KR20140126294A - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board - Google Patents
Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board Download PDFInfo
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- KR20140126294A KR20140126294A KR1020147017450A KR20147017450A KR20140126294A KR 20140126294 A KR20140126294 A KR 20140126294A KR 1020147017450 A KR1020147017450 A KR 1020147017450A KR 20147017450 A KR20147017450 A KR 20147017450A KR 20140126294 A KR20140126294 A KR 20140126294A
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- resin composition
- photosensitive resin
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Abstract
The present invention relates to a photosensitive resin composition containing a binder polymer, a photopolymerizable compound and a photopolymerization initiator, wherein the binder polymer has a constituent unit based on ethyl (meth) acrylate and a constituent unit based on ethyl (meth) Is less than 9% by mass based on the total amount of the binder polymer and the photopolymerizable compound.
Description
The present invention relates to a photosensitive resin composition, a photosensitive element, a method of forming a resistor pattern, and a method of manufacturing a printed wiring board.
BACKGROUND ART [0002] In the field of manufacturing printed wiring boards, photosensitive resin compositions are widely used as resist materials used for etching or plating. The photosensitive resin composition is often used as a photosensitive element (laminate) comprising a support film and a layer formed using the photosensitive resin composition on the support film (hereinafter referred to as a " photosensitive resin composition layer ").
The printed wiring board is manufactured, for example, as follows. First, the photosensitive resin composition layer of the photosensitive element is laminated (laminated) on a substrate for circuit formation (lamination step). Next, after the support film is peeled off, a predetermined portion of the photosensitive resin composition layer is irradiated with an actinic ray to cure the exposed portion (exposure step). Thereafter, a resist pattern made of a cured product of the photosensitive resin composition is formed on the substrate (development step) by removing (developing) the unexposed portion from the substrate (development). A circuit is formed on the substrate by performing an etching treatment or a plating treatment on the obtained resist pattern (circuit forming step), and finally the resist is peeled off to produce a printed wiring board (peeling step).
As a method of exposure, conventionally, a method of exposing through a photomask using a mercury lamp as a light source has been used. In recent years, a direct imaging exposure method has been used, in which digital data of a pattern is directly drawn on a photosensitive resin composition layer, called DLP (Digital Light Processing) or LDI (Laser Direct Imaging). This direct imaging exposure method has been introduced for manufacturing a high-density package substrate because the alignment accuracy is better than the exposure method through a photomask and a high-precision pattern can be obtained.
In the exposure step, it is necessary to shorten the exposure time to improve the production efficiency. However, in the above-described direct imaging exposure method, since monochromatic light such as a laser is used for a light source, a light beam is irradiated while a substrate is scanned. Therefore, compared to a conventional exposure method using a photomask, There is a tendency to need. Therefore, in order to shorten the exposure time and increase the production efficiency, it is necessary to improve the sensitivity of the photosensitive resin composition.
In addition, in the peeling step, it is necessary to shorten the peeling time of the resistor in order to improve the production efficiency. It is also necessary to reduce the size of the stripper to prevent the stripper strips from being reattached to the circuit board to improve the production yield. Thus, there is a demand for a photosensitive resin composition having excellent peeling properties (peeling time, peel size, etc.) after curing.
Further, with the recent increase in the density of printed wiring boards, there is a growing demand for photosensitive resin compositions that are excellent in resolution (resolution) and adhesion.
With respect to these demands, various photosensitive resin compositions have conventionally been studied (see, for example,
However, when a conventional photosensitive resin composition is used, the sensitivity, resolution, and adhesion are excellent, but the size of the peeling piece becomes large when the photosensitive resin composition layer after curing is peeled, and may adhere to the circuit board. On the other hand, if it is attempted to improve the peeling property of the photosensitive resin composition layer after curing, foaming may occur in the developing step, and the developer may overflow.
SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a photosensitive resin composition which can sufficiently reduce foaming at the time of development and has excellent peeling properties after curing and a photosensitive element using the photosensitive resin composition, It is another object of the present invention to provide a method for producing a printed wiring board.
The present invention relates to a photosensitive resin composition containing a binder polymer, a photopolymerizable compound and a photopolymerization initiator, wherein the binder polymer has a constituent unit based on ethyl (meth) acrylate and a constituent unit based on ethyl (meth) Is less than 9% by mass based on the total amount of the binder polymer and the photopolymerizable compound.
The photosensitive resin composition of the present invention has the above-described constitution, and it can form a photosensitive resin composition which can maintain excellent sensitivity, resolution and adhesion, can sufficiently reduce foaming at the time of development and is excellent in peeling property after curing can do.
The binder polymer may further have a constitutional unit based on styrene or a styrene derivative. The content of the constituent unit based on the styrene or the styrene derivative is preferably 15 to 50 mass% with respect to the total mass of the polymerizable monomer constituting the binder polymer.
Further, from the viewpoint of further improving the sensitivity and resolution, the photopolymerization initiator may include an acridine compound having one or two acridinyl groups.
The present invention also provides a photosensitive element comprising a support film and a photosensitive resin composition layer provided on the support film, wherein the photosensitive resin composition layer is a layer formed using the photosensitive resin composition. By using such a photosensitive element, it is possible to sufficiently reduce foaming at the time of development and to form a resist pattern excellent in peeling property after curing.
The present invention further relates to a process for producing a photosensitive resin composition, comprising the steps of: laminating a photosensitive resin composition layer formed using the photosensitive resin composition on a substrate; irradiating a predetermined portion of the photosensitive resin composition layer with actinic light to expose the predetermined portion, And a developing step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate by removing a portion other than a predetermined portion of the photosensitive resin composition layer from above the substrate. According to the above method, it is possible to efficiently form a resist pattern having good resolution, adhesion, resist shape and exfoliated characteristics after curing with good sensitivity.
Further, the present invention provides a method for manufacturing a printed wiring board, which comprises a step of etching or plating a substrate on which a resist pattern is formed by the above method. According to this manufacturing method, a printed wiring board having high-density wiring such as a high-density package substrate can be manufactured with high precision and efficiency.
