JP2005004197A - Apparatus and method for processing developing solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for processing development aggregates produced in a developing machine for a photosensitive resin composition used for the manufacture of a printed wiring board, lead frame, semiconductor package, back plate of a plasma display or the like. <P>SOLUTION: The apparatus for processing a developing solution includes a combination of a mixing means and a separating means. The invention presents a developing apparatus equipped with the above apparatus, and presents a method for removing aggregates in the developing solution produced in a developing machine after exposing a photosensitive resin composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a developer processing apparatus, a developing apparatus, and a developer processing method, and in particular, a photosensitive resin composition is coated or laminated on a surface of a substrate to be processed, and then exposed and developed to form a pattern. The present invention relates to a system for removing development agglomerates generated at the time.

  Conventionally, as resist materials used for etching, plating, sand blasting, etc. in the fields of printed wiring board manufacturing, precision metal processing, plasma display back plate processing, etc., photosensitive resin compositions and dry film resists (hereinafter referred to as “resin materials”) DFR) is widely used. The DFR usually consists of three layers: a light transmissive support film, a photosensitive resin composition layer, and a protective film. The method of use is as follows. First, the protective film is peeled off, and then the photosensitive resin layer is pressure-bonded (laminated) so that it directly touches the surface of the substrate to be processed, and the patterned negative film is adhered onto the light-transmitting film. A method of forming (developing) a resist pattern by irradiating (exposure) (often using ultraviolet rays), and then spraying an organic solvent or an aqueous alkali solution to remove unnecessary portions can be mentioned as a general method. In particular, from the viewpoint of environmental problems, a developer using an alkaline aqueous solution is demanded.

  However, it is difficult to completely dissolve the photosensitive resin composition in the alkaline developer. By using a compound having a surfactant function, micelles mainly having undissolved components are formed, and the alkaline developer has an emulsion state. In general, development is performed by finely dispersing (see Patent Documents 1 and 2). Here, the generated micelles are subjected to shearing processes such as spray nozzles, spraying on the substrate surface, liquid feeding by a pump, filtration by a filter, etc., and the micelles are destroyed and undissolved components of the photosensitive resin composition are aggregated. There is a problem that the substrate processing is hindered by depositing in an alkali developing tank or adhering to the substrate surface to be processed. Such an aggregate of undissolved components in the developer of the photosensitive resin composition is generally called an aggregate or a development aggregate.

In order to solve this problem, development of a photosensitive resin composition having a composition that hardly causes aggregation, addition of a dispersion stabilizer for stabilizing the micelles, and a device on a device that does not apply shear to the micelles as much as possible were studied. It has been improved considerably, but it has not yet reached a radical solution.
JP-A-5-011446 Japanese Patent Laid-Open No. 2002-214779

  The present invention aims to solve the development aggregation problem, and in particular, development generated in a developing machine for a photosensitive resin composition used in the manufacture of printed wiring boards, lead frames, semiconductor packages, plasma display back plates and the like. The purpose is to solve the aggregate problem.

The present inventors worked on the development of a method for drastically solving the development aggregation problem, and deviated from the common sense of stabilizing the conventional micelle, which was caused by actively destroying the micelle and causing aggregation. A new idea of efficiently removing the aggregates out of the system was reached and the present invention was completed.
That is, the present invention provides the following inventions.
(1) Development characterized in that it comprises a mixing means for aggregating undissolved components that have flowed into the developer after development from the development object, and a separating means for separating the agglomerated undissolved components from the developer. Liquid processing equipment.
(2) The developing solution processing apparatus according to (1), wherein the mixing means comprises a mixer having a mixing blade and / or a static mixer.
(3) The developing solution processing apparatus according to (1), wherein the separation unit is a filter and / or a liquid cyclone.
(4) Development means for bringing the object to be developed into contact with the developer, the processing apparatus according to any one of (1), (2) or (3), and the developer processed by the processing apparatus as the development means A developing device comprising a supply means for supplying.
(5) The developing device according to (4), further including a storage unit that stores the developer after development, and has an oil adsorption mat at least at one location in the storage unit.
(6) A developer comprising: a step of aggregating undissolved components that have flowed into the developer after development from the development object; and a step of separating the agglomerated undissolved components from the developer. Processing method.
(7) A developing solution processing method, wherein the developing solution processed by the processing method according to (6) is returned to the developing means.
(8) The developer after development is obtained by developing an alkali-developable photosensitive resin layer of a dry film resist with an alkali developer, (6) or (7) Developer processing method.

  According to the processing apparatus of the present invention, the development aggregation problem is solved, and in particular, the developing device for the photosensitive resin composition used for manufacturing printed wiring boards, lead frames, semiconductor packages, plasma display back plates and the like in the developing machine. It is possible to efficiently remove the development agglomerates generated in step 1, and stable development processing can be performed. Further, the developing device of the present invention has less deposit of aggregates in the developing tank than the conventional developing device, so that cleaning and maintenance are easy, and there is less adhesion of aggregates on the substrate surface, so that the production yield is also improved. Play.

Hereinafter, the present invention will be described in detail.
The developer processing apparatus of the present invention is characterized by having a mixing means and a separating means. The mixing means used in the present invention aggregates undissolved components in the developer.
The mixing means is preferably a stirring tank having a mixing blade, a mixer, a static mixer or the like, and can be combined to form a mixing means. The static mixer is a static mixer, and generally has a mixing weir provided in multiple stages inside a pipe. Mixing can be performed by flowing the liquid at a linear speed above a certain level. For this purpose, a developer designed so that the developer is sufficiently sheared and the destruction of micelles proceeds. In addition to the mixing means used in the present invention, a stirring tank, stirring blades, etc. can be freely provided for making the developer concentration uniform and adjusting the developer temperature.

The separation means used in the present invention is a device for separating the aggregate in the developer from the developer, and a filter and a liquid cyclone having an appropriate hole diameter are preferable. Further, the filter and the liquid cyclone can be combined to be used as a separating means.
The specifications of the mixing means and the separating means are to determine the conditions under which the undissolved material efficiently precipitates from the developer in which the photosensitive resin composition to be used exists in an emulsion state, and the conditions under which the aggregate can be separated. Can be determined. The emulsion state described in the present invention refers to a state in which the photosensitive resin composition component is dispersed and emulsified in the developer.
As the developer used in the present invention, a developer corresponding to the photosensitive resin composition, such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, can be used.

In the present invention, examples of the developing means for bringing the object to be developed into contact with the developer include a developing machine. In the developing machine, the photosensitive resin composition can be developed with a developer. For example, development can be performed by a known method such as spraying, rocking dipping, brushing, scraping or the like. As the developing solution, a safe and stable solution having good operability such as an alkaline aqueous solution is used.
Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate, potassium phosphate, and phosphoric acid. Alkali metal phosphates such as sodium, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and alkali borates such as lithium, sodium or potassium borate are used.

Moreover, as alkaline aqueous solution used for image development, 0.1-5 mass% dilute solution of sodium carbonate, 0.1-5 mass% dilute solution of potassium carbonate, 0.1-5 mass% dilute solution of sodium hydroxide, A dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
The aqueous developer comprises water or an alkaline aqueous solution and one or more organic solvents. Here, as the alkaline substance, in addition to the base of the alkaline aqueous solution, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, 3- Examples include propanediol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the aqueous developer is preferably as low as possible within a range where the development of the development object can be sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.

Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. It is done. These are used alone or in combination of two or more. The concentration of the organic solvent in the aqueous developer is usually preferably from 2 to 90% by mass, and the temperature can be adjusted according to the developability. Further, a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.
Examples of the organic solvent developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by mass in order to prevent ignition.

Moreover, you may use together 2 or more types of image development methods as needed. Development methods include a dip method, a battle method, a spray method, brushing, scraping, and the like, and a high-pressure spray method is most suitable for improving resolution. As the treatment after development, the resist pattern may be further cured and used by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² as necessary.
The developing machine can have storage means for storing the developer after development. Examples of the storage means include a developing tank inside the developing machine, a developing tank outside the developing machine, and the like.
The developer is used in the developing tank, but the dispersed developer can be returned to the developer tank and recycled. In this case, if an oil adsorbing mat is installed in the developing tank or the developing tank, an oily substance such as a monomer can be removed from the developer. Examples of the oil adsorption mat include a porous mat made of a solvent-resistant and water-resistant material such as polyolefin. Examples of commercially available products include K-format (manufactured by Takaha Shoji Co., Ltd., registered trademark).

