JP4095342B2 - Positive photosensitive composition - Google Patents

Description

【００２１】
【実施例】
表１中に示すように、ポジ型感光性組成物の原液を以下の４種類作った。
(a) 原液Ａ・・・ノボラック樹脂と波長域６５０〜１３００ｎｍの近赤外線領域の一部又は全部に吸収帯を有しレーザ光を吸収して熱分解する光ディスク用色素からなるもの、
このノボラック樹脂は、ｍ−クレゾールとｐ−クレゾールと２，５−キシレノールと３，５−キシレノールとレゾルシノールとの混合フェノール類と、ホルムアルデヒドとの重縮合体を使用した。
(b) 原液Ｂ・・・レゾール樹脂と上記光ディスク用色素からなる原液、
(c) 原液Ｃ・・・ポリビニルフェノール樹脂と上記光ディスク用色素からなる原液、
(d) 原液Ｄ・・・フェノール性水酸基を有するアクリル酸誘導体の共重合体と上記光ディスク用色素からなる原液、
そして、溶剤のＭＥＫに溶解してグラビア印刷用の被製版ロールの硫酸銅メッキ面に塗布してバーニングして感光膜を形成した。表中の実施例１から７は、４５℃のバーニングで光沢が良好であり固い感光膜となった。近赤外線で露光して現像したところ、極めて良好なパターンが切れた。
表中の比較例１から４は、バーニング温度を１３０℃にしても硫酸銅メッキ面に対する密着性が極めて小さく造膜されず、近赤外線で露光して現像したところ、パターンが全く切れず、全面的にボロボロと剥離した。
表中の比較例５から９は、バーニング温度を１００℃〜１３０℃にすることで光沢が良好であり固い感光膜となり、パターンが概ね良好にきれた。
表中の比較例１０と１１は、バーニング温度を８０℃〜１００℃に下げて光沢が良好であり固い感光膜となり、パターンが概ね良好にきれた。
【００２２】
【発明の効果】
本願発明によれば、近赤外波長域のレーザーに露光感応して該感応部が現像液に可溶になる近赤外波長域レーザー感応性を有し、バーニング温度を低くしても銅メッキ面又は銅合金メッキ面に対する低温での密着性が極めて良好であるため高感度になり現像が良好にできるポジ型感光性組成物を提供することができる。
本願発明は、グラビア印刷用の被製版ロールの硫酸銅メッキ面にポジ型感光膜を形成するのに好ましいが、これに限定されるものではなく、アルミニウム、亜鉛、鋼等の金属板、アルミニウム、亜鉛、銅、鉄、クロム、ニッケル等をメッキ又は蒸着した金属板、樹脂を塗布した紙、アルミニウム等の金属箔を貼着した紙、プラスチックフィルム、親水化処理したプラスチックフィルム、及びガラス板等に適用しても低温での密着性が良好であり、高感度が得られ、従って、感光性平版印刷版、簡易校正印刷用プルーフ、配線板やグラビア用銅エッチングレジスト、フラットディスプレイ製造に用いられるカラーフィルター用レジスト、ＬＳＩ製造用フォトレジスト等に好適に使用できる。
【図面の簡単な説明】
【図１】 イミダゾールシランの密着機能を示す模式図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a positive photosensitive composition having a near-infrared wavelength region laser sensitivity in which the sensitive part becomes soluble in a developer upon exposure to a near-infrared wavelength region laser.
[0002]
[Prior art]
As one of the plate making methods for gravure printing rolls, there is a so-called etching method in which a photosensitive film is applied and formed on the copper sulfate plating surface of a plate making roll, an image is printed with a laser, developed, etched, resist stripped and chromium plated. It is done.
In the conventional etching method, a negative photosensitive film is applied to a plate-making roll, and the coating film is dried at room temperature to form a negative photosensitive film, which is baked with an argon ion laser to form a positive photosensitive film. Therefore, no baking is performed with a laser in the near-infrared wavelength region.
High-resolution laser-sensitive direct plate making systems using high-power semiconductor lasers, YAG lasers, etc. are not in practical use. Compared to using argon ion lasers, the size of the equipment is reduced, and ambient light during plate making operations is reduced. The realization is strongly desired from the aspect.