According to the present invention, it is possible to provide a photosensitive resin composition which can sufficiently reduce foaming at the time of development and is excellent in peeling property after curing, and a photosensitive element using the same, a method of forming a resistor pattern, and a method of manufacturing a printed wiring board have.
1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention.
Carrying out the invention Form for
Hereinafter, a preferred embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid. "EO-modified" means a compound having a (poly) oxyethylene chain, "PO-modified" means a compound having a (poly) oxypropylene chain, "EO- (Poly) oxyethylene chain and a (poly) oxypropylene chain.
(Photosensitive resin composition)
The photosensitive resin composition of the present embodiment is also referred to as a binder polymer (hereinafter also referred to as "component (A)"), a photopolymerizable compound (hereinafter also referred to as "component (B)") and a photopolymerization initiator Wherein the binder polymer has a constitutional unit based on ethyl (meth) acrylate and the content of the constitutional unit based on ethyl (meth) acrylate is in the range of (A) component and (B) Is less than 9% by mass based on the total amount of the components.
The inventors of the present invention have found that the effect of the present invention can be obtained by adjusting the content of the structural unit of the ethyl (meth) acrylate in the photosensitive resin composition to within the specified range, .
≪ Component (A): Binder polymer >
The component (A) has a structural unit based on ethyl (meth) acrylate from the viewpoint of improving resolution and adhesion. The content of the constituent unit based on ethyl (meth) acrylate of the component (A) is preferably from 0.1 to 50 parts by weight, more preferably from 0.5 to 30 parts by weight, per 100 parts by weight of the component (A) in the photosensitive resin composition from the viewpoints of suppressing foaming at the time of development of the photosensitive resin composition layer and improving peelability after curing. Is preferably less than 9 mass%, more preferably 1 mass% or more and less than 9 mass%, and more preferably 3 to 8 mass%, based on the total amount of the components (A) and (B)
The content of the constituent unit based on ethyl (meth) acrylate as the component (A) is preferably from 1 to 100 parts by weight based on the total weight of the polymerizable monomer constituting the component (A) from the viewpoint of further improving the adhesion and the peeling property. Is preferably 25 mass%, more preferably 1 mass% to 20 mass%. When the content is 1% by mass or more, the adhesion can be further improved. When the content is 20% by mass or less, more excellent peeling properties can be obtained.
The component (A) can be obtained, for example, by radical polymerization of ethyl (meth) acrylate and other polymerizable monomers (monomers).
Examples of other polymerizable monomers include (meth) acrylic acid; (Meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, benzyl (meth) acrylate, benzyl (meth) acrylate derivative, furfuryl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, dibutyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid esters such as? -furyl (meth) acrylic acid and? -styryl (meth) acrylic acid; Styrene; Polymerizable styrene derivatives substituted in the? -Position or aromatic ring such as vinyltoluene and? -Methylstyrene; Acrylamide such as diacetone acrylamide; Acrylonitrile; Esters of vinyl alcohols such as vinyl-n-butyl ether; Maleic acid; Maleic anhydride; Maleic monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; Fumaric acid, cinnamic acid,? -Cyano cinnamic acid, itaconic acid, crotonic acid and propiolic acid. These may be used alone or in combination of two or more.
From the viewpoint of improving resolution and adhesion, the component (A) may further have a structural unit based on styrene or a styrene derivative.
When the component (A) has a constituent unit based on styrene or a styrene derivative, the content of the component (A) is preferably from 1 to 50 parts by weight based on the total weight of the polymerizable monomer constituting the component (A) , More preferably from 10 to 50 mass%, even more preferably from 15 to 50 mass%, and still more preferably from 20 to 50 mass%. From the viewpoint of excellent adhesiveness, the content is preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more. From the viewpoint of excellent peelability, the content is preferably 70 mass% or less, more preferably 60 mass% or less, and even more preferably 50 mass% or less.
The component (A) may further have a structural unit based on methyl (meth) acrylate from the viewpoint of better resolution and adhesion.
When the component (A) has a constituent unit based on methyl (meth) acrylate, the content thereof is preferably 1 to 50% by mass based on the total mass of the polymerizable monomer constituting the component (A) , More preferably from 10 to 50 mass%, even more preferably from 20 to 49 mass%, particularly preferably from 30 to 48 mass%. When the content is 1% by mass or more, the adhesion can be further improved. When the content is 50% by mass or less, more excellent peeling properties can be obtained.
From the viewpoint of improving alkali developing property and peeling property, the component (A) may have a constituent unit based on (meth) acrylic acid.
The acid value of the component (A) is preferably 90 to 250 mgKOH / g, more preferably 100 to 230 mgKOH / g, even more preferably 110 to 210 mgKOH / g, Is particularly preferable. When the acid value is 90 mgKOH / g or more, the development time can be shortened. When the acid value is 250 mgKOH / g or less, the adhesion can be further improved. In the case of performing the solvent development, it is preferable to prepare a small amount of a polymerizable monomer (monomer) having a carboxyl group such as (meth) acrylic acid.
The weight average molecular weight (Mw) of the component (A) is preferably 10,000 to 100,000, more preferably 30,000 to 100,000 as measured by gel permeation chromatography (GPC) (converted to a calibration curve using standard polystyrene) More preferably 50,000 to 95,000. When the Mw is 10,000 or more, the adhesion can be further improved. When the Mw is 100000 or less, the development time can be shortened.
The component (A) may have, in its molecule, a characteristic group having photosensitivity to light having a wavelength within a range of 350 to 440 nm, if necessary.
As the component (A), one type of binder polymer may be used alone, or two or more kinds of binder polymers may be arbitrarily used in combination. Examples of the binder polymer for use in combination of two or more kinds include, for example, two or more kinds of binder polymers (including other monomer units as copolymer components), and two or more kinds of binder polymers having different weight average molecular weights , And two or more kinds of binder polymers having different degrees of dispersion. A polymer having a multimode molecular weight distribution described in JP-A-11-327137 may also be used.
