WO2012118031A1 - Photosensitive resin composition, photoresist film using same, resist pattern forming method, and conductor pattern forming method - Google Patents

Photosensitive resin composition, photoresist film using same, resist pattern forming method, and conductor pattern forming method Download PDF

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Publication number
WO2012118031A1
WO2012118031A1 PCT/JP2012/054824 JP2012054824W WO2012118031A1 WO 2012118031 A1 WO2012118031 A1 WO 2012118031A1 JP 2012054824 W JP2012054824 W JP 2012054824W WO 2012118031 A1 WO2012118031 A1 WO 2012118031A1
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Prior art keywords
resin composition
photosensitive resin
meth
group
acrylate
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PCT/JP2012/054824
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French (fr)
Japanese (ja)
Inventor
大貴 豊田
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ニチゴー・モートン株式会社
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Priority to KR1020137026142A priority Critical patent/KR101811091B1/en
Priority to CN201280011581.8A priority patent/CN103430100B/en
Publication of WO2012118031A1 publication Critical patent/WO2012118031A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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

Definitions

  • the present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photoresist film comprising a photosensitive resin composition layer comprising the photosensitive resin composition and a support layer, and a substrate using the photoresist film.
  • the present invention relates to a method for forming a resist pattern and a method for forming a conductor pattern using the photoresist film.
  • the present invention relates to a photosensitive resin composition that provides a resist pattern suitable for manufacturing a member such as an ITO electrode, an address electrode, or an electromagnetic wave shield in the field of flat panel displays, and a related technique.
  • the photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate.
  • a method of forming a conductor pattern on a substrate by forming a pattern, forming a conductor pattern by etching or plating, and then peeling and removing the resist pattern from the substrate.
  • a method for producing a printed wiring board using the photoresist film will be briefly described below.
  • a photoresist film has a protective layer, for example, a polyethylene film
  • this is peeled from the photosensitive resin composition layer.
  • a photosensitive resin composition layer and a support layer are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin composition layer, and the support layer are in this order.
  • the exposed portion is polymerized and cured by exposing the photosensitive resin composition layer with active energy rays such as ultraviolet rays including i rays (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern.
  • the support layer for example, a polyethylene terephthalate film is peeled off.
  • an unexposed portion of the photosensitive resin composition layer is dissolved or dispersed and removed with a developer, for example, an aqueous solution having weak alkalinity, to form a resist pattern on the substrate.
  • a developer for example, an aqueous solution having weak alkalinity
  • the process for forming a circuit is roughly divided into two methods.
  • the first method is a method (etching method) in which after removing the copper surface of the substrate not covered with the resist pattern by etching, the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer.
  • the second method is a method (plating method) in which the copper surface of the substrate is plated with copper, solder, and nickel, and then the resist pattern portion is removed and the copper surface of the substrate that appears is etched. is there.
  • a semi-additive construction method is used to create a high-density wiring with a uniform conductor shape.
  • a resist pattern is first formed on a seed copper thin film by the above-described method.
  • plating is performed between the resist patterns to form a plated copper wiring, and after the resist is peeled off, the plated copper wiring and the seed copper thin film are simultaneously etched by a technique called flash etching.
  • the semi-additive method has a thin seed copper thin film and is hardly affected by etching, and can form rectangular and high-density wiring.
  • a semi-cured resist called a soot (cured resist foot) may be generated at the boundary between the cured resist and the substrate after development (see FIG. 1).
  • a soot cured resist foot
  • the surface area of the seed copper thin film that appears after the development due to the soot is reduced, and the ground area of the plated copper wiring formed by the plating method and the copper thin film is reduced. Therefore, it leads to a problem that the plated copper wiring is easily peeled off. Further, since the sushi is under the plated copper wiring, it is caught when the resist is peeled off, which causes a peeling failure.
  • Patent Document 1 proposes a method for preventing halation on the substrate surface of transmitted light and suppressing the generation of sedge by using a triazine compound.