[0003]
[Problems to be solved by the invention]
If the beam diameters of the argon ion laser and the laser in the near-infrared wavelength region are the same, the resolution of the laser is higher in the positive type than in the negative type.
In addition, printing a positive image on a photosensitive film of a positive photosensitive composition with a laser in the near-infrared wavelength region cuts the pattern more than printing a negative image on a photosensitive film of a negative photosensitive composition with an argon ion laser. Is good. This is considered to be a difference in pattern cut due to a difference in composition between the positive photosensitive composition and the negative photosensitive composition.
The high-power semiconductor laser head of Creositex, Canada, emits a laser in the near-infrared wavelength region, and is mounted on an offset printing machine to irradiate a positive photosensitive composition for good development. It is in practical use worldwide.
[0004]
Therefore, with regard to the etching method as one of the plate making methods of the gravure printing roll, a positive type photosensitive composition photosensitive film is applied and formed on the copper sulfate plating surface of the plate making roll, and a high-power semiconductor laser head of Creositex Co., Ltd. When we tested the improvement in which a positive image was printed by irradiating a laser in the near infrared wavelength range with an exposure device equipped with, developed, etched, resist stripped and chrome plated, no satisfactory plate was obtained. I found out there was a problem.
In this case, as the positive photosensitive composition, a positive photosensitive composition in which a novolak resin, which is a composition of the positive photosensitive composition disclosed in JP-A-11-231515, which is practically used for offset printing, and a cyanine dye are blended. The stock solution was prepared, and this stock solution was applied to a plate-making roll for a gravure plate and burned to form a positive photosensitive film.
[0005]
First, a positive photosensitive composition is applied and burned so that the film surface temperature becomes 60 ° C., and is adhered to a roll, a photosensitive film is formed, developed by laser exposure, and due to poor adhesion of the photosensitive film. Development was poor due to inability to expose. As a result of various tests, even if the burning process was performed so that the film surface temperature was 130 ° C., it was defective.
Therefore, only when a silane coupling agent (γ-glycidoxypropyltrimethoxysilane) is added as an adhesion agent, the adhesion of the photosensitive film is improved, and exposure and development can be performed slightly better.
There are the following types of silane coupling agents.
Vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, γ-glycidoxy Propylmethyldiethoxysilane, NB (aminoethyl) γ-aminopropyltrimethoxysilane, NB (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ- I tried blending aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane, but the adhesion to the film was not the best and exposure / development did not exceed a slightly good range. . Moreover, the burning temperature of the film surface could not be lowered from 80 ° C. to 100 ° C.
Next, I changed the silane coupling agent as an adhesion agent and tried to put imidazole as a curing accelerator, but there was no particular difference from the case of the silane coupling agent, and the film surface burning temperature was also the case of the silane coupling agent. It was the same.
The imidazole is described in JP-A-9-015857, and as imidazole of Shikoku Kasei Kogyo Co., Ltd., 2E4MZ, 1B2MZ, 1M2EZ, 1B2PZ, 2MZ, 2PZ, C11Z, C17Z, 2P4MZ, 2E4MZ-CN, C11Z-CN 2PZ-CN, 2PZ-CNS, 2MZ-A, 2E4MZ-A, C11Z-A, 2MA-OK, 2PZ-OK, 2PHZ, 2P4MHZ, TBZ, 2MZL-F, 2PZL, SFZ, VT, MAVT. There may be some overlap.
[0006]
The reason why it is necessary to perform the burning treatment at a high film surface temperature is that the film is not formed due to poor adhesion of the positive photosensitive composition to the copper plating surface or copper alloy plating surface. It is.
In addition, a good photosensitive film can be formed without burning on the offset printing plate, but it is necessary to perform a burning process at a high film surface temperature for forming a photosensitive film on a plate-making roll for a gravure plate. The offset printing plate has a thin aluminum plate as the base material on which the photosensitive film is formed, and has good adhesion, whereas the plate roll for gravure printing has a copper sulfate plating surface and has extremely poor adhesion. This is due to the fact that by setting the film surface temperature to 80 ° C. to 130 ° C., the hydrogen bond of the alkali-soluble organic polymer substance having a phenolic hydroxyl group is strengthened and the adhesion is enhanced.
[0007]
However, the plate making rolls for gravure plates are made of aluminum and iron, and the roll diameters are different and the wall thicknesses are all different when the roll diameters are different. Because of the difference in specific heat capacity, even if the heater is heated for the same time, the heat is transferred to the roll base and the film surface temperature is not always heated to 130 ° C. It is important to reduce the temperature and eliminate the problem of specific heat capacity.
When the film surface temperature was 130 ° C., it took 100 minutes or more for burning and subsequent cooling, a large amount of heat energy was required, the running cost was high, and this proved to be impractical.
On the other hand, when the film surface temperature is 130 ° C., the hydrogen bond of the alkali-soluble organic polymer substance having a phenolic hydroxyl group is strengthened and development is difficult, and the cyanine dye is denatured and sensitivity is lowered.
[0008]
Thus, four types of stock solutions of the positive photosensitive composition were prepared, and various adhesives were added to each stock solution to form a photosensitive film. In particular, the photosensitive composition of the positive photosensitive composition to which imidazole silane was added was formed. It was confirmed that the film could be satisfactorily formed under conditions of a burning temperature of 45 ° C. and a room temperature of 25 ° C., and that the sensitivity was good and development was easy, and the invention was completed.
[0009]
The present invention has a near-infrared wavelength region laser sensitivity in which the sensitive part becomes soluble in a developer upon exposure to a near-infrared wavelength region laser, and even if the burning temperature is lowered, An object of the present invention is to provide a positive photosensitive composition that has extremely good adhesion to a copper alloy plated surface at a low temperature, high sensitivity, and good development.
[0010]
[Means for Solving the Problems]
The invention according to claim 1 comprises an alkali-soluble organic polymer substance having a phenolic hydroxyl group, a photothermal conversion dye that absorbs near-infrared rays of an image exposure light source and converts it into heat, and imidazole silane. Is a positive photosensitive composition.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to an alkali-soluble organic polymer substance having at least one phenolic hydroxyl group, such as a novolak resin, a resole resin, a polyvinylphenol resin, a copolymer of an acrylic acid derivative having a phenolic hydroxyl group, and a wavelength range of 650 to 1300 nm. Organic or inorganic pigments, dyes, organic pigments, metals, metal oxides, metal carbides, metal borides, etc. that have an absorption band in part or all of the near infrared region and absorb near infrared rays to convert them into heat A positive photosensitive composition comprising a photothermal conversion dye and imidazolesilane.
The content of the alkali-soluble organic polymer substance in the positive photosensitive composition is preferably 2 to 98% by weight, and more preferably 30 to 90% by weight.
The content ratio of the photothermal conversion dye in the positive photosensitive composition is preferably 2 to 60% by weight, and more preferably 3 to 50% by weight.
The content of imidazolesilane in the positive photosensitive composition is preferably 1 to 2% by weight.
The positive photosensitive composition of the present invention usually has a copper-plated surface of a plate-making roll for gravure printing that is a support surface as a solution in which the above-described components are dissolved in a solvent such as a cellosolve solvent or a propylene glycol solvent. After coating on the copper sulfate plating surface, the positive photosensitive film having the photosensitive composition layer formed on the support surface is obtained by heating and drying with a heater. The use ratio of the solvent is usually in the range of about 1 to 20 times by weight with respect to the total amount of the photosensitive composition.
As a coating method, kiss coating, dip coating, spin coating, roll coating, wire bar coating, air knife coating, blade coating, curtain coating and the like can be used. The coating amount is preferably in the range of 1 to 6 μm.
In addition, it is preferable to add a small amount of dicarboxylic acid, amines or glycols as a development accelerator. Further, a dissolution inhibitor may be contained. Furthermore, an applicability improver, a sensitivity improver, a sensitizer, and the like may be contained.
[0012]
An alkali-soluble organic polymer substance having a phenolic hydroxyl group is a main component of resist formation, and is a binder resin having low adhesion to a copper plating surface or a copper sulfate plating surface. A part of the chain is cleaved to become a small molecule with higher alkali solubility, and a part is ablated.
