ and R ² , which are more preferably alkoxyalkyl groups, they may be the same or different. It is preferable that at least one of R ¹ and R ² is a hydrogen atom, a is 0 or an integer of 1 or more, 1 to 3 is preferable, b is an integer of 1 or more, and 6 to 12 are preferable. ]

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

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

  In addition, as the polymer substance (A), the copolymer (b1) is modified with a compound having a reactive double bond [hereinafter referred to as copolymer (b2). ] May be used. In this case, the ratio of the structure represented by the formulas (2) and (3) to the structure represented by the formula (4) is preferably about 1. Specifically, the copolymer (b2) can be produced by reacting a compound having a reactive double bond with the acid anhydride group or carboxy group in the copolymer (b1). . In this case, it is necessary that the carboxyl group necessary for alkali development remains in the copolymer.

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

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

  The method for producing the copolymers (b1) and (b2) is not particularly limited, and known methods (for example, JP-B 47-25470, JP-B 48-85679, JP-B 51-21572, etc.) Refer to this). Reactive double bonds can also be introduced in a polymer substance having a carboxy group other than the styrene / maleic acid polymer in the same manner as described above. Giving a reactive double bond to the copolymer is preferable from the viewpoint of increasing the degree of curing and improving printing durability.

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

  The photothermal conversion substance (B) is not particularly limited as long as it is a compound capable of converting the absorbed light into heat, but is an organic having an absorption band in part or all of the infrared region having a wavelength of 700 to 1,100 nm. Examples include inorganic pigments and dyes, organic pigments, metals, metal oxides, metal carbides, metal borides, and the like, and infrared absorbing pigments having an absorption band in part or all of the infrared region having a wavelength of 700 to 1,100 nm are preferable. More preferred is an infrared absorbing dye that efficiently absorbs light in the wavelength region and hardly absorbs light in the ultraviolet region or does not substantially react even if absorbed. For example, the following general formula (5) or (6 ) Or a derivative thereof is preferably used.

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

[In Formula (6), R < ¹³ > -R < ¹⁸ > shows a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group each independently. X ⁻ represents a counter anion, and examples of X include a halogen atom, ClO ₄ , BF ₄ , p-CH ₃ C ₆ H ₄ SO ₃ , or PF ₆ . ]

  Examples of other infrared absorbing dyes include polymethine (—CH═) n such as a heterocycle containing a nitrogen atom, an oxygen atom, or a sulfur atom as described in JP-A-11-231515. The so-called cyanine dyes in a broad sense bound to each other can be cited as representative examples. Specifically, for example, quinoline (so-called cyanine), indole (so-called indocyanine), benzothiazole (so-called) , Thiocyanine series), iminocyclohexadiene series (so-called polymethine series), pyrylium series, thiapyrylium series, squarylium series, croconium series, azurenium series, etc. Among them, quinoline series, indole series, benzothiazole series, iminocyclo Hexadiene, pyrylium, or thiapyrylium are preferred. In particular, phthalocyanine and cyanine are preferable.

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

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

The thermal acid generator (M) is a substance that generates an acid by heat. For example, the thermal acid generator (M) is one selected from the group consisting of p-toluenesulfonic anhydride, p-toluenesulfonic acid esters, and diphenylsulfone, or Two or more kinds are preferably used.
Examples of the p-toluenesulfonic acid ester include p-toluenesulfonic acid glycidyl ester, p-toluenesulfonic acid-n-heptyl ester, p-toluenesulfonic acid-n-hexyl ester, and p-toluenesulfonic acid 2-methoxy. Ethyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid 3-nitrophenyl ester, p-toluenesulfonic acid pentafluorobenzyl ester, p-toluenesulfonic acid phenethyl ester, p-toluenesulfonic acid cyclohexyls (for example, Suitable examples include p-toluenesulfonic acid cyclohexyl ester, p-toluenesulfonic acid- (4-tert-butylcyclohexyl), p-toluenesulfonic acid- (2-isopropyl-5-methylcyclohexyl), and the like. And the like to.

