JP2005057018A - Resist ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide resist ink that is used for forming a resist pattern which can be peeled easily in a short time with an aqueous alkali solution by a direct resist drawing method, and to provide methods of manufacturing resist pattern, conductor pattern, and printed wiring board using the resist ink. <P>SOLUTION: (1) Resist ink having a swelling factor of ≥50% when a formed resist pattern is dipped in a 3% aqueous alkali solution for 40 seconds is used as the resist ink used for forming a resist pattern by the direct resist drawing method. (2) The resist ink described in (1) having a photosensitive property is used. (3) The resist pattern is formed by the direct resist drawing method by using the resist ink described in (1) or (2). (4) A conductor pattern is formed by using the method described in (3). (5) A printed wiring board is manufactured by using the method described in (4). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resist ink used for creating a resist pattern, a resist pattern, a conductor pattern, a printed wiring board, and methods for producing them.

  Conventionally, a photolithography method has been used as a specific example of a method for manufacturing a printed wiring board. In this photolithography method, for example, a photoresist layer made of a dry film resist or the like is formed on a copper clad laminate made of an insulating layer and a copper foil. Next, the dry film resist is photocured by irradiating the surface of the photoresist layer with ultraviolet rays through a photomask. Thereafter, using a developing solution such as an organic solvent or an alkaline aqueous solution, the dry film resist in the uncured portion is removed to form a resist pattern. Next, after removing the copper foil of the portion not covered with the resist pattern by etching, and removing the resist pattern to form a conductor pattern, a printed wiring board is obtained.

However, such a method for producing a printed wiring board has a drawback that it takes a very long time to produce a photomask, and thus the time required for producing the printed wiring board becomes long. In addition, since development is performed using an organic solvent, an alkaline aqueous solution, or the like, the time required for producing a printed wiring board is increased and there is a problem of waste liquid treatment.
In order to solve this problem, a method is disclosed in which a resist material is directly sprayed onto a substrate using an ink jet method to form a resist pattern to be a conductor pattern (Patent Document 1).
In this method, when the resist pattern is peeled after the wiring is formed, waste liquid treatment becomes a problem when cleaning with an organic solvent is required. In addition, even a resist that can be stripped with an alkaline aqueous solution is difficult to completely strip in a short time.
Japanese Patent Application Laid-Open No. 06-237063

  In resist inks used to form resist patterns using the resist direct-drawing method, we provide resist inks that can be easily and quickly removed with an alkaline aqueous solution. Resist patterns, conductor patterns, and prints using the resist ink A method for manufacturing a wiring board is provided.

The present inventor has found that the above problem can be solved by using a resist ink having a specific swelling ratio in an alkaline aqueous solution. That is, the present invention
(1) In a resist ink used for forming a resist pattern by a resist direct drawing method, the swelling rate when the formed resist pattern is immersed in a 3% alkaline aqueous solution for 40 seconds is 50% or more. Resist ink.
(2) The resist ink as described in (1), which is photosensitive.
(3) A method of forming a resist pattern by a resist direct drawing method using the resist ink according to (1) or (2).
(4) A method of forming a conductor pattern by forming a resist pattern by the method described in (3) and etching or plating a portion not covered with the resist pattern.
(5) A method for producing a printed wiring board using the method described in (4).

According to the present invention, a resist pattern can be uniformly formed even on an uneven substrate without providing a gap between the substrate and the resist pattern. There is no need to create a pattern mask. There is no problem of developing waste liquid treatment, and there is no concern about deterioration of the resist pattern in the developing process.
After the conductor pattern is formed, the resist pattern can be easily removed with an alkaline aqueous solution. The time required for forming the conductor pattern is shortened, there is no peeling residue, and the conductor pattern and the printed wiring board can be manufactured with high yield.
According to the present invention, all of the above effects can be satisfied simultaneously.

The resist direct drawing method in the present invention is a method in which a resist pattern is directly formed on a substrate without going through an exposure step and a development step through a pattern mask. The process of creating a resist pattern and a conductor pattern by the resist direct drawing method includes a resist pattern forming process, a conductor pattern forming process, and a resist pattern peeling process. The resist pattern forming process includes a drawing process and a curing process.
The drawing step is a step of applying a resist ink on a base material by discharging the resist ink from a nozzle and attaching the resist ink in accordance with a desired wiring shape. A method for drawing a resist pattern by discharging a resist ink from a nozzle includes spraying by an ink jet method, drawing by a plotter, and the like.

  In the curing step, the volatile solvent component can be cured by volatilization. Further, the resist ink heated and melted at the nozzle portion may be cooled and naturally effected by adhering to the substrate. It can also be thermally cured by heating. The resist pattern can be cured by irradiation with visible light, ultraviolet light, or the like, that is, by exposure. You may make it harden | cure combining exposure and a heating. Such curing is mainly performed in order to increase resistance in an etching or plating process when forming a conductor later, and to form a good conductor pattern with a high yield.

In the conductor pattern forming step, the conductor pattern is formed by etching or plating the base material on which the resist pattern is formed. For the etching and plating processes, the apparatus and processes normally used in the production of printed wiring boards can be used as they are.
A resist pattern peeling process means the process of removing the resist pattern which became unnecessary, and, thereby, a conductor pattern is completed. The peeling method is preferably a swelling peeling method using a strong alkali or the like or a dissolution peeling method.

As an example, a direct drawing method for directly forming a resist pattern by spraying resist ink onto a substrate by an inkjet method, and a method for manufacturing a conductor pattern and a printed wiring board in the present invention will be described.
First, a copper clad laminate 1 and an ink 5 are prepared as shown in FIG. The copper clad laminate 1 is obtained by laminating a copper foil 3 on the surface of an insulating layer 2 such as a glass / epoxy resin laminate, a paper / phenol resin laminate, a polyimide film, or a polyester film. The thickness of the copper foil 3 is selected according to the use of the wiring board.

  The ink 5 is ejected from the inkjet nozzle 4. The resist ink is not particularly limited as long as it has etching resistance. For example, a resist ink in which a wax or a thermoplastic resin is dissolved or dispersed in a liquid medium composed of an organic solvent, water, or the like is used. A preparation agent, a surface tension preparation agent, a wetting agent, a pH preparation agent, a crosslinking agent, an adhesion improver, various stabilizers, a coloring agent, and the like are added. The ink 5 may be liquid when it is ejected from the nozzle 4. Therefore, the ink 5 may be a composition that does not include a liquid medium, is solid at room temperature, and becomes liquid when heated. Among the above-mentioned substances, the photosensitive resist ink is preferable because it can easily form a cured film having high etching resistance by irradiation with active energy rays. In particular, a photosensitive resist ink containing a thermoplastic polymer having a carboxyl group and a photocrosslinkable monomer is preferable because the cured film can be peeled off with an alkaline solution.

  Next, ultraviolet or visible light is applied while spraying ink 5 from the inkjet nozzle 4 onto the copper foil 3 of the copper clad laminate 1 so as to cover the portion where the conductor pattern is to be formed, as shown in FIG. A resist pattern 6 is formed. The resist pattern 6 may be cured with energy other than ultraviolet rays or visible light, for example, active energy rays such as electron beams, as necessary. Next, as shown in FIG. 1C, the copper foil 3 in the portion not covered with the resist pattern 6 is removed by etching the copper-clad laminate 1 with the resist pattern 6 formed thereon. Etching solutions such as copper chloride, iron chloride, and ammonia are used.

  Finally, the resist pattern 6 is peeled from the copper foil 3 to form a conductor pattern 7 as shown in FIG. For the stripper, an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide is used according to the ink 5 used.

  In this method of manufacturing a printed wiring board, a resist pattern 6 is formed on the copper foil 3 of the copper-clad laminate 1 by using an ink 5 by ink jetting, and then a portion not covered by the resist pattern 6 is formed. After removing the copper foil 3 by etching, the resist pattern 6 is peeled off from the portion of the copper foil 3 covered with the resist pattern 6 to form the conductor pattern 7, so that no photomask is required and an alkaline aqueous solution or Since there is no development process using an organic solvent or the like, there is no problem of developing waste liquid treatment, and there is an advantage that it is possible to greatly reduce the time required for producing a printed wiring board. In this example, the example in which the copper foil 3 is laminated on one side of the insulating layer 2 has been described. However, the same can be applied to the case where the copper foil is laminated on both sides of the insulating layer 2.

Next, the resist ink of the present invention will be described.
The resist ink of the present invention means a resist ink used for a resist direct drawing method. After the resist ink is formed on the base material, it becomes a resist pattern, which acts as an etching resist when forming a conductor pattern by etching the base material. Also, a plating resist when forming a conductor pattern by plating As a role. Furthermore, the resist ink can be stripped by the method described in the resist pattern stripping step after forming a conductor pattern by etching, plating, or the like.

The resist ink preferably has photosensitivity, and the resist ink having photosensitivity is called photosensitive resist ink. When a photosensitive resist ink is used, it is preferable to expose the resist ink with active light such as visible light or ultraviolet light at an appropriate time.
The resist ink of the present invention is required to have the following basic performance. The resist ink cures quickly and a resist pattern can be created in a short time. After the resist pattern is obtained, a conductor pattern having high etching resistance or plating resistance and having few disconnection defects or shorts can be formed with high yield.

The resist ink of the present invention contains (A) a carboxyl group-containing binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator. Can do.
(A) As for the binder polymer which has a carboxyl group, 200-500 are preferable for an acid equivalent, More preferably, it is 200-400. Here, the acid equivalent means the weight of the 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 curability, and 50,000 or more is preferable from the viewpoint of maintaining the thickness and flexibility of the resist pattern.
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 that various characteristics such as resistance in etching and plating processes and flexibility of a resist pattern are maintained. 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 the viewpoint of the brittleness or peelability of the resist pattern. 90 mass% or less is preferable from a sclerosing | hardenable viewpoint.
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 that the bisphenol A type (meth) acrylate compound or the (meth) acrylate compound which has a urethane bond is included. 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 can 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) acryloxyhexaethoxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane, dialkyl methacrylate of polyalkylene glycol in which 2 mol of propylene oxide and 15 mol of ethylene oxide are added to both ends of bisphenol A, respectively. Can be mentioned. These can 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) acryl 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, 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. The amount of the photopolymerization initiator is preferably 15% by mass or less in order to suppress the actinic ray absorption rate of the resist ink and sufficiently cure the bottom of the resist pattern. Moreover, 0.01 mass% or more is preferable from a viewpoint of a sensitivity.

As a photopolymerization initiator, effective performance is obtained when p-aminophenyl ketone and lophine dimer are combined. In this case, it is preferable to contain 0.01 to 1% by mass of p-aminophenyl ketone and 0.1% by mass or more of lophine dimer. From the viewpoint of curability, the p-aminophenyl ketone is preferably 0.01% by mass or more and the lophine dimer is preferably 0.1% by mass or more. From the viewpoint of the adhesion of the resist pattern, the p-aminophenyl ketone is preferably 1% by mass or less.
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 resist ink in the present invention includes, if necessary, a dye such as malachite green, a photochromic agent such as leuco crystal violet, a thermochromic inhibitor, a plasticizer such as p-toluenesulfonic acid amide, a pigment, and a filler. , Antifoaming agent, flame retardant, adhesion-imparting agent, leveling agent, peeling accelerator, antioxidant, fragrance, imaging agent, thermal crosslinking agent, etc. with respect to 100 parts by mass of the total amount of component (A) and component (B) About 0.01 to 20 parts by mass. In addition to p-toluenesulfonic acid amide and the like, these can be used alone or in combination of two or more.
Moreover, additives, such as a radical polymerization inhibitor and a plasticizer for improving thermal stability and storage stability, can be added to the resist ink of the present invention as necessary.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol naphthylamine cuprous chloride, pentaerythrityltetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) ( IRGANOX (registered trademark) 1010 manufactured by Ciba-Geigy Corporation of Japan, triethylene glycol-bis (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate) (IRGANOX (registered trademark) 245 manufactured by Ciba-Geigy Corporation of Japan) And octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX (registered trademark) 1076 manufactured by Ciba-Geigy Japan).

  Examples of the plasticizer include phthalate compounds such as diethyl phthalate and diphenyl phthalate, sulfonamide compounds such as p-toluenesulfonamide, petroleum resin, rosin, polyethylene glycol, polypropylene glycol (Toa Gosei Chemical Co., Ltd.) ) Carbodiol (registered trademark) D-2000), ethylene glycol-propylene glycol block copolymer, compound Adecanol (registered trademark) SDX-1569 with ethylene oxide or propylene oxide added to both ends of bisphenol A, Adecanol (registered) Trademarks) SDX-1570, Adecanol (registered trademark) SDX-1571, Adecanol (registered trademark) SDX-479 (manufactured by Asahi Denka Co., Ltd.), New Pole (registered trademark) BP-23P, New Pole ( (Registered trademark) BP-3P, New Pole (registered trademark) BP-5P, New Pole (registered trademark) BPE-20T, New Pole (registered trademark) BPE-60, New Pole (registered trademark) BPE-100, New Pole ( (Registered trademark) BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), UNIOR (registered trademark) DB-400, UNIOR (registered trademark) DAB-800, UNIOR (registered trademark) DA-350F, UNIOR (registered trademark) DA- 400, Uniol (registered trademark) DA-700 (manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.) and the like.

Examples of the color former include tris (4-dimethylaminophenyl) methane {leuco crystal violet}, tris (4-diethylamino 2-methylphenyl) methane {leucomalachite green}, and the like.
Examples of the adhesion-imparting agent include benzotriazole, carboxybenzotriazole, N (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, and N (N, N-di-2-hydroxyethyl) amino. Methylenebenzotriazole, N (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole, 1-N-diethylaminomethylcarboxybenzotriazole, 1-N-dipropylaminomethylcarboxybenzotriazole, 1-N-dibutylamino And methyl carboxybenzotriazole.

The resist ink of the present invention is used as an ink having an appropriate viscosity after being diluted with a suitable solvent.
In the present invention, the swelling rate when the resist pattern is immersed in an aqueous alkali solution for 40 seconds is 50% or more. An upper limit of 500% is conceivable. More preferably, it is 80% or more, More preferably, it is 100% or more. From the viewpoint of defective peeling, the swelling rate is preferably 50% or more. Although it does not specifically limit as aqueous alkali solution, About 0.1 to 10% of sodium hydroxide and potassium hydroxide aqueous solution is used. Moreover, organic amine aqueous solution can also be used.

  The swelling ratio of the present invention is measured by the following method. First, a resist ink is discharged on a polyethylene terephthalate film in a range of 2 cm square from a nozzle. When the resist ink is not a photosensitive resist ink, the resist ink is removed as a discharged 2 cm square resist pattern and immersed in a 3% aqueous sodium hydroxide solution for 40 seconds. If a process such as drying is required when forming the conductor pattern, the resist ink is cured in the same manner as when forming the conductor pattern, and then peeled off from the polyethylene terephthalate film and immersed in a 3% sodium hydroxide solution. To do. When the resist ink is a photosensitive resist ink, irradiation with a high-pressure mercury lamp is performed after the discharge of the resist ink. The irradiation dose is set according to the dose required to cure the resist pattern and form the conductor pattern. The cured 2 cm square resist ink is peeled off as a resist pattern and immersed in a 3% aqueous sodium hydroxide solution for 40 seconds.

The resist pattern soaked as described above is taken out from the aqueous sodium hydroxide solution, and the area S (cm ² ) is calculated by measuring four sides. The swelling ratio is calculated by the following formula (I).
(Swelling ratio) (%) = (S / 4−1) × 100 (I)

  Next, an embodiment of the present invention will be described with reference to FIG. Ink 5 is obtained by dissolving the resin compositions shown in Tables 1 and 2 in a mixed solvent of methyl ethyl ketone / isopropanol.

[Example]
A flexible copper-clad laminate 1 in which a copper foil 3 having a thickness of 18 μm is laminated on one side of a polyimide film having a thickness of 25 μm is prepared. Next, the ink 5 is sprayed from the nozzle 4 onto the copper foil 3 of the copper-clad laminate 1 to form a resist pattern 6 so as to cover the portion where the conductor pattern is to be formed. Next, irradiation with a high-pressure mercury lamp is performed to cure the resist pattern.
Next, the copper foil 3 in a portion not covered with the resist pattern 6 is removed using a copper chloride etching solution. Finally, when the resist pattern 6 is peeled from the copper foil 3 using a stripping solution (3% NaOH aqueous solution) to form a conductor pattern 7, a printed wiring board is obtained.

<Evaluation>
The swelling ratio of the resist pattern is measured according to the above, and calculated by the formula (I). In any ink composition, the swelling rate is 150% or more.
Regardless of the composition, the curability of the resist pattern is good.
The presence or absence of peeling defects on the substrate is visually observed. There is no peeling residue in any composition.
The conductor pattern is observed with an optical microscope. There is no backlash, chipping or disconnection of the conductor in any composition.

  The present invention can be used for manufacturing a conductor pattern, and can be suitably used for manufacturing a printed wiring board. Since the mask pattern is not required and the development process is not required, the conductor pattern creation time can be greatly shortened, and the environmental burden due to the development waste liquid treatment can be eliminated, which is industrially useful.

It is the figure which showed the preparation methods of the conductor pattern etc. of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Copper clad laminated board 2 Insulating layer 3 Copper foil 4 Nozzle 5 Resist ink 6 Resist pattern 7 Conductor pattern

Claims (5)

A resist ink, which is used for forming a resist pattern by a direct resist drawing method, and has a swelling ratio of 50% or more when the formed resist pattern is immersed in a 3% alkaline aqueous solution for 40 seconds. 2. The resist ink according to claim 1, wherein the resist ink is photosensitive. A method for forming a resist pattern by a resist direct drawing method using the resist ink according to claim 1. A method for forming a conductor pattern, comprising: forming a resist pattern by the method according to claim 3; and etching or plating a portion not covered with the resist pattern. The manufacturing method of the printed wiring board using the method of Claim 4.

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