The content of the component (A) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, and more preferably 40 to 60 parts by mass, per 100 parts by mass of the total amount of the components (A) Is particularly preferable. When the content is 30 parts by mass or more, the film tends to be easily formed. When the content is 70 parts by mass or less, the sensitivity and resolution can be further improved.
≪ Component (B): photopolymerizable compound >
The component (B) is not particularly limited as long as it is capable of photo-crosslinking, but it is preferable to use a compound having an ethylenically unsaturated bond. As the component (B), for example, a compound obtainable by reacting an?,? - unsaturated carboxylic acid with a polyhydric alcohol; Compounds obtainable by reacting an?,? - unsaturated carboxylic acid with a glycidyl group-containing compound; Urethane monomers such as (meth) acrylate compounds having a urethane bond; ? - (meth) acryloyloxyethyl (meth) acrylate, nonylphenoxy octaethylene oxy (meth) acrylate,? -Chloro-? (meth) acryloyloxyethyl-o-phthalate,? -hydroxypropyl-? '- (meth) acryloyloxyethyl-o-phthalate and alkyl And a photopolymerizable compound having one ethylenic unsaturated bond. These may be used alone or in combination of two or more.
Examples of the compound obtainable by reacting the above polyhydric alcohol with?,? - unsaturated carboxylic acid include 2,2-bis (4 - ((meth) acryloxypolyethoxy) Bisphenol A based (meth) acrylate such as bis (4 - ((meth) acryloxypolypropoxy) phenyl) propane and 2,2-bis (4- (meth) acryloxypolyethoxypolypropoxy) Acrylate compounds, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol propane di (meth) acrylate, trimethylol propane tri (meth) acrylate, EO- Propane tri (meth) acrylate (having repeating total number of oxyethylene groups of 1 to 5), PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) Tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra ( Other) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more. Of these, 2,2-bis (4 - ((meth) acryloxypolyethoxy) phenyl) propane is used as FA-321M (product name, manufactured by Hitachi Chemical Co., Ltd.), tetramethylol methane triacrylate EM-modified trimethylolpropane trimethacrylate was changed to TMPT-21E and TMPT-30E (manufactured by Hitachi Chemical Co., Ltd.) as A-TMM-3 (product of Shin Kagaku Kagaku Kogyo K.K.) , ≪ / RTI > sample name).
The component (B) preferably contains a photopolymerizable compound having one ethylenic unsaturated bond from the viewpoint of improving resolution, adhesiveness, resist shape, and releasing property after curing in a balanced manner. In this case, the content thereof is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, based on the total amount of the component (B).
Examples of the photopolymerizable compound having one ethylenic unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compound and alkyl (meth) acrylate. Of these, nonylphenoxypolyethyleneoxyacrylate or a phthalic acid compound is preferable from the viewpoint of improving the resolution, the adhesion, the shape of the resistor and the exfoliating characteristics after curing in a balanced manner, and a combination of nonylphenoxypolyethyleneoxyacrylate and a phthalic acid compound .
Examples of the nonylphenoxy polyethylene oxyacrylate include nonylphenoxy triethylene oxyacrylate, nonylphenoxy tetraethylene oxyacrylate, nonylphenoxypentaethylene oxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, Phenoxyheptane ethyleneoxyacrylate, nonylphenoxy octaethylene oxyacrylate, nonylphenoxynone ethyleneoxyacrylate, nonylphenoxydecethyleneoxyacrylate, nonylphenoxydocetheyleneoxyacrylate, and the like. These may be used alone or in combination of two or more. In addition, "nonylphenoxypolyethyleneoxyacrylate" is also referred to as "nonylphenoxypolyethylene glycol acrylate".
Examples of the phthalic acid compound include? -Chloro? -Hydroxypropyl-? '- (meth) acryloyloxyethyl-o-phthalate,? -Hydroxyethyl-?' - (meth) Hydroxyethyl-o-phthalate and? -Hydroxypropyl-? '- (meth) acryloyloxyethyl-o-phthalate. Of these,? -Chloro-? -Hydroxypropyl-?' - Methacryloyloxyethyl-o-phthalate is preferable. ? -chloro? -hydroxypropyl-? '- methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (product name, manufactured by Hitachi Chemical Co., Ltd.). These may be used alone or in combination of two or more.
≪ Component (C): photopolymerization initiator >
The component (C) may be used without particular limitation, but may contain an acridine compound having one or two acridinyl groups. That is, the component (C) is an acridine compound having two acridinyl groups (hereinafter also referred to as a "component (C1)") and an acridine compound having one acridinyl group (Hereinafter also referred to as " component ").
Examples of the component (C1) include an acridine compound represented by the following general formula (1).
In the formula (1), R 1 represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thioalkylene group having 2 to 20 carbon atoms. From the viewpoint of more reliably obtaining the effect of the photosensitive resin composition of the present embodiment, R 1 is preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 4 to 14 carbon atoms.
Examples of the compound represented by the general formula (1) include 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) octane, 1,9- (9-acridinyl) dodecane, 1,14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) alkane such as decane, 1,18-bis (9-acridinyl) octadecane and 1,20-bis (9-acridinyl) -2-thiopropane and 1,5-bis (9-acridinyl) -3-thiapentane . These may be used alone or in combination of two or more.
From the viewpoint of improving the sensitivity and resolution, an acridine compound (for example, product name "N-1717" made by ADEKA Co., Ltd.) in which R 1 in the formula (1) is a heptylene group is used as the component (C1) .
The content of the component (C1) is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of the components (A) and (B) from the standpoint of sensitivity, More preferably from 1 to 5 parts by mass, and particularly preferably from 1 to 3 parts by mass. When the blending amount is 0.1 parts by mass or more, better sensitivity, resolution, or adhesion is easily obtained, and when it is 10 parts by mass or less, a more excellent register shape can be obtained.
Examples of the component (C2) include an acridine compound represented by the following general formula (2).
In the formula (2), R 2 represents a halogen atom, an amino group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an alkylamino group having 1 to 6 carbon atoms, and a represents an integer of 0 to 5 .
Examples of the acridine compound represented by the general formula (2) include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, Noacridine. These may be used alone or in combination of two or more.
The component (C) may contain a photopolymerization initiator other than the components (C1) and (C2).
Examples of the photopolymerization initiator other than the components (C1) and (C2) include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Mihira ketone), N, Ethyl 4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Aromatic ketones such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; Diethylanthraquinone, 2,3-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl 1,4-naphthoquinone and 2,3-dimethyl anthraquinone Quinones; 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o- (O-methoxyphenyl) -4,5-diphenylimidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- , 2,4,5-triarylimidazole dimer such as 5-diphenylimidazole dimer; Benzyl derivatives such as benzyl dimethyl ketal; Substituted anthracene compounds such as 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene and 9,10-diphenoxyanthracene; Coumarin compounds, oxazole compounds, pyrazoline compounds, and triarylamine compounds. These may be used alone or in combination of two or more. In addition, a thioxanthone compound and a tertiary amine compound may be used in combination, such as a combination of diethylthioxanthone and dimethylamino benzoic acid.
When the photosensitive resin composition contains a photopolymerization initiator other than the components (C1) and (C2), the content thereof is preferably from 100 parts by mass as the total amount of the solid components of the component (A) and the component (B) More preferably 0.1 to 7 parts by mass, and particularly preferably 0.2 to 5 parts by mass.
The content of the component (C) is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass based on 100 parts by mass of the total solid content of the components (A) and (B) from the viewpoints of sensitivity, More preferably from 0.1 to 5 parts by mass, and particularly preferably from 0.1 to 5 parts by mass.
<Amine compound>
The photosensitive resin composition of this embodiment may further contain (D) an amine compound (hereinafter also referred to as " component (D) ").
Examples of the component (D) include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane and leuco crystal violet. These may be used alone or in combination of two or more.
When the photosensitive resin composition contains the component (D), the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the components (A) and (B) More preferably from 0.6 to 2 parts by mass, and particularly preferably from 1 to 2 parts by mass. When the content is 0.01 part by mass or more, more excellent sensitivity is easily obtained. When the content is less than 10 parts by mass, excess component (D) tends to be hardly precipitated as a foreign matter after film formation.
≪ Other components >
The photosensitive resin composition of the present embodiment may contain a photopolymerizable compound (e.g., oxetane compound) having at least one cyclic ether group capable of cation polymerization in a molecule, a cation polymerization initiator, a dye such as maracat green, a tribromomethylphenyl A light stabilizer, a coloring agent, a coloring agent, a coloring agent such as p-toluenesulfonamide, a pigment, a filler, a defoaming agent, a flame retardant, a stabilizer, an adhesion promoter, a leveling agent, , Thermal crosslinking agents, and the like. These may be used alone or in combination of two or more. The content thereof is preferably about 0.01 to 20 parts by mass per 100 parts by mass of the total amount of the component (A) (binder polymer) and the component (B) (photopolymerizable compound).
(Solution of photosensitive resin composition)
The photosensitive resin composition of the present embodiment can be dissolved in an organic solvent and used as a solution (coating liquid) having a solid content of about 30 to 60 mass%. Examples of the organic solvent include organic solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, .
The above-mentioned coating liquid is coated on the surface of a metal plate or the like, followed by drying, whereby a photosensitive resin composition layer comprising the photosensitive resin composition of the present embodiment can be formed. Examples of the metal plate include copper, copper-based alloys, iron-based alloys such as nickel, chromium, iron and stainless steel, preferably copper, copper-based alloys and iron-based alloys.
The thickness of the photosensitive resin composition layer varies depending on the application, but it is preferably about 1 to 100 mu m in thickness after drying. The surface of the photosensitive resin composition layer opposite to the metal plate may be coated with a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.
(Photosensitive element)
1 is a schematic cross-sectional view showing a preferred embodiment of the
The photosensitive resin composition layer 3 made of the photosensitive resin composition described above can be formed on the supporting film by applying the solution of the photosensitive resin composition on the supporting film 2 and then drying the solution. That is, the photosensitive resin composition layer (3) is a layer formed using the above photosensitive resin composition. Thus, the
As the supporting film, a polymer film formed of a polymer having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene, and the like can be used.
The thickness of the support film (polymer film) is preferably 1 to 100 占 퐉, more preferably 5 to 50 占 퐉, and still more preferably 5 to 30 占 퐉. If the thickness is 1 mu m or more, the supporting film is hardly broken at the time of peeling the supporting film, and if it is 100 mu m or less, the resolution can be improved.
The
The thickness of the protective film is preferably 1 to 100 占 퐉, more preferably 5 to 50 占 퐉, still more preferably 5 to 30 占 퐉, and particularly preferably 15 to 30 占 퐉. When the thickness is 1 占 퐉 or more, the protective film is hardly broken when the photosensitive resin composition layer and the protective film are laminated (laminated) on the substrate, and when the thickness is 100 占 퐉 or less, the thickness is excellent.
The application of the solution of the photosensitive resin composition onto the support film can be carried out by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating and the like.
The solution is preferably dried at 70 to 150 DEG C for 5 to 30 minutes. After drying, the amount of the residual organic solvent in the photosensitive resin composition layer is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.
The thickness of the photosensitive resin composition layer in the photosensitive element varies depending on the use, but it is preferably 1 to 100 占 퐉, more preferably 1 to 50 占 퐉, and even more preferably 5 to 40 占 퐉 in thickness after drying . When the thickness is 1 탆 or more, it is easy to industrially coat (coat), and when it is 100 탆 or less, excellent adhesion and resolution can be obtained.
The photosensitive element may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
The obtained photosensitive element can be wound in a sheet form or in a roll in a winding core. In the case of winding in a roll form, it is preferable to wind the support film so as to be outside. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). It is preferable that a cross-section separator is provided on the end face of the roll-shaped photosensitive element roll obtained in this way from the viewpoint of the cross-sectional protection, and it is preferable to provide the moisture-proof cross-section separator in view of the edge fusion. As a packing method, it is preferable to wrap and wrap in a black sheet having low moisture permeability.
(Method of Forming Resistor Pattern)
A resist pattern can be formed using the above photosensitive resin composition. The resist pattern forming method according to the present embodiment includes the steps of (i) laminating a photosensitive resin composition layer formed using the photosensitive resin composition on a substrate, (ii) forming a resist pattern on a predetermined portion of the photosensitive resin composition layer, (Iii) a step of removing a portion of the photosensitive resin composition layer other than the predetermined portion from the substrate, thereby forming a resist pattern made of a cured product of the photosensitive resin composition And a developing step of forming a resist pattern.
(i) a laminating step
First, a photosensitive resin composition layer formed by using a photosensitive resin composition is laminated on a substrate. As the substrate, a substrate (substrate for circuit formation) having an insulating layer and a conductor layer formed on the insulating layer can be used.
The lamination of the photosensitive resin composition layer on the substrate is carried out, for example, by removing the protective film of the photosensitive element and then pressing the photosensitive resin composition layer of the photosensitive element onto the substrate while heating. Thereby, a laminate comprising a substrate, a photosensitive resin composition layer, and a support film, which are laminated in this order, can be obtained.
This lamination operation is preferably carried out under reduced pressure in view of adhesion and followability. The heating of the photosensitive resin composition layer and / or the substrate at the time of pressing is preferably performed at a temperature of 70 to 130 캜, and it is preferable that the pressing is performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm 2 ) , These conditions are not particularly limited. When the photosensitive resin composition layer is heated to 70 to 130 占 폚, it is not necessary to preheat the substrate in advance, but in order to further improve the lamination property, the substrate may be preheated.
(ii) exposure step
Next, a predetermined portion of the photosensitive resin composition layer on the substrate is irradiated with an actinic ray to expose a predetermined portion thereof to be cured. In this case, when the support film present on the photosensitive resin composition layer is transparent to the actinic ray, the actinic ray can be irradiated through the support film. However, if the support film is shielded from light, The layer is irradiated with an actinic ray.
Examples of the exposure method include a method of irradiating an actinic ray onto an image through a negative or positive mask pattern called an artwork (mask exposure method). It is also possible to adopt a method of irradiating an active light beam to an image shape by a direct imaging exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method.
The photosensitive resin composition of this embodiment can be suitably used in a direct imaging exposure method. That is, one of the preferred embodiments of the present invention is a photosensitive resin composition containing a binder polymer, a photopolymerizable compound and a photopolymerization initiator, wherein the binder polymer has a structural unit based on ethyl (meth) acrylate, The content of the constituent unit based on the total amount of the binder polymer and the photopolymerizable compound is less than 9% by mass, the application to the direct drawing exposure method of the photosensitive resin composition.
As the light source of the active light beam, a known light source can be used. For example, a gas laser such as a carbon arc, a mercury vapor arc, a high pressure mercury lamp, a xenon lamp or an argon laser, a solid laser such as a YAG laser, And ultraviolet rays, visible light, and the like of the ultraviolet rays are effectively used.
The wavelength (exposure wavelength) of the active light ray is preferably in the range of 340 to 430 nm, more preferably in the range of 350 to 420 nm, more preferably in the range of 400 to 420 nm, in view of more surely obtaining the effect of the present invention .
(iii) development process
Further, by removing the portion of the photosensitive resin composition layer other than the predetermined portion from above the substrate, a resist pattern made of the cured product of the photosensitive resin composition is formed on the substrate. When the support film is present on the photosensitive resin composition layer, the support film is removed, and then a portion (unexposed portion) other than the predetermined portion (exposed portion) is removed (developed). The developing method includes a wet phenomenon and a dry phenomenon, but a wet phenomenon is widely used.
In the case of the wet phenomenon, a developer corresponding to the photosensitive resin composition is used and developed by a known developing method. Examples of the developing method include a dipping method, a batting method, a spraying method, a brushing method, a slapping method, a scraping method, and a method using a swinging dipping method. These two or more kinds of methods may be combined to perform development.
Examples of the developer include an alkaline aqueous solution, an aqueous developer, and an organic solvent-based developer.
When used as a developer, the alkaline aqueous solution is safe, stable, and operable. Examples of the base of the alkaline aqueous solution include alkaline hydroxides such as hydroxides of lithium, sodium or potassium; Alkaline carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium; Alkali metal phosphates such as potassium phosphate and sodium phosphate; Alkali metal pyrophosphates such as sodium pyrophosphate, potassium pyrophosphate and the like are used.
The alkaline aqueous solution is preferably a lean solution of 0.1 to 5 mass% sodium carbonate, a lean solution of 0.1 to 5 mass% potassium carbonate, a lean solution of 0.1 to 5 mass% sodium hydroxide, a lean solution of sodium salt of 0.1 to 5 mass% Do. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted in accordance with the alkali developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surface active agent, a defoaming agent, and a small amount of an organic solvent for promoting development may be mixed.
(Manufacturing method of printed wiring board)
The printed wiring board can be manufactured by etching or plating the substrate on which the resistor pattern is formed by the above method. The etching or plating of the substrate is carried out with respect to the conductor layer or the like of the substrate, using the formed resist pattern as a mask.
Examples of the etching solution for etching include a cupric chloride solution, a ferric chloride solution, an alkali etching solution and a hydrogen peroxide etching solution. Of these, an etch factor is good It is preferable to use a ferric chloride solution.
Examples of the plating method for plating include copper plating such as copper sulfate plating, copper pyrophosphate plating, solder plating such as high slow solder plating, plating with a watt bath (nickel sulfate-nickel chloride plating) Nickel plating such as nickel sulfate and nickel plating, hard gold plating, and soft gold plating.
After the etching or plating, the resist pattern can be peeled off by, for example, a strong alkaline aqueous solution more than the alkaline aqueous solution used for development. As the alkaline aqueous solution, for example, 1 to 10 mass% aqueous sodium hydroxide solution and 1 to 10 mass% potassium hydroxide aqueous solution are used. Among them, 1 to 10 mass% aqueous sodium hydroxide solution or potassium hydroxide aqueous solution is preferably used, and more preferably 1 to 5 mass% aqueous sodium hydroxide solution or potassium hydroxide aqueous solution is used.
Examples of the resist pattern peeling method include an immersion method and a spray method, and these may be used alone or in combination. The printed wiring board on which the resistor pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.
The photosensitive resin composition of the present embodiment can be suitably used for producing a printed wiring board. That is, one of the preferred embodiments of the present invention is a photosensitive composition comprising a binder polymer, a photopolymerizable compound and a photopolymerization initiator, wherein the binder polymer contains a constituent unit based on ethyl (meth) acrylate, Based on the total amount of the binder polymer and the photopolymerizable compound, is less than 9% by mass based on the total amount of the binder polymer and the photopolymerizable compound.
Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.
Example
Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
(Preparation of solution of photosensitive resin composition)
Solutions of the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were prepared by mixing the components (A) to (D) shown below in Table 1 in the amounts shown in the same table (g). The compounding amount of the component (A) shown in Table 1 is the mass (solid content) of the nonvolatile matter, and the compounding amount of the component (B) is the solid content. Details of each component shown in Table 1 are as follows.
≪ (A) Binder polymer &
[Synthesis of binder polymer (A-1)] [
A solution obtained by mixing 130 g of methacrylic acid as a polymerizable monomer (monomer), 205 g of methyl methacrylate, 50 g of ethyl acrylate and 115 g (weight ratio: 26/41/10/23) of styrene and 5.5 g of azobisisobutyronitrile Was referred to as " solution a ".
A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixed solution of 60 g of methyl cellosolve and 40 g of toluene (mass ratio 3: 2) was referred to as " solution b ".
In a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introducing tube, 450 g of a mixed solution (mass ratio 3: 2) of 270 g of methylcellosolve and 180 g of toluene was introduced, and nitrogen gas was blown into the flask The mixture was heated to raise the temperature of the mixed solution to 80 캜.
The solution a was added dropwise to the mixed solution in the flask over a period of 4 hours, and the solution was kept at 80 ° C for 2 hours while stirring. Subsequently, the solution b was dropped into the solution in the flask over a period of 10 minutes, and then the solution in the flask was kept at 80 DEG C for 3 hours with stirring. Further, the solution in the flask was heated to 90 DEG C over 30 minutes, kept at 90 DEG C for 2 hours, and cooled to obtain a solution of the binder polymer (A-1).
The nonvolatile matter (solid content) of the binder polymer (A-1) was 45.0% by mass, the weight average molecular weight was 75,000, and the acid value was 170 mgKOH / g.
The weight average molecular weight was determined by gel permeation chromatography (GPC) and calculated by using a standard polystyrene calibration curve. The conditions of GPC are shown below.
GPC conditions
Pump: Hitachi L-6000 (manufactured by Hitachi Seisakusho Co., Ltd., product name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (trade name, product of Hitachi Chemical Co., Ltd.)
Eluent: tetrahydrofuran
Measuring temperature: 40 ° C
Flow rate: 2.05 mL / min
Detector: Hitachi L-3300 type RI (product name of Hitachi Seisakusho Co., Ltd.)
[Synthesis of binder polymer (A-2)] [
A solution obtained by mixing 130 g of methacrylic acid as a polymerizable monomer (monomer), 230 g of methyl methacrylate, 25 g of ethyl acrylate and 115 g (weight ratio 26/46/5/23) of styrene and 5.5 g of azobisisobutyronitrile A solution of the binder polymer (A-2) was obtained in the same manner as in the preparation of the solution of the binder polymer (A-1) except that the solution " solution a " The nonvolatile matter (solid content) of the binder polymer (A-2) was 45.0% by mass, the weight average molecular weight was 75,000, and the acid value was 170 mgKOH / g.
[Synthesis of binder polymer (A-3)] [
A solution obtained by mixing 130 g of methacrylic acid as a polymerizable monomer (monomer), 195 g of methyl methacrylate, 75 g of ethyl acrylate and 100 g of styrene (weight ratio 26/39/15/20) and 4.0 g of azobisisobutyronitrile A solution of the binder polymer (A-3) was obtained in the same manner as in the preparation of the solution of the binder polymer (A-1), except that "solution a" The nonvolatile matter (solid content) of the binder polymer (A-3) was 45.0% by mass, the weight average molecular weight was 75,000, and the acid value was 170 mgKOH / g.
[Synthesis of binder polymer (A-4)] [
A solution obtained by mixing 130 g of methacrylic acid as a polymerizable monomer (monomer), 170 g of methyl methacrylate, 100 g of ethyl acrylate and 100 g of styrene (weight ratio 26/34/20/20) and 4.0 g of azobisisobutyronitrile A solution of the binder polymer (A-4) was obtained in the same manner as in the preparation of the solution of the binder polymer (A-1) except that "solution a" The non-volatile fraction (solid content) of the binder polymer (A-4) was 45.0 mass%, the weight average molecular weight was 75000, and the acid value was 170 mgKOH / g.
[Synthesis of binder polymer (A-5)] [
A solution obtained by mixing 130 g of methacrylic acid as a polymerizable monomer (monomer), 145 g of methyl methacrylate, 125 g of ethyl acrylate and 100 g of styrene (weight ratio 26/29/25/20) and 4.0 g of azobisisobutyronitrile A solution of the binder polymer (A-5) was obtained in the same manner as in the preparation of the solution of the binder polymer (A-1), except that "solution a" The nonvolatile matter (solid content) of the binder polymer (A-5) was 45.0% by mass, the weight average molecular weight was 75,000, and the acid value was 170 mgKOH / g.
[Synthesis of binder polymer (A-6)] [
A solution obtained by mixing 125 g of methacrylic acid as a polymerizable monomer (monomer), 250 g of methyl methacrylate and 125 g of styrene (weight ratio 25/50/25) and 6.5 g of azobisisobutyronitrile was referred to as "solution a" , A solution of the binder polymer (A-6) was obtained in the same manner as in the preparation of the solution of the binder polymer (A-1). The nonvolatile matter (solid content) of the binder polymer (A-6) was 45.0% by mass, the weight average molecular weight was 55,000, and the acid value was 163 mgKOH / g.
[Synthesis of binder polymer (A-7)] [
A solution obtained by mixing 100 g of methacrylic acid as a polymerizable monomer (monomer), 250 g of methyl methacrylate, 100 g of ethyl acrylate, and 50 g (weight ratio: 20/50/20/10) of styrene and 4.0 g of azobisisobutyronitrile A solution of the binder polymer (A-7) was obtained in the same manner as in the preparation of the solution of the binder polymer (A-1), except that "solution a" The non-volatile fraction (solid content) of the binder polymer (A-7) was 45.0% by mass, the weight average molecular weight was 80000, and the acid value was 163 mgKOH / g.
[Synthesis of binder polymer (A-8)] [
A solution obtained by mixing 125 g of methacrylic acid as a polymerizable monomer (monomer), 200 g of methyl methacrylate, 75 g of ethyl acrylate and 100 g of styrene (mass ratio 25/40/15/20) and 4.0 g of azobisisobutyronitrile A solution of the binder polymer (A-8) was obtained in the same manner as in the preparation of the solution of the binder polymer (A-1) except that "solution a" The non-volatile fraction (solid content) of the binder polymer (A-8) was 45.0% by mass, the weight average molecular weight was 80,000, and the acid value was 163 mgKOH / g.
Next, the materials shown in Table 1 were blended to obtain a solution of the photosensitive resin composition.
≪ (B) Photopolymerizable compound >
(4 - ((meth) acryloxypolyethoxy) phenyl) propane (trade name) manufactured by Hitachi Chemical Co.,
FA-MECH (product name, product of Hitachi Chemical Co., Ltd.):? -Chloro -? - hydroxypropyl -? '- methacryloyloxyethyl-ophthalate
FA-314 A (product of Hitachi Chemical Co., Ltd.): nonylphenoxypolyethylene glycol acrylate
PDE-400 (product name, product of Nitecy Co., Ltd.): polypropylene glycol dimethacrylate
TMPT-21 E (trade name, manufactured by Hitachi Chemical Co., Ltd.): EO-modified trimethylolpropane trimethacrylate (average addition amount of ethylene oxide: 21 mol)
<(C) Photopolymerization initiator>
N-1717 (product of ADEKA, product name): 1,7-bis (9,9-acridinyl) heptane
<(D) Amine compound>
LCV (product of Yamada Kagaku Co., Ltd.): Loico crystal violet
<Others>
MKG (product of Osaka Yuga-gaku Kogyo Co., Ltd., product name): Maracal Green
BMPS (product of Sumitomo Seika Co., Ltd.): tribromomethylphenyl sulfone
<Photosensitive element>
The solution of the above photosensitive resin composition was uniformly coated on a polyethylene terephthalate film (product name: " G2 ") each having a thickness of 16 탆 and dried with a hot air convection type drier at 100 캜 for 10 minutes, Thereby forming a photosensitive resin composition layer having a thickness of 35 mu m. A polyethylene terephthalate film (support film), a photosensitive resin composition layer, and a protective film were laminated in this order on the photosensitive resin composition layer with a protective film made of polyethylene (product name: "NF-13" Thereby obtaining a laminated photosensitive element.
<Laminated Substrate>
The copper surface of a copper-clad laminate (product name: MCL-E-679F, made by Hitachi Chemical Co., Ltd.) comprising a glass epoxy material and copper foil (thickness: And polished using a polishing machine (product name, manufactured by SANKE CO., LTD.) Having a brush equivalent to 600, washed, and dried in an air flow. The resulting copper-clad laminate was heated and heated to 80 DEG C, and then the photosensitive elements related to Examples 1 to 4 and Comparative Examples 1 to 5 were laminated (laminated) on the copper surface of the substrate. The laminate was formed under conditions of a temperature of 110 캜, a laminate pressure of 4 kgf / cm 2 , and a lamination speed of 1.5 m / min so that the photosensitive resin composition layer of each photosensitive element was brought into close contact with the copper surface of the substrate while removing the protective film. Thus, a laminated substrate having a photosensitive resin composition layer and a polyethylene terephthalate film laminated on the copper surface of the substrate was obtained.
≪ Evaluation of sensitivity &
A Hitachi 41 step (step) tablet was placed on the polyethylene terephthalate film of the laminate substrate, and a direct imaging apparatus (product name: DE-1 UH manufactured by Hitachi Biomedical Co., Ltd.) using a semiconductor laser having a wavelength of 405 nm as a light source Quot; manufactured by Mitsui Chemicals, Inc.). Thereafter, the polyethylene terephthalate film was peeled off, and a 1.0% by mass aqueous sodium carbonate solution was sprayed at 30 占 폚 for 24 seconds to remove the unexposed portion. The number of steps of the step tablet of the photocured film formed on the copper clad laminate was measured, The amount of energy (mJ / cm 2 ) at which the number of steps remaining after development was 17.0 was determined, and the sensitivity of the photosensitive resin composition was evaluated. The evaluation of the sensitivity shows that the smaller the value is, the higher the sensitivity.