  In the present invention, the supply means for supplying the developer processed by the developer processing apparatus to the developing means may be a simple pipe. A pump may be provided in the supply means so that an appropriate amount of developer can be secured in the developing means. Further, a filter for removing a small amount of development aggregates and dust may be provided. In addition, it is also preferable to newly mix the developing effective component in the developer and keep the effective component constant and supply it to the developing means. For example, when an aqueous sodium carbonate solution is used as the developer, sodium carbonate or an aqueous sodium carbonate solution is appropriately mixed and supplied to the developing means so as to keep the sodium ion concentration in the developer constant.

  Examples of an object to be developed in the present invention include an alkali-developable photosensitive resin composition of a dry film resist, which includes (A) a carboxyl group-containing binder polymer, and (B) at least one in the molecule. A photopolymerizable compound having two polymerizable ethylenically unsaturated groups and (C) a photopolymerization initiator can be contained. In an alkaline developer, the photopolymerizable compound (B) and the photopolymerization initiator (C) are often precipitated as undissolved substances. The carboxyl group-containing binder as component (A) is alkali-soluble and often has a function of surrounding micelles (B) and (C) to form micelles and emulsify them. Further, for the component (B) or (C) component having both a hydrophilic site or alkalized soluble site and a lipophilic site in the molecule, they surround micelles in the developer to form micelles, It can also be emulsified. In addition, the components (A) to (C) can be dispersed, emulsified and emulsified with a surfactant, an antifoaming agent, an organic solvent, etc. present in the developer.

The binder polymer having a carboxyl group (A) in the present invention preferably has an acid equivalent of 200 to 500, more preferably 200 to 400. Here, the acid equivalent means the mass of a polymer having 1 equivalent of carboxylic acid therein. The acid equivalent is measured by potentiometric titration with 0.1N sodium hydroxide. The acid equivalent is preferably 200 or more from the viewpoint of compatibility with the coating solvent or the monomer, and preferably 500 or less from the viewpoint of peelability.
The weight average molecular weight of the binder polymer is preferably 50,000 to 400,000, more preferably 100,000 to 400,000. The molecular weight is measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. 400,000 or less is preferable from the viewpoint of developability, and 50,000 or more is preferable from the viewpoint of keeping the thickness of the photosensitive resin composition layer uniform.

The binder polymer contains a carboxylic acid having one polymerizable unsaturated group such as a carbon-carbon double bond in the molecule as the first monomer. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid half ester, and the like.
The binder polymer contains a non-acidic monomer having a polymerizable unsaturated group such as a carbon-carbon double bond in the molecule as the second monomer. The non-acidic monomer is selected so as to maintain various characteristics such as developability of the photosensitive resin layer, resistance in etching and plating processes, and flexibility of the cured film. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Alkyl (meth) acrylates such as 2-hydroxyethyl acrylate, benzyl (meth) acrylate, esters of vinyl alcohol such as vinyl acetate, styrene or polymerizable styrene derivatives and (meth) acrylonitrile. Most suitable are methyl methacrylate and styrene. Here, (meth) acryl represents methacryl and / or acryl.

The binder polymer can be used alone or in combination of two or more.
The binder polymer having a carboxyl group (A) is preferably in the range of 10 to 90 parts by weight, more preferably 30 to 70 parts by weight, with respect to 100 parts by weight of the total amount of the components (A) and (B). %. 10 mass% or more is preferable from a cold-flow-resistant viewpoint. 90 mass% or less is preferable from a viewpoint of the brittleness of the photosensitive resin layer.
The binder polymer is prepared by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile to a solution obtained by diluting a mixture of monomers with a solvent such as acetone, methyl ethyl ketone, isopropanol or ethanol. It is preferable to synthesize by stirring. In some cases, a part of the mixture is synthesized while being dropped into the reaction solution. In addition, a solvent may be further added after completion of the reaction to prepare a desired concentration. In addition to solution polymerization, it can also be synthesized by bulk polymerization, suspension polymerization and emulsion polymerization.