  The content ratio of the thermal acid generator (M) in the positive photosensitive composition of the present invention is as follows: (A) component, (B) component, (C) component, (D) component, (E) component, (F) The total solid content of the component and the component (M) is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight.

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

As the dissolution inhibitor (C), a compound represented by the following formula (7) (4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol ) Is preferably used.

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

  The content ratio of the dissolution inhibitor (C) in the positive photosensitive composition of the present invention is as follows: (A) component, (B) component, (C) component, (D) component, (E) component, (F) component And it is preferable that it is 0.5-8 weight% with respect to the solid content total amount of (M) component, and 1-5 weight% is more preferable. These dissolution inhibitors may be used alone or in combination of two or more.

  The photoacid generator (D) is a substance that generates an acid by light, and acts as a sensitizer. Examples of the photoacid generator (D) include compounds described in Patent Document 1, diphenyliodonium salts, triphenylsulfonium salts, aromatic sulfonic acid esters, triazine compounds, diazodisulfone compounds, and the like. The compound represented by 8) is particularly preferred.

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

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

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

  The content ratio of the resin (E) in the positive photosensitive composition of the present invention is as follows: (A) component, (B) component, (C) component, (D) component, (E) component, (F) component and ( It is preferable that it is 1 to 40 weight% with respect to the solid content total amount of M) component, and 5 to 30 weight% is more preferable.

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

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

  The content ratio of the dye (F) in the positive photosensitive composition of the present invention is as follows: (A) component, (B) component, (C) component, (D) component, (E) component, (F) component and ( It is preferable that it is 0.1 to 10 weight% with respect to the solid content total amount of M) component, and 1-4 weight% is more preferable.

  In addition to the above-described components, the poly-type photosensitive composition of the present invention may include other colorants such as pigments or dyes, sensitizers, development accelerators, adhesion modifiers, and coating properties as necessary. You may mix | blend various additives, such as an agent. The development accelerator is preferably added with a small amount of, for example, dicarboxylic acid, amines or glycols.

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

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

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

As a coating method, meniscus coating, fountain coating, dip coating, spin coating, roll coating, wire bar coating, air knife coating, blade coating, curtain coating, and the like can be used. The thickness of the coating film is preferably in the range of 1 to 6 μm, more preferably 3 to 5 μm.
The positive photosensitive composition of the present invention does not require heat treatment after coating, and has sufficient adhesion and sensitivity.

As a light source for image exposure of the positive photosensitive composition layer, a semiconductor laser or a YAG laser that generates an infrared laser beam having a wavelength of 700 to 1,100 nm is preferable. In addition, a solid laser such as a ruby laser or an LED can be used. The light intensity of the laser light source is preferably 2.0 × 10 ⁶ mJ / s · cm ² or more, and more preferably 1.0 × 10 ⁷ mJ / s · cm ² or more.

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

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

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

(Examples 1-4 and Comparative Example 1)
A positive photosensitive composition was prepared with the compounding substances and blending ratios (parts by weight) shown in Table 1, and used as a test photosensitive solution.

Each component in Table 1 is as follows.
Resin A1: SMA 1440 (manufactured by SARTOMER, partially esterified product of styrene / maleic anhydride copolymer with butyl cellosolve).
Infrared absorbing dye: Infrared absorbing dye represented by the formula (5) Thermal acid generator 1: Diphenyl sulfone Thermal acid generator 2: Para-toluenesulfonic acid 3-nitrophenyl ester Thermal acid generator 3: Para-toluenesulfonic acid Phenethyl ester dissolution inhibitor: TrisP-PA (a compound represented by the above formula (7), manufactured by Honshu Chemical Industry Co., Ltd.).
Photoacid generator: IRGACURE 250 (a compound represented by the above formula (8), manufactured by Ciba Specialty Chemicals Co., Ltd.)
Resin E1: PVP / VA copolymer (copolymer of vinylpyrrolidone and vinyl acetate having a molecular weight of 46,000 and a glass transition point of 96 ° C., vinylpyrrolidone / vinyl acetate 50/50)
Coloring pigment: Oil Blue 613 (Orient Chemical Industry Co., Ltd., Color Index (CI) No. 42595)
PM: Propylene glycol monomethyl ether IPA: Isopropyl alcohol MEK: Methyl ethyl ketone

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

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

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

  Subsequently, the test roll was set to 100 r. p. After rotating at m for 20 minutes and stopping, the residual solvent concentration in the photosensitive film was measured and found to be 2%.