<Evaluation of resolution>
Drawing data having a line width / space width of 3/3 to 100/100 (unit: 占 퐉) was used, and with the amount of energy at which the remaining step number after development of the Hitachi 41-step tablet was 17.0, The photosensitive resin composition layer of the substrate was exposed. The resist pattern is observed using an optical microscope after the developing process is performed under the same conditions as the above evaluation of the sensitivity and the resist pattern can be completely removed so that the resist pattern can be formed without causing the lines to meander, The resolution was evaluated based on the minimum value between the line widths of the pixels. The smaller this number is, the better the resolution is.
≪ Evaluation of adhesion &
Drawing data having a wiring pattern with a line width / space width of n / 400 (unit: 占 퐉) was used and the amount of energy at which the remaining step number of steps after development of the Hitachi 41- The composition layer was exposed. The resist pattern is observed using an optical microscope after the developing process is performed under the same conditions as the above evaluation of the sensitivity, and the unexposed portion can be completely removed. Further, The adhesion was evaluated by the minimum value. The smaller the number, the better the adhesion.
≪ Evaluation of foaming property &
The amount of dissolution of the photosensitive resin composition layer on the developing solution dissolved in the recommended conditions (0.4m 2 / L) 1.5 times, 0.6m 2 / L photosensitive resin composition layer with a developing solution (1 mass% Na 2 CO 3 aqueous solution) of which corresponds to the The solution was circulated and stirred with a small developing machine for 90 minutes, and the foaming was visually observed, and the foaming height was measured. The lower the foaming height, the lower the foaming property.
≪ Evaluation of peeling property &
Drawing data having a pattern of 60 mm x 40 mm was used as the pattern for peelability evaluation and exposure was performed on the photosensitive resin composition layer of the laminate substrate at an energy amount that the residual step number after development of the Hitachi 41 step tablet was 17.0 Respectively. Subsequently, the substrate having the cured film formed thereon was immersed in an aqueous solution of 3.0 mass% sodium hydroxide at 50 占 폚 and the time from when the cured film was completely peeled off from the substrate (Unit: second). The size of the peeling piece after peeling was visually observed and evaluated according to the following criteria. The shorter the peeling time and the smaller the size of the peeling piece, the better the peeling property. The results are shown in Table 2.
Peel Size
L: Sheet.
M: 30-40 mm square.
S: Less than 30mm square.
As shown in Table 2, it can be confirmed that the photosensitive resin compositions of Examples 1 to 4 have good adhesion and resolution, can reduce foaming at the time of development, and are excellent in peeling properties after curing .
One … Photosensitive element
2 … Support film
3 ... The photosensitive resin composition layer
4 … Protective film
Claims (7)
Wherein the binder polymer has a constitutional unit based on ethyl (meth) acrylate and the content of the constituent unit based on ethyl (meth) acrylate is 9% by mass or more based on the total amount of the binder polymer and the photopolymerizable compound, Lt; / RTI >
Wherein the binder polymer further comprises a constituent unit based on styrene or a styrene derivative.
Wherein the content of the structural unit based on the styrene or styrene derivative is 10 to 50 mass% with respect to the total mass of the polymerizable monomer constituting the binder polymer.
Wherein the photopolymerization initiator comprises an acridine compound having one or two acridinyl groups.
Wherein the photosensitive resin composition layer is a layer formed by using the photosensitive resin composition according to any one of claims 1 to 4.
An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to expose and cure the predetermined portion,
A developing step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate by removing a portion of the photosensitive resin composition layer other than the predetermined portion from above the substrate
And forming a resist pattern on the resist pattern.
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| JPJP-P-2012-034065 | 2012-02-20 | ||
| PCT/JP2013/053487 WO2013125429A1 (en) | 2012-02-20 | 2013-02-14 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
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| KR20140126294A true KR20140126294A (en) | 2014-10-30 |
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| JP (1) | JPWO2013125429A1 (en) |
| KR (1) | KR20140126294A (en) |
| CN (1) | CN104040431A (en) |
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| JP6814237B2 (en) * | 2018-03-23 | 2021-01-13 | 株式会社ノリタケカンパニーリミテド | Photosensitive compositions and their use |
| WO2021029039A1 (en) * | 2019-08-14 | 2021-02-18 | 昭和電工マテリアルズ株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board |
| WO2021137546A1 (en) | 2019-12-31 | 2021-07-08 | 코오롱인더스트리 주식회사 | Photosensitive resin composition, and dry film photoresist, photosensitive element, circuit board, and display device, each using same |
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| JP2003330182A (en) * | 2002-05-09 | 2003-11-19 | Hitachi Chem Co Ltd | Photosensitive resin composition and its utilization |
| JP2004077653A (en) * | 2002-08-13 | 2004-03-11 | Toagosei Co Ltd | Crosslink hardening type resin composition |
| WO2005050318A1 (en) * | 2003-11-19 | 2005-06-02 | Hitachi Chemical Co., Ltd. | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed circuit board |
| JP4632117B2 (en) * | 2004-07-27 | 2011-02-16 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern manufacturing method, and printed wiring board manufacturing method |
| JP2006220863A (en) * | 2005-02-09 | 2006-08-24 | Fuji Photo Film Co Ltd | Pattern formation material, pattern formation apparatus and pattern formation method |
| US20100129752A1 (en) * | 2005-05-30 | 2010-05-27 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element employing the same, method of forming resist pattern, and process for producing printed wiring board |
| JP2007010794A (en) * | 2005-06-28 | 2007-01-18 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element |
| JP2008009404A (en) * | 2006-05-30 | 2008-01-17 | Fujifilm Corp | Pattern forming material, pattern forming apparatus and pattern forming method |
| CN105182688B (en) * | 2008-06-02 | 2019-11-12 | 日立化成株式会社 | The manufacturing method of photosensitive polymer combination, photosensitive element, the manufacturing method of resist figure and printed circuit board |
| JP2010282001A (en) * | 2009-06-04 | 2010-12-16 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using the same |
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| CN104040431A (en) | 2014-09-10 |
| TW201337461A (en) | 2013-09-16 |
| JPWO2013125429A1 (en) | 2015-07-30 |
| WO2013125429A1 (en) | 2013-08-29 |
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