  As the photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule of the component (B), for example, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxypolyethoxypolypropyne) phenyl) A compound obtained by reacting an α, β-unsaturated carboxylic acid with a bisphenol A-based (meth) acrylate compound such as propane, a glycidyl group-containing compound, and a urethane bond Urethane monomers such as (meth) acrylate compounds, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydride Xylpropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β '-(meth) acryloyloxyethyl- Although o-phthalate, (meth) acrylic acid alkyl ester, etc. are mentioned, it is preferable to make a bisphenol A type (meth) acrylate compound or the (meth) acrylate compound which has a urethane bond into an essential component. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It is done. Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- 00 (made by Shin-Nakamura Chemical Co., Ltd., product name) and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin-Nakamura Chemical) It is commercially available as a product name manufactured by Kogyo Co., Ltd. These may be used alone or in combination of two or more.

Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These may be used alone or in combination of two or more.
Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy) phenyl, and the like.

  Examples of the urethane monomer include diisocyanates such as a (meth) acrylic monomer having an OH group at the β-position and isophorone diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, and 1,6-hexamethylene diisocyanate. Examples include addition reaction products with compounds, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

Examples of the EO-modified urethane di (meth) acrylate include the product name UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of EO and PO-modified urethane di (meth) acrylates include the product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like. . These may be used alone or in combination of two or more.
(B) As a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, the following polyurethane prepolymer can also be used.

The polyurethane prepolymer reacts with a polymer or monomer having a hydroxyl group at the terminal and a terminal isocyanate group of polyurethane derived from polyisocyanate with a functional group having active hydrogen and a compound having both ethylenically unsaturated bonds in the molecule. To obtain.
Examples of the polymer having a hydroxyl group at the terminal include polyols such as polyester polyol and polyether polyol, 1,4-polybutadiene having a terminal hydroxyl group, hydrogenated or non-hydrogenated 1,2-polybutadiene, butadiene-styrene copolymer, and butadiene. -Acrylonitrile copolymer, as a monomer having a hydroxyl group at the terminal, glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, triethylene glycol, and diols having a carboxyl group in the molecule such as dimethylolpropionic acid Etc.

  As polyisocyanate, toluylene diisocyanate, diphenylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, O-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α, α′-dimethyl- O-xylylene diisocyanate, α, α′-dimethyl-m-xylylene diisocyanate, α, α′-dimethyl-p-xylylene diisocyanate, α, α, α′-trimethyl-O-xylylene diisocyanate, α, α , Α′-trimethyl-m-xylylene diisocyanate, α, α, α′-trimethyl-p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-O-xylylene diisocyanate, α, α, α ', α'-tetrame Le -m- xylylene diisocyanate, α, α, α ', α'- tetramethyl -p- diisocyanate, cyclohexane diisocyanate.

Examples of the compound having both a functional group having active hydrogen and an ethylenically unsaturated bond in the molecule include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (Meth) acrylate, polypropylene glycol mono (meth) acrylate and the like can be mentioned.
As the photopolymerization initiator of component (C), generally known photopolymerization initiators can be used. The photopolymerization initiator is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass. When the actinic ray absorption rate of the photosensitive resin composition is suppressed and used as a photosensitive resin laminate, the amount of the photopolymerization initiator is preferably 15% by mass or less in order to sufficiently cure the bottom of the photosensitive resin layer. Moreover, 0.01 mass% or more is preferable from a viewpoint of a sensitivity.

As a photopolymerization initiator, it exhibits the most effective performance when p-aminophenyl ketone and lophine dimer are combined. In this case, 0.01 to 1% by mass of p-aminophenyl ketone and 0.1 to 6% by mass of lophine dimer are required. When the p-aminophenyl ketone is less than 0.01% by mass and when the lophine dimer is less than 0.1% by mass, sufficient sensitivity cannot be obtained. If the amount of p-aminophenyl ketone is more than 1% by mass, the adhesiveness is lowered. When the amount of the lophine dimer is more than 6% by mass, the development aggregation property is deteriorated.
As an example of p-aminophenyl ketone, aromatic ketones such as Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone are used.