  • Patent Document 2 proposes a method of suppressing the generation of a semi-cured resist (soo) by using a photopolymerizable compound having a fluorene skeleton in the molecule.
  • a photosensitive resin composition having good resolution and adhesion, extremely small susceptibility of the cured resist after development, and good peelability
  • the photosensitive resin Photoresist film comprising a photosensitive resin composition layer comprising a composition and a support layer, a method for forming a resist pattern on a substrate using the photoresist film, and a method for forming a conductor pattern using the photoresist film
  • the purpose is to provide.
  • a photopolymerizable monomer component in a photosensitive resin composition containing a binder polymer as a main component and containing a photopolymerizable monomer and a photopolymerization initiator.
  • a monomer having an amino group and a benzotriazole derivative having a carboxyl group as a peelability-imparting component, high resolution and high adhesiveness are expressed, and the cured resist has a very small skirt after development. It has been found that the peelability is good and the above object can be achieved, and the present invention has been completed.
  • the gist of the present invention includes (A) a binder polymer, (B) a photopolymerizable monomer having an amino group, (C) a photopolymerization initiator, and (D) a benzotriazole derivative having a carboxyl group. It is related with the photosensitive resin composition characterized by these.
  • the present invention also relates to a photoresist film comprising a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention and a support layer.
  • the present invention relates to a method for forming a resist pattern, which includes a step of forming a photosensitive resin composition layer on a substrate using the photoresist film of the present invention, exposing and developing.
  • the present invention also includes a step of forming a photosensitive resin composition layer on a circuit-forming substrate using the photoresist film of the present invention, exposing and developing to form a resist pattern, and the resist pattern It is related with the formation method of the conductor pattern which has the process of etching or plating the said board
  • Photosensitivity comprising (A) a binder polymer, (B) a photopolymerizable monomer having an amino group, (C) a photopolymerization initiator, and (D) a benzotriazole derivative having a carboxyl group. Resin composition.
  • R 1 in the formula is independently each .R 2 and R 3 is H or CH 3, represents a hydrogen atom, an alkyl group, a group selected from the group consisting of alkoxy group and a halogen group, R 2 And R 3 may be bonded to each other to form a ring containing N.
  • X represents an alkylene group having 1 to 10 carbon atoms, or (C 2 H 4 O) m or (C 3 H 6 O) n.
  • M and n are each an integer of 1 to 10 polyoxyalkylene groups, and the polyoxyalkylene groups are random polymerization or block polymerization.
  • the photopolymerizable monomer having an amino group (B) is contained in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the (A) binder polymer [1] or [2] The photosensitive resin composition as described in 2. [4] Any of [1] to [3], wherein (D) the benzotriazole derivative having a carboxyl group is contained in an amount of 0.01 to 2 parts by weight with respect to 100 parts by weight of the (A) binder polymer.
  • a photoresist film comprising a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [5] and a support layer.
  • a method for forming a resist pattern comprising forming a photosensitive resin composition layer on a substrate using the photoresist film according to [6], exposing and developing.
  • a photosensitive resin composition layer is formed on a circuit-forming substrate, exposed and developed to form a resist pattern, and the resist pattern
  • a method for forming a conductor pattern comprising: etching or plating the circuit forming substrate on which is formed, and peeling the resist pattern.
  • the photosensitive resin composition and the photoresist film of the present invention have the effect that the resolution and adhesion are good, and the cured resist has a very small skirt and a good peelability after development. Therefore, the resist pattern forming method and the conductor pattern forming method using the photoresist film of the present invention can provide an effect that the resist pattern peeling failure and the conductor pattern (wiring) peeling are reduced.
  • FIG. A shows a cross-sectional view after development, B after plating, and C after peeling.
  • (meth) acryl means acryl or methacryl corresponding thereto
  • (meth) acrylate means acrylate or methacrylate corresponding thereto
  • (meth) acrylo means acrylo or methacrylo corresponding thereto.
  • the photosensitive resin composition of the present invention contains (A) a binder polymer, (B) a photopolymerizable monomer having an amino group, (C) a photopolymerization initiator, and (D) a benzotriazole derivative having a carboxyl group. It is characterized by doing.
  • Examples of the (A) binder polymer include acrylic polymers, styrene polymers, epoxy polymers, amide polymers, amide epoxy polymers, alkyd polymers, phenol polymers, and the like. One of these polymers can be used alone or in combination of two or more. Among these polymers, a carboxyl group-containing polymer is preferable.
  • Examples of the carboxyl group-containing polymer include acrylic polymers, polyester polymers, polyamide polymers, epoxy polymers and the like. Among them, (meth) acrylic acid esters and ethylenically unsaturated carboxylic acids and as necessary. It is preferable to use an acrylic polymer obtained by copolymerizing other copolymerizable monomers.
  • the content of the structural unit based on the (meth) acrylic acid ester is from the viewpoint of improving the alkali developability, resolution, and release properties.
  • the content is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass.
  • the content of the structural unit based on the ethylenically unsaturated carboxylic acid is high in resolution and adhesion, soot generation suppression, and peelability. From the viewpoint, it is preferably 12 to 50 parts by mass, more preferably 15 to 40 parts by mass, and particularly preferably 18 to 30 parts by mass. If the content of the ethylenically unsaturated carboxylic acid is too small, the alkali reactivity tends to be inferior and the development time and the peeling time tend to be long. If the content is too large, the developer resistance tends to decrease and the adhesion tends to decrease.
  • the content of structural units based on other copolymerizable monomers is preferably 10 to 80 parts by mass, It is preferably 20 to 70 parts by mass, particularly preferably 30 to 60 parts by mass.
  • These carboxyl group-containing polymers are used alone or in combination of two or more.
  • Examples of the carboxyl group-containing polymer used in combination of two or more types include, for example, two or more types of carboxyl group-containing polymers composed of different copolymerization components, two or more types of carboxyl group-containing polymers having different weight average molecular weights, and different dispersions. And two or more kinds of carboxyl group-containing polymers.
  • the acrylic polymer will be described. However, the acrylic polymer used in the present invention is not limited to the following.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Aliphatic (meth) acrylates having an alkyl group such as cyclohexyl (meth) acrylate having 1 to 20, preferably 1 to 10 carbon atoms; Aromatic (meth) acrylates such as benzyl (meth) acrylate; Diethylaminoethyl (meth) acrylate Amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate; hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; glycidyl (me
  • Examples of the ethylenically unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and anhydrides thereof.
  • Half esters can also be used, and these can be used alone or in combination of two or more. Of these, acrylic acid and methacrylic acid are particularly preferable.
  • Examples of the other copolymerizable monomers include (meth) acrylamide, 2,2,3,3-tetrafluoropropyl (meth) acrylate, acrylamide, diacetone acrylamide, styrene, ⁇ -methylstyrene, vinylnaphthalene, Examples include vinylcyclohexane, vinyltoluene, vinyl acetate, alkyl vinyl ether, (meth) acrylonitrile and the like, and these can be used alone or in combination of two or more.
  • the weight average molecular weight is preferably 50,000 to 200,000, more preferably 10,000 to 100,000, from the viewpoints of resolution and adhesion, soot generation suppression, and peelability.
  • the value is preferably 100 to 300 mgKOH / g, more preferably 120 to 250 mgKOH / g, and particularly preferably 140 to 190 mgKOH / g.
  • the weight average molecular weight (Mw) is a value obtained by measuring a THF (tetrahydrofuran) solution of a dry polymer on a polystyrene basis using a GPC (gel permeation chromatography) apparatus.
  • the acid value is the weight of KOH (potassium hydroxide) necessary to neutralize 1 g of the polymer.
  • the acid value is determined by adding alcohols such as methanol, ketones such as acetone and methyl ethyl ketone, or a mixed solvent thereof. It is measured by neutralizing titrating the dissolved polymer.
  • the weight average molecular weight is too small, the cured photosensitive resin composition tends to be brittle, whereas if it is too large, the resolution and resist peelability tend to decrease.
  • the acid value is too small, the effect of suppressing a decrease in resolution and resist peelability tends to be weakened.
  • the acid value is too large, the effect of suppressing a decrease in fine line adhesion of the cured resist tends to be weakened. is there.
  • the glass transition temperature (Tg) of the acrylic polymer is preferably in the range of 30 to 150 ° C, more preferably in the range of 60 to 120 ° C. If the glass transition temperature is too low, the photosensitive resin composition tends to flow and tends to cause edge fusion when it is rolled into a photoresist film. On the other hand, if the glass transition temperature is too high, it is used as a photoresist film. There is a tendency that the followability to the unevenness of the substrate surface at the time is lowered.
  • the glass transition temperature (Tg) may be measured by DSC (Differential Scanning Colorimetry) or may be calculated using the Fox equation when the glass transition temperature of the homopolymer of the copolymer monomer of the binder polymer is known. it can. In the present invention, it is calculated by the Fox equation.
  • Tg represents the glass transition temperature of the copolymer.
  • Wa, Wb,... represent the weight fraction of the a component, b component,... Ta, Tb,.
  • B represents the glass transition temperature of the homopolymer of component.
  • Examples of the photopolymerizable monomer having an amino group include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth).
  • acrylamide normal propyl (meth) acrylamide, isopropyl (meth) acrylamide, N- (meth) acryloylmorpholine, at least one photopolymerizable unsaturated compound selected from the group represented by the following general formula (I) Also mentioned.
  • R 1 in the formula represents H or CH 3 a is .
  • R 2 and R 3 are each independently a hydrogen atom, an alkyl group, a group selected from the group consisting of alkoxy group and a halogen group, R 2 and R 3 may be bonded to each other to form a ring containing N.
  • X represents an alkylene group having 1 to 10 carbon atoms, or (C 2 H 4 O) m or (C 3 H 6 O) n.
  • M and n are each an integer of 1 to 10 polyoxyalkylene groups, and the polyoxyalkylene groups are random polymerization or block polymerization.
  • R 1 in the formula is H or CH 3 .
  • R 2 and R 3 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen group, and R 2 and R 3 may be bonded to each other to form a ring containing N. good.
  • the alkyl group and alkoxy group usually have 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • X is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or (C 2 H 4 O) m or (C 3 H 6 O) n, and m and n are each an integer of 1 to 10 It is a polyoxyalkylene group.
  • the polyoxyalkylene group may be random polymerization or block polymerization.
  • Specific examples of the compound represented by the general formula (I) include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethyl.
  • the occurrence of scum in the cured resist is due to the partial reaction of the acidic groups of the semi-cured resist, which is weakly cured, with the developer, and the semi-cured resist moves to the bottom of the resist during drying after development without being removed. It is presumed to be.
  • the amino group of the photopolymerizable monomer (B) causes a neutralization reaction with the acidic group in the binder polymer (A) in the photosensitive resin composition, and (A) the acidic group of the binder polymer is covered. It can be considered that the developer resistance is improved and the reattachment of the semi-cured resist is reduced, that is, the sash is reduced.
  • the monomer (B) since the monomer (B) has a photopolymerizable structure, the degree of cure is increased and an improvement in adhesion can be expected. Therefore, the monomer (B) can have the same effect as long as it has an amino group and can be photopolymerized.
  • the content of the photopolymerizable monomer (B) having an amino group is preferably 0.01 to 30 parts by weight, more preferably 0.8 parts per 100 parts by weight of the (A) binder polymer.
  • the amount is 1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and particularly preferably 1 to 15 parts by weight.
  • the photopolymerizable monomer shown below can be used together with the photopolymerizable monomer having an amino group.
  • a monomer having one polymerizable unsaturated group 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxy Propyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate , Half (meth) acrylates of phthalic acid derivatives, and the like, and these can be used alone or in combination of two or more.
  • Examples of the monomer having two polymerizable unsaturated groups include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol / polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, oxyethylene group-containing bisphenol A Type di (meth) acrylate, oxypropylene group-containing bisphenol A type di (meth) acrylate, oxyethylene / oxypropylene group-containing bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth)
  • a monomer having three or more polymerizable unsaturated groups for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyl
  • examples thereof include oxyethoxytrimethylolpropane and glycerin polyglycidyl ether poly (meth) acrylate, and these can be used alone or in combination of two or more.
  • urethane (meth) acrylate may be mentioned.
  • urethane (meth) acrylates include diisocyanates such as hexamethylene diisocyanate and tolylene diisocyanate, and hydroxyl groups in one molecule such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and oligopropylene glycol monomethacrylate.
  • examples thereof include a hydroxyl group-containing (meth) acrylate having a (meth) acryl group and, if necessary, a compound obtained by reacting with a polyol. These may be used alone or in combination of two or more.
  • the total amount of the photopolymerizable monomer (B) having an amino group and the photopolymerizable monomer other than (B) is 10 to 200 parts by weight with respect to 100 parts by weight of the (A) binder polymer. It is preferably 30 to 160 parts by weight, more preferably 50 to 120 parts by weight, and particularly preferably 60 to 100 parts by weight. When the content is too small, curing tends to be insufficient, and when the content is too large, cold flow tends to occur.
  • Examples of (C) photopolymerization initiators include (C1) hexaarylbisimidazole derivatives, (C2) alkylaminobenzophenone derivatives, N-arylglycine derivatives, acridine derivatives, anthraquinone derivatives such as diaminoanthraquinone, N, N, N ', N'-tetraarylbenzidine derivatives, riboflavin triacetate, benzophenone, benzyldimethyl ketal, thioxanthone derivatives, alkylaminobenzoic acid alkyl esters, triazine derivatives, coumarin derivatives such as coumarin 6, triphenylphosphine, tolylphosphine, trixylyl And triarylphosphine such as phosphine, tribiphenylphosphine, trinaphthylphosphine, trianthrylphosphine, triphenanthrylpho
  • Examples of (C1) hexaarylbisimidazole derivatives include 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (3-methoxyphenyl) bisimidazole, 2,2 '-Bis (2,3-dichlorophenyl) -4,4', 5,5'-tetrakis (4-methoxyphenyl) bisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5′-tetrakis (3-methoxyphenyl) phenylbisimidazole, 2,2′-bis (2,5-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxy
  • Examples of (C2) alkylaminobenzophenone derivatives include 4,4′-bis (diethylamino) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bis (dimethylamino) benzophenone, and the like.
  • 4,4′-bis (diethylamino) benzophenone is particularly preferable, and these can be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention preferably contains at least (C1) hexaarylbisimidazole derivative as the photopolymerization initiator (C) from the viewpoint of increasing sensitivity, and in particular, (C1) hexaarylbis. It preferably contains an imidazole derivative and another photopolymerization initiator, and further preferably contains a (C1) hexaarylbisimidazole derivative and (C2) an alkylaminobenzophenone derivative.
  • the content of the (C) photopolymerization initiator is preferably 1 to 20 parts by weight, particularly 2 to 16 parts by weight, more preferably 3 to 12 parts by weight with respect to 100 parts by weight of the (A) binder polymer. It is preferable that (C) If the content of the photopolymerization initiator is too small, the required sensitivity, resolution, and adhesion tend to be not obtained, and if too large, insoluble matter tends to be generated in the photosensitive resin composition. It is in.
  • (C1) a hexaarylbisimidazole derivative and another photopolymerization initiator are used in combination, for example, when (C1) a hexaarylbisimidazole derivative and (C2) an alkylaminobenzophenone derivative are used in combination, (A) 100 weight of binder polymer
  • the amount of (C1) hexaarylbisimidazole derivative is preferably 1 to 16 parts by weight, particularly 2 to 13 parts by weight, more preferably 3 to 10 parts by weight, and (C2) the alkylaminobenzophenone derivative is 0 parts by weight. It is preferably 0.01 to 4 parts by weight, particularly 0.02 to 3 parts by weight, and more preferably 0.06 to 2 parts by weight.
  • Examples of (D) benzotriazole derivatives having a carboxyl group include 4-carboxybenzotriazole, 5-carboxybenzotriazole, 1- (1 ′, 2′-dicarboxyethyl) benzotriazole, 1- (2 ′, 3 '-Dicarboxypropyl) benzotriazole, 1-((bis (2-ethylhexyl) amino) methyl) -1H-benzotriazolecarboxylic acid is preferably used, and these may be used alone or in combination of two or more. it can. Note that 4-carboxybenzotriazole and 5-carboxybenzotriazole are particularly preferable because of their availability.
  • the benzotriazole derivative is known to have good affinity with copper metal, and it is considered that the benzotriazole derivative is coordinated on the copper substrate after laminating a photoresist film on the copper substrate.
  • the strong alkaline aqueous solution at the time of stripping and the carboxyl group cause a neutralization reaction, so that the resist can be easily stripped from the interface of the copper substrate.
  • the content of the (D) carboxyl group-containing benzotriazole derivative is preferably 0.01 to 2 parts by weight, particularly 0.04 to 1.6 parts by weight, based on 100 parts by weight of the (A) binder polymer. Part, more preferably 0.08 to 1 part by weight.
  • the weight ratio (B) / (D) of the component is preferably in the range of 1 to 500.
  • the weight ratio (B) / (D) is preferably in the range of 3 to 200, and the weight ratio (B) / (D) is preferably in the range of 5 to 50. If the ratio is too low, peeling can be easily performed, but the soot tends to increase. If the ratio is too high, the generation of soot can be suppressed, but the peeling tends to be difficult.
  • the photosensitive resin composition of the present invention preferably further contains a dye.
  • dyes include crystal violet, malachite green, and malachite. Green Lake, Brilliant Green, Diamond Green, Patent Blue, Chill Violet, Victoria Blue, Victoria Pure Blue, Oil Blue, Basic Blue 20, Rose Aniline, Parafuchsin, Ethylene Violet and other Coloring Dyes, Tris (4-Dimethylamino-2- And leuco dyes such as methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye.
  • the photosensitive resin composition of the present invention may contain a halogen compound.
  • the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like.
  • the photosensitive resin composition of the present invention may contain an additive such as a plasticizer, if necessary.
  • additives include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl Glycol esters such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, citric acid Tributyl, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, tri-n-acetyl citrate Chill, and the like.
  • the photosensitive resin composition of the present invention it is also possible to contain a radical polymerization inhibitor in the photosensitive resin composition.
  • the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis. (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.
  • the photosensitive resin composition of the present invention is optionally mixed with a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. It is good also as a solution with a solid content of about 30 to 60% by weight. This solution can be used as a coating solution for forming a photosensitive resin composition layer of a photoresist film described later.
  • a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. It is good also as a solution with a solid content of about 30 to 60% by weight. This solution can be used as a coating solution for
  • a photosensitive resin composition layer by applying this coating solution on a substrate such as a circuit-forming substrate and drying it, from the viewpoint of work efficiency and the like, a photoresist film described later It is preferably used for forming a photosensitive resin composition layer.
  • the photosensitive resin composition of the present invention includes adhesion promoters, antioxidants, thermal polymerization inhibitors, surface tension modifiers, stabilizers, chain transfer agents, antifoaming agents, