JP2005057019A - Photosensitive resist ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide photosensitive resist ink which is used for forming a resist pattern by a direct resist drawing method and has sufficiently high resist pattern curing speed, etching resistance, peelability, etc., and with which the manufacturing yield and manufacturing time of a conductor pattern can be improved; and to provide methods of manufacturing resist pattern, conductor pattern, and printed wiring board. <P>SOLUTION: (1) Photosensitive resist ink containing a 2,4,5-triallyl imidazole dimer or its derivative, or acridine or its derivative is used as the photosensitive resist ink used for forming the resist pattern by the direct resist drawing method. (2) The photosensitive resist ink described in (1) containing an N-aryl-α-amino acid-based compound is used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive 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. After that, using a developing solution such as an organic solvent or an alkaline aqueous solution, the dry film resist in the uncured portion is dissolved and 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 manufacturing a printed wiring board has a drawback that it takes a very long time to manufacture a photomask, and thus the time required for manufacturing the printed wiring board becomes long. In addition, since development is performed using an organic solvent, an alkaline aqueous solution, etc., the time required for producing the 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).
However, in this method, the resist pattern curing rate, resist pattern etching resistance, resist pattern peelability, and the like are not sufficient, and the production yield and production time of the conductor pattern are not satisfactory.
Japanese Patent Application Laid-Open No. 06-237063

  Resist ink used for resist pattern formation using the resist direct drawing method has sufficient resist pattern curing speed, resist pattern etching resistance, resist pattern peelability, etc., conductor pattern manufacturing yield and required time Provides a photosensitive resist ink, and provides a method for producing a resist pattern, a conductor pattern, and a printed wiring board using the same.

As a result of intensive studies, the present inventor has found that the above-mentioned problems can be solved by containing a specific compound that is cured by ultraviolet rays or visible rays in the photosensitive resist ink, and has reached the present invention.
That is, the present invention
(1) A photosensitive resist ink used for forming a resist pattern by a resist direct drawing method contains 2,4,5-triarylimidazole dimer or a derivative thereof, or acridine or a derivative thereof. Photosensitive resist ink.
(2) The photosensitive resist ink according to (1), comprising an N-aryl-α-amino acid compound.
(3) A resist pattern forming method by a resist direct drawing method using the photosensitive 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. The resist ink cures quickly and a resist pattern can be created in a short time. A conductor pattern having high etching resistance and few disconnection defects can be formed with high yield. The peelability of the cured resist is good and no peeling residue remains. Compared with the photolithography method, the conductor pattern creation time can be greatly reduced.
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 of drawing a resist pattern by discharging a resist ink from a nozzle includes spraying by an ink jet method, drawing by a plotter, a dispenser, and the like.

In the curing step, 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 may be a swelling peeling method using a strong alkali or the like, a dissolution 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 photosensitive 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. For example, a solution prepared by dissolving or dispersing wax or thermoplastic resin in a liquid medium composed of an organic solvent, water, etc. is used. If necessary, a viscosity adjusting agent, a surface tension adjusting agent, a wetting agent, a pH adjusting agent, a crosslinking agent. , 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. 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 the 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 formed as shown in FIG. An ink pattern 6 is formed on the substrate. The ink pattern 6 may be cured with energy other than ultraviolet light or visible light, for example, active energy rays such as an electron beam, if necessary. Next, as shown in FIG. 1C, the copper foil 3 in the portion not covered with the ink pattern 6 is removed by etching the copper clad laminate 1 on which the ink pattern 6 is formed. Etching solutions such as copper chloride, iron chloride, and ammonia are used.
Finally, the ink 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, an ink 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 the copper foil 3 in a portion not covered with the ink pattern 6 is etched. After the removal, the ink pattern 6 is peeled off from the copper foil 3 in the portion covered with the ink pattern 6 to form the conductor pattern 7, so that a photomask is not required and development using an alkaline aqueous solution or an organic solvent is performed. Since there is no process, there is no problem in 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 photosensitive resist ink of the present invention will be described.
The photosensitive resist ink of this invention means the resist ink used for a resist direct drawing system. After the photosensitive 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, and when forming a conductor pattern by plating. Plays a role as a plating resist. Furthermore, the photosensitive 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.

Hereinafter, a photosensitive resist ink suitable for forming a resist pattern by a resist direct drawing method will be described.
The photosensitive 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 resist ink and to sufficiently cure the bottom of the resist ink. Moreover, 0.01 mass% or more is preferable from a viewpoint of a sensitivity.

  As a photopolymerization initiator in the present invention, including 2,4,5-triaryimidazole dimer represented by the following general formula (I) or a derivative thereof is hardenability, etching resistance, plating resistance This is a preferred embodiment from the viewpoint of the property, plating bath contamination, and peelability.

(In the formula, X, Y, and Z represent hydrogen, an alkyl group, an alkoxy group, or a halogen group, and p, q, and r are integers of 1 to 5.)
In the compound represented by the above general formula (I), the covalent bond connecting two triarylimidazol groups is 1,1′-, 1,2′-, 1,4′-, 2, It is in the 2'-, 2,4'- or 4,4'-position, but compounds in the 1,2'-position are preferred.
Examples of 2,4,5-triarylimidazole dimers include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5. -Bis- (m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc., among others 2- (o-chlorophenyl) More preferred is -4,5-diphenylimidazole dimer.