The lophine dimer includes 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-chlorophenyl) -4,5-bis (p-methoxyphenyl) imidazolyl dimer, 2- Biimidazole compounds such as (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer are used.
As photopolymerization initiators other than p-aminophenyl ketone and lophine dimer, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2,3-diphenylanthraquinone, 1 -Chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro- Quinones such as 2-methylanthraquinone, benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, benzoin ethers such as methylbenzoin and ethylbenzoin, acridines such as 9-phenylacridine, and N-aryl such as N-phenylglycine -Α-amino acids, thioki Combinations of sandones and aminobenzoic acid, such as ethylthioxanthone and ethyl dimethylaminobenzoate, 2-chlorothioxanthone and ethyl dimethylaminobenzoate, combinations of isopropylthioxanthone and ethyl dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, etc. Alkyl benzoic acids, 1-phenyl-1,2-propanedione-2-o-benzoin oxime, 1-phenyl-1,2-propanedione-2-o-ethoxycarbonyloxime, and the like.

In addition, the photosensitive resin composition that is a development object in the present invention includes a dye such as malachite green, a photochromic agent such as leuco crystal violet, a thermochromic inhibitor, p-toluenesulfonic acid amide, etc. Plasticizers, pigments, fillers, antifoaming agents, flame retardants, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. (A) and (B) About 0.01 to 20 parts by mass can be contained for each 100 parts by mass of the total amount of components. These can be used alone or in combination of two or more.
In addition, to the photosensitive resin composition to be developed used in the present invention, additives such as radical polymerization inhibitors and plasticizers for improving thermal stability and storage stability are added as necessary. can do.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol naphthylamine cuprous chloride, pentaerythrityl tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} ( IRGANOX (registered trademark) 1010, manufactured by Ciba-Geigy, Japan), triethylene glycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate} (IRGANOX (registered trademark) 245, manufactured by Ciba-Geigy, Japan) , Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX (registered trademark) 1076, manufactured by Ciba Geigy Japan, Inc.) and the like. Examples of the plasticizer include diethyl phthalate and diphenyl. Lids such as phthalates Examples thereof include a sulfonic acid ester compound, a sulfonamide compound such as p-toluenesulfonamide, a petroleum resin, rosin, polyethylene glycol, polypropylene glycol, and an ethylene glycol-propylene glycol block copolymer. Examples of the color former include tris (4-dimethylaminophenyl) methane {leuco crystal violet}, tris (4-diethylamino 2-methylphenyl) methane {leucomalachite green}, and the like.

As for the thickness of the photosensitive resin layer after drying of the photosensitive resin composition used for this invention, 1-150 micrometers is preferable, More preferably, 3-50 micrometers is used. The thickness of the photosensitive resin layer is preferably 1 μm or more from the viewpoint of film formation coating, and is preferably 150 μm or less from the viewpoint of resolution and adhesion.
The photosensitive resin composition layer is irradiated with actinic rays in an image form through a negative or positive mask pattern called an artwork. Under the present circumstances, when the polymer film which exists on the photosensitive resin composition layer is transparent, you may irradiate actinic light as it is, and when it is opaque, it is necessary to remove naturally. As the light source of actinic light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that emits ultraviolet rays effectively is used. Moreover, what emits visible light effectively, such as a photographic flood light bulb and a solar lamp, is also used. Next, after the exposure, when a support is present on the photosensitive resin composition layer, after removing the support, the unexposed portion is removed and developed to produce a resist pattern.

Hereinafter, the embodiments of the present invention will be described in more detail by way of examples.
[Example 1]
A photosensitive resin composition having the composition shown in Table 1 is applied to a support film to obtain a DFR. Laminate DFR to substrate. After passing through a cartridge filter having an average hole diameter of 50 μm using a 0.5% by mass aqueous sodium carbonate solution as a developer, the exposed substrate with DFR is developed with a spray type developing machine. There is 200 liters of developer in the developer tank. Development is carried out by extracting the developer from the developer tank in the developing device with a pump and spraying it onto the substrate by spraying. The dispersed developer returns to the developing tank and is circulated and reused until a predetermined amount of substrate processing. A static mixer and a liquid cyclone are installed in the arrangement shown in FIG. 1 between the pump and the filter of the developer tank. The developer that has passed through the static mixer is in a state in which micelles are destroyed and aggregates of undissolved components float, and the liquid is separated into a developer and aggregates with a liquid cyclone. Aggregates are discarded after separation. The developer passes through the filter and is again sprayed from the nozzle of the spray type developing machine. 40 μm thick DFR was developed to 0.4 m ² per unit (1 liter) of developer, but development aggregates did not deposit inside the spray nozzle, substrate surface, and developer tank, spray pressure, development time, etc. Stable development processing was possible. It was easy to collect and discard the separated aggregates.