Examples of the alkali-soluble organic polymer substance having a phenolic hydroxyl group include novolak resins, resole resins, polyvinylphenol resins, copolymers of acrylic acid derivatives having a phenolic hydroxyl group, and the phenolic compounds described in JP-A-11-231515. An alkali-soluble organic polymer substance having a hydroxyl group can be applied exactly, and a novolac resin or a polyvinylphenol resin is particularly preferable.
The novolac resin is a resin obtained by polycondensing at least one phenol with at least one aldehyde or ketone under an acidic catalyst. In particular, a mixed phenol of m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and resorcinol, or a mixed phenol of phenol, m-cresol and p-cresol, and formaldehyde Polycondensates having a polystyrene-reduced weight average molecular weight (MW) of 1,500 to 10,000 as measured by gel permeation chromatography are preferred.
The resole resin is a resin obtained by polycondensation in the same manner except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin.
The polyvinyl phenol resin is, for example, a resin obtained by polymerizing one or more hydroxystyrenes in the presence of a radical polymerization initiator or a cationic polymerization initiator. A polymer of hydroxystyrenes having a C 1-4 alkyl group as a substituent on the benzene ring or a polymer of hydroxystyrenes having an unsubstituted benzene ring is preferred.
[0013]
The photothermal conversion dye has an absorption band in a part or all of the near infrared wavelength region of 650 to 1300 nm and has a property of absorbing and thermally decomposing laser light in the near infrared wavelength region, Involved in alkali-soluble molecular weight reduction and ablation by thermal cleavage of molecules of alkali-soluble organic polymer materials having hydroxyl groups.
Photothermal conversion dyes include organic or inorganic pigments or dyes having an absorption band in part or all of the near infrared region of the wavelength range of 650 to 1300 nm, organic dyes, metals, metal oxides, metal carbides, metal borides and the like. The photothermal conversion dye described in Kaihei 11-231515 can be applied exactly, and a heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom or the like is bonded with polymethine (-CH =) n, in a broad sense Typical examples of so-called cyanine dyes include quinoline (so-called cyanine), indole (so-called indocyanine), benzothiazole (so-called thiocyanine), and imino. Examples include cyclohexadiene (so-called polymethine), pyrylium, thiapyrylium, squarylium, croconium, and azurenium. , In, quinoline, indole type, benzothiazole type, iminocyclohexadiene system, pyrylium type or thiapyrylium are preferred.
[0014]
The imidazole silane supplements the alkali-soluble organic polymer substance having a phenolic hydroxyl group, which is a binder resin, but has very low adhesion to the copper plating surface or the copper sulfate plating surface.
Imidazole silane can capture adhesion at low temperatures. FIG. 1 shows the adhesion function of imidazole silane.
Imidazolesilane is a patent product of Japan Energy Corporation. JP 07-068256 (Japan), US5258522 (USA), DE69207989 (Germany), GB526847EP (UK), FR526847EP (France)
The imidazole silane may be any of the product names IS-1000, IS-1000D, IM-1000, and SP-1000.
When the content ratio of imidazole silane is large, a good coating film can be obtained. However, when the content ratio is too large, the solubility in an alkali developer is reduced, and the exposed pattern is insufficient and the resist pattern is insufficient. It tends to be difficult to obtain. This corresponds to the fact that when the molecular weights of the novolak resin, the resol resin, and the polyvinylphenol resin are too large, the solubility in an alkali developer is reduced, and the resist pattern tends to be difficult to obtain.
[0015]
The dissolution inhibitor is preferably an acid color-forming dye having a lactone skeleton, and forms a hydrogen bond with an alkali-soluble organic polymer substance for the purpose of increasing the difference in solubility in an alkali developer between an exposed area and an unexposed area. It has a function of lowering the solubility of the polymer substance, has a function of hardly absorbing light in the near infrared region, and not being decomposed by light in the near infrared region.
Other dissolution inhibitors include sulfonic acid esters, phosphoric acid esters, aromatic carboxylic acid esters, aromatic disulfones, carboxylic acid anhydrides, aromatic ketones, aromatic aldehydes, aromatic amines, aromatic ethers, thiolactone skeletons, There are an acid coloring dye having an N, N-diarylamide skeleton, a diarylmethylimino skeleton, a base coloring dye having a sulfolactone skeleton, a nonionic surfactant, and the like.
The content of the dissolution inhibitor in the positive photosensitive composition is preferably 0 to 20% by weight.
[0016]
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 cellosolve solvents 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.
Ester solvents include 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 alcohol solvents include heptanol, hexanol, diacetone alcohol, and furfuryl alcohol.
Examples of highly polar solvents 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.
[0017]
As a light source for image exposure of the positive photosensitive composition layer, a semiconductor laser or a YAG laser that generates a near infrared laser beam of 650 to 1300 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, particularly preferably 1.0 × 10 7 mJ / s · cm 2 or more.
[0018]
As the developer used for the photosensitive film formed using the positive photosensitive composition of the present invention, inorganic alkali, Na, K salt, organic alkali, TMAH, choline, etc., inorganic or organic alkali can be used. Is preferred.
[0019]
The development is usually performed at a temperature of about 15 to 45 ° C. by immersion development, spray development, brush development, ultrasonic development or the like.
[0020]
[Table 1]

[0021]
【Example】
As shown in Table 1, the following four types of stock solutions of positive photosensitive compositions were prepared.
(a) Stock solution A: composed of a novolak resin and a dye for optical discs that has an absorption band in part or all of the near infrared region in the wavelength range of 650 to 1300 nm and absorbs laser light to thermally decompose;
As this novolak resin, a polycondensate of m-cresol, p-cresol, a mixed phenol of 2,5-xylenol, 3,5-xylenol and resorcinol, and formaldehyde was used.
(b) Stock solution B: Stock solution comprising a resole resin and the above-mentioned dye for optical disc,
(c) Stock solution C: Stock solution comprising polyvinylphenol resin and the above-mentioned dye for optical disc,
(d) Stock solution D: Stock solution comprising a copolymer of an acrylic acid derivative having a phenolic hydroxyl group and the above-mentioned dye for optical discs,
And it melt | dissolved in MEK of a solvent, apply | coated to the copper sulfate plating surface of the plate-making roll for gravure printing, and burned, and formed the photosensitive film | membrane. In Examples 1 to 7 in the table, the gloss was good by burning at 45 ° C. and a hard photosensitive film was obtained. When developed by exposure with near infrared rays, a very good pattern was cut.
In Comparative Examples 1 to 4 in the table, even when the burning temperature was set to 130 ° C., the adhesion to the copper sulfate plating surface was extremely small, and no film was formed. It peeled off.
In Comparative Examples 5 to 9 in the table, by setting the burning temperature to 100 ° C. to 130 ° C., the gloss was good and a hard photosensitive film was obtained, and the pattern was generally good.
In Comparative Examples 10 and 11 in the table, the burning temperature was lowered to 80 ° C. to 100 ° C., the gloss was good and a hard photosensitive film was obtained, and the pattern was generally good.
[0022]
【The invention's effect】
According to the present invention, it is sensitive to exposure to a laser in the near-infrared wavelength region, and the sensitive part becomes soluble in a developer, and has a near-infrared wavelength region laser sensitivity. Even if the burning temperature is lowered, copper plating is performed. Since the adhesion at low temperature to the surface or the copper alloy plating surface is very good, it is possible to provide a positive photosensitive composition that has high sensitivity and good development.
The present invention is preferable for forming a positive photosensitive film on a copper sulfate plating surface of a plate-making roll for gravure printing, but is not limited to this, a metal plate such as aluminum, zinc or steel, aluminum, For metal plates plated or vapor-deposited with zinc, copper, iron, chromium, nickel, paper coated with resin, paper with affixed metal foils such as aluminum, plastic films, plastic films treated with hydrophilic treatment, glass plates, etc. Adhesion at low temperature is good even when applied, and high sensitivity is obtained. Therefore, photosensitive lithographic printing plates, proofs for simple proof printing, copper etching resists for wiring boards and gravure, colors used in flat display manufacturing It can be suitably used for a resist for filters, a photoresist for manufacturing LSIs, and the like.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an adhesion function of imidazolesilane.

Claims (1)

A positive photosensitive composition comprising an alkali-soluble organic polymer substance having a phenolic hydroxyl group, a photothermal conversion dye that absorbs near-infrared rays of an image exposure light source and converts it into heat, and imidazole silane. object.

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