In addition, inclusion of acridine or a derivative thereof as a photopolymerization initiator in the present invention is a preferred embodiment from the viewpoints of curability, etching resistance, plating resistance, and peelability.
Examples of acridine and derivatives thereof include acridine, 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (pn-propylphenyl) acridine, 9- (p -Iso-propylphenyl) acridine, 9- (pn-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) Acridine, 9- (p-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) ) Acridine, 9- (m-methylphenyl) acridine, 9- (mn-pro Ruphenyl) acridine, 9- (m-iso-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (m-cyanophenyl) acridine 9- (m-chlorophenyl) acridine, 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-iso-propylacridine, 9-cyanoethylacridine, 9-hydroxyethyl acridine, 9-chloroe Ruakurijin, 9-methoxy acridine, 9-ethoxy acridine, 9-n-propoxy acridine, 9-an iso-propoxy acridine, 9-chloro-ethoxy acridine, and the like. Of these, 9-phenylacridine is preferable.

  The 2,4,5-triary imidazole dimer or its derivative and the acridine or its derivative may be used simultaneously. Furthermore, it is more preferable from the viewpoint of curability that the 2,4,5-triarylimidazole dimer or derivative thereof and acridine or derivative thereof are used in combination with an N-aryl-α-amino acid compound. .

  Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N- (n-propyl) -N-phenylglycine, N- (N-butyl) -N-phenylglycine, N- (2-methoxyethyl) -N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N- (n-propyl) -N -Phenylalanine, N- (n-butyl) -N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N- (p-tolyl) glycine, N-ethyl- N- (p-tolyl) glycine, N- (n-propyl) -N- (p-tolyl) glycine, N- (n-butyl) -N- (p-tolyl) glycine N-methyl-N- (p-chlorophenyl) glycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (n-propyl) -N- (p-chlorophenyl) glycine, N-methyl-N- (P-bromophenyl) glycine, N-ethyl-N- (p-bromophenyl) glycine, N- (n-butyl) -N- (p-bromophenyl) glycine, N, N'-diphenylglycine, N- Examples include methyl-N- (p-iodophenyl) glycine, N- (p-bromophenyl) glycine, N- (p-chlorophenyl) glycine, N- (o-chlorophenyl) glycine. In particular, N-phenylglycine is preferably used.

In addition to N-aryl-α-amino acid compounds, it is also a preferred embodiment to use p-aminophenyl ketone in combination. Examples of p-aminophenyl ketone include p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p'-bis (ethylamino) benzophenone, p, p'- Bis (dimethylamino) benzophenone [Michler's ketone], p, p′-bis (diethylamino) benzophenone, p, p′-bis (dibutylamino) benzophenone, and the like.
Of course, in addition to the compounds shown above, other photopolymerization initiators can be used in combination. A photoinitiator here is a compound which can be activated by various actinic rays, for example, an ultraviolet ray, visible light, etc., and can start superposition | polymerization.

Examples of the other photopolymerization initiator include 2-ethylanthraquinone and 2-tert.
There are quinones such as butyl anthraquinone, aromatic ketones such as benzophenone, benzoin ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether, benzyl dimethyl ketone, benzyl diethyl ketone and the like. Further, for example, there are combinations of thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds. Further, there are oxime esters such as 1-phenyl-1,2-propanedione-2-ο-benzoyloxime and 1-phenyl-1,2-propanedione-2- (ο-ethoxycarbonyl) oxime.

Further, the photosensitive resist ink in the present invention, 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, Filler, antifoaming agent, flame retardant, adhesion-imparting agent, leveling agent, peeling accelerator, antioxidant, fragrance, imaging agent, thermal cross-linking agent, etc. (A) component and (B) component total amount 100 parts by mass Each can be contained in an amount of 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, the photosensitive resist ink of the present invention may contain additives such as radical polymerization inhibitors and plasticizers for improving thermal stability and storage stability, 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.
Further, the photosensitive resist ink of the present invention is used as an ink having an appropriate viscosity after being diluted with an appropriate solvent.

  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 the ink pattern 6 so as to cover the portion where the conductor pattern is to be formed. The ink 5 used here is one in which the following composition is dissolved in a mixed solvent of methyl ethyl ketone / isopropanol. The obtained resist pattern is exposed with a high-pressure mercury lamp to cure the resist pattern.

Next, the portion of the copper foil 3 not covered with the ink pattern 6 is removed using a copper chloride etching solution. Finally, when the ink pattern 6 is peeled from the copper foil 3 using a peeling solution (3% NaOH aqueous solution) to form the conductor pattern 7, a printed wiring board is obtained. In this embodiment, the time required for producing the printed wiring board is 20 minutes.
In any ink composition, the photosensitive resist ink cures quickly.
In any ink composition, no disconnection or chipping is observed in the conductor pattern.
In any ink composition, the used resist is peeled off quickly, and no peeling residue remains.

  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 photosensitive resist ink used for forming a resist pattern by a resist direct drawing method, comprising a 2,4,5-triarylimidazole dimer or a derivative thereof, or acridine or a derivative thereof. ink. The photosensitive resist ink according to claim 1, comprising an N-aryl-α-amino acid compound. A method of forming a resist pattern by a resist direct drawing method using the photosensitive resist ink according to claim 1. A method of forming a conductor pattern by forming a resist pattern by the method according to claim 3 and etching or plating a portion not covered with the resist pattern. A method for producing a printed wiring board using the method according to claim 4.

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