[Example 2]
The development process was carried out in the same manner as in Example 1 except that the oil adsorption mat was floated in the developing tank during development in the developing machine. No oil suspended matter was found in the developing tank.

[Comparative Example 1]
The same development treatment as in Example 1 was performed except that a static mixer and a liquid cyclone were not used. At the stage of development treatment up to 0.4 m ² , the agglomerates adhered to the substrate surface and the agglomerates in the development tank. Deposition was observed. It was difficult to collect the agglomerates deposited in the tank.
Explanation of Symbols in Table 1 P-1: Copolymer having a composition of methacrylic acid / methyl methacrylate / n-butyl acrylate (mass ratio 20/40/40) and a weight average molecular weight of 100,000. 29% methyl ethyl ketone solution.

M-1: Urethane prepolymer A
(Production of urethane prepolymer A)
100 parts by mass of poly (propylene glycol adipate) diol (hydroxyl value 44.9) and polyoxyethylene (EO) -oxypropylene (PO) block copolymer diol (EO / PO molar ratio 1/4, hydroxyl value 44.9) ) 100 parts by mass and 0.01 g of BTL (2-butyltin laurate) as a catalyst were placed in a reaction vessel and mixed well. 17.8 parts by mass of m-xylylene diisocyanate was added thereto, and after stirring well, the external temperature was raised from 40 ° C. to 80 ° C. and reacted as it was for about 5 hours, and then 2-hydroxyethyl acrylate (molecular weight 116) 3.9 parts by mass) was added and stirred well. When the reaction was allowed to proceed for about 2 hours, the reaction was stopped to obtain urethane prepolymer A. The number average molecular weight of the urethane prepolymer A was 21,000.

M-2: Trimethylolpropane triacrylate M-3: Urethane product of hexamethylene diisocyanate and tripropylene glycol monomethacrylate M-4: Polyethylene glycol added with an average of 8 moles of propylene oxide further added with ethylene oxide at both ends Moleculed glycol dimethacrylate M-5: Dimethacrylate obtained by reacting bisphenol A with 8 mol of propylene oxide and 8 mol of ethylene oxide and then ester-bonding methacrylic acid

I-1: Benzyldimethyl ketal I-2: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer I-3: 2,4-diethylthioxanthone I-4: ethyl p-dimethylaminobenzoate D -1: leuco crystal violet D-2: diamond green

FIG. 3 is a diagram illustrating an example of a configuration of a developing device according to the present invention.

Claims (8)

  Processing of a developer characterized by comprising a mixing means for aggregating undissolved components that have flowed into the developer after development from the development object, and a separating means for separating the agglomerated undissolved components from the developer. apparatus.   2. The developer processing apparatus according to claim 1, wherein the mixing means comprises a mixer having mixing blades and / or a static mixer.   The developing solution processing apparatus according to claim 1, wherein the separating means is a filter and / or a liquid cyclone.   A developing means for bringing a developing object into contact with a developing solution, a processing apparatus according to any one of claims 1, 2, and 3, a supply means for supplying the developing solution processed by the processing apparatus to the developing means, A developing device comprising:   The developing device according to claim 4, further comprising a storage unit that stores the developer after development, and an oil adsorption mat at least at one location in the storage unit.   A processing method for a developing solution, comprising: a step of aggregating undissolved components that have flowed into a developing solution after development from a development object; and a step of separating the agglomerated undissolved components from the developing solution. .   A developing solution processing method, wherein the developing solution processed by the processing method according to claim 6 is returned to the developing means.   8. The processing method for a developing solution according to claim 6, wherein the developing solution after development is obtained by developing an alkali-developable photosensitive resin layer of a dry film resist with an alkali developing solution. .

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