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

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

As shown in Table 2, the positive photosensitive compositions of Examples 1 to 4 have significantly improved sensitivity as compared with Comparative Example 1 in which no thermal acid generator was added, and although the film ratio was small, Also improved.
Furthermore, there is an advantage that the life of the light source is prolonged by exposing at a low illuminance.

  In addition, although it experimented about the case where it carried out similarly to Example 1 except having used the copper surface or the aluminum surface instead of the copper sulfate plating surface, as in Example 1, the favorable result was obtained. In the case of the aluminum surface, a particularly wide development latitude was obtained.

(Example 5)
As component (E), instead of resin E1, resin E2: GAFQUAT 734 (manufactured by ISP, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer), resin E3: GAFFIX VC-713 (manufactured by ISP, vinylpyrrolidone / vinylcaprolactam / Dimethylaminoethyl methacrylate terpolymer), resin E4: Sacnol SN-09T (manufactured by Denki Kagaku Kogyo Co., Ltd., polyvinyl acetate), resin E5: Denka Butyral # 3000 (manufactured by Denki Kagaku Kogyo K.K., polyvinyl butyral), resin E6: Vinylec-K type (manufactured by Chisso Corp., polyvinyl formal), resin E7: Tamanoru 803L (Arakawa Chemical Industries, terpene phenol resin), resin E8: Tamanoru 520S (Arakawa Chemical Industries, Ltd., alkylphenol resin) ), Fat E9: Vanserin SM-960 (manufactured by Harima Kasei Co., Ltd., melamine / formaldehyde resin), resin E10: Hilac 111 (manufactured by Hitachi Chemical Co., Ltd., cyclohexanone ketone resin), or resin E11: Hilac 110H (Hitachi) When an experiment was performed in the same manner as in Example 1 except that Kasei Chemical Co., Ltd. (acetophenone ketone resin) was used, good results were obtained as in Example 1.

Claims (12)

(A) a polymer substance having at least one carboxyl group in the molecule;
(B) A positive-type photosensitive composition comprising a photothermal conversion substance that absorbs infrared rays from an image exposure light source and converts it into heat, and (M) a thermal acid generator.   2. The thermal acid generator (M) is one or more selected from the group consisting of p-toluenesulfonic acid ester, p-toluenesulfonic acid anhydride, and diphenylsulfone. The positive photosensitive composition as described.   The positive photosensitive composition according to claim 1 or 2, wherein the photothermal conversion substance (B) is an infrared absorbing dye.   The positive photosensitive composition according to claim 1, further comprising (C) a dissolution inhibitor.   The positive photosensitive composition according to any one of claims 1 to 4, further comprising (D) a photoacid generator.   (E) (1) vinylpyrrolidone / vinyl acetate copolymer, (2) vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) vinylpyrrolidone / vinylcaprolactam / dimethylaminoethyl methacrylate copolymer, (4) polyvinyl acetate, (5) At least one resin selected from the group consisting of polyvinyl butyral, (6) polyvinyl formal, (7) terpene phenol resin, (8) alkylphenol resin, (9) melamine / formaldehyde resin, and (10) ketone resin The positive photosensitive composition according to claim 1, wherein the positive photosensitive composition is contained.   (F) The positive photosensitive composition according to any one of claims 1 to 6, further comprising a triarylmethane dye.   A photofabrication method using the positive photosensitive composition according to claim 1.   9. The photofabrication method according to claim 8, wherein the photofabrication method is applied to manufacture a printing plate, an electronic component, a precision instrument component, or an anti-counterfeiting related member.   A plate making method using the positive photosensitive composition according to any one of claims 1 to 7. Applying the positive photosensitive composition to the object to be coated;
Exposing the applied coating without performing heat treatment; and
The plate-making method according to claim 10, comprising:   The plate making method according to claim 10, wherein the plate making method is a gravure plate making method.