JP2005057039A - Resist ink for forming conductor pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide resist ink which is used for the formation of a resist pattern by a direct resist drawing method, and with which the resist pattern having a stable film thickness and a cross-sectional shape can be formed; and to provide methods of manufacturing resist pattern, conductor pattern, and printed wiring board using the resist ink. <P>SOLUTION: (1) Resist ink containing a solvent having a boiling point of <80°C is used as the resist ink used for forming the 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 forming the resist pattern by using the method described in (3) and etching or plating the portions not covered with the resist pattern. (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 therefore 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 sprayed directly onto a substrate using an ink jet method to form a resist pattern to be a conductor pattern (Patent Document 1).
However, by simply spraying the resist ink onto the substrate by the inkjet method, the resist ink flows until the solvent volatilizes after the resist ink has landed on the substrate, and a resist pattern with a desired film thickness cannot be obtained. Furthermore, there is a problem that the cross-sectional shape of the pattern is deformed.
Japanese Patent Application Laid-Open No. 06-237063

  Provided is a resist ink that can obtain a stable film thickness and cross-sectional shape of a resist pattern in a resist ink used for resist pattern formation by a resist direct drawing method. Moreover, the manufacturing method of the resist pattern, conductor pattern, and printed wiring board using the same is provided.

The present inventor has found that the above problem can be solved by including a solvent having a boiling point of less than 80 ° C. in the resist ink. That is, the present invention
(1) A resist ink used for forming a resist pattern by a resist direct drawing method, which contains a solvent having a boiling point of less than 80 ° C.
(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. Compared with the conventional photolithography method, it is possible to greatly shorten the time for creating the conductor pattern.
According to the present invention, the photosensitive resin composition does not flow until it volatilizes, and a resist pattern having a desired film thickness and shape can be obtained stably and easily. Further, by combining an appropriate solvent, it is possible to balance viscosity, fluidity after discharge, and volatility.
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 step of forming the conductor pattern, 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 may be a dissolution peeling method using a strong alkali or the like, a swelling peeling method, a swelling peeling method using hot water, or a physical peeling method such as sandblasting or a peeling tape.

As an example, a direct drawing method for directly forming a resist pattern by spraying a resist ink on a substrate by an inkjet method, and a method for manufacturing a conductor pattern and a printed wiring board 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. As the resist ink, for example, a solution obtained by dissolving or dispersing a wax or a thermoplastic resin in a liquid medium composed of an organic solvent, water, or the like is used. If necessary, a viscosity adjusting agent, a surface tension adjusting agent, a wetting agent, a pH adjusting agent are used. Formulations, crosslinking agents, adhesion improvers, various stabilizers, colorants, 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 materials described above, the photosensitive resin composition is preferable because it can easily form a cured film having high etching resistance and plating resistance by irradiation with active energy rays. In particular, a photosensitive resin composition 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. Depending on the ink 5 used, for example, an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, or an organic solvent such as methylene chloride or methyl ethyl ketone (MEK) is used for the stripping solution.
In this example, a resist pattern 6 is formed on the copper foil 3 of the copper-clad laminate 1 by using an ink jet ink 5, and then the copper foil 3 that is not covered with the resist pattern 6 is removed by etching. After that, the resist pattern 6 is peeled off from the copper foil 3 in the portion covered with the resist pattern 6 to form the conductor pattern 7, so that a photomask is unnecessary and a developing process using an alkaline aqueous solution or an organic solvent is used. Therefore, there is no problem of developing waste liquid treatment, and there is an advantage that the time required for producing a printed wiring board can be greatly shortened. 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.

  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 formed, a conductor pattern having high etching resistance or plating resistance and having few disconnection defects or shorts can be formed with a high yield. The resist pattern has good releasability and no residue remains.

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 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 photosensitive resin composition and to 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.

The resist ink of the present invention is diluted with the following appropriate solvent and used as an ink having an appropriate viscosity.
Various solvents having a boiling point of less than 80 ° C. used in the present invention can be used. For example, monoalcohols such as methanol (boiling point 64.6 ° C) and ethanol (boiling point 78.3 ° C), ketones such as acetone (boiling point 56.5 ° C) and methyl ethyl ketone (boiling point 79.6 ° C), Carboxylic acid esters such as ethyl acetate (boiling point 77 ° C.) can be used.
In the present invention, the solvent having a boiling point of less than 80 ° C. can be arbitrarily selected from, for example, the solvents listed above. Among them, those having good compatibility with each component in the resist ink are preferable. For example, methyl ethyl ketone, ethanol, a mixed solvent thereof and the like can be mentioned.

  These solvents can be used in combination with each other, or can be used in combination with a solvent having a boiling point of 80 ° C. or higher. By combining, the viscosity of resist ink, the fluidity after ejection, and the volatility can be adjusted. Thereby, the balance of discharge property, thickness, cross-sectional shape of a resist pattern, and curability can be maintained.

  In addition, the resist ink of the present invention may contain, 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, 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 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 added with ethylene oxide or propylene oxide at both ends of bisphenol A, Adecanol (registered trademark) ) 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.

Next, an embodiment of the present invention will be described with reference to FIG. The composition of the ink 5 is shown in Tables 1 and 2. Table 3 shows the solvent blending amounts.

[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 discharged 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, the portion of the copper foil 3 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.
In any ink composition, there is no disorder in the shape of the resist pattern due to flow deformation of the resist ink. Regardless of the composition, resist patterns having film thicknesses of 1 μm, 5 μm, 20 μm, 40 μm, and 80 μm can be stably formed.

  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 used for forming a resist pattern by a resist direct drawing method, comprising a solvent having a boiling point of less than 80 ° C. 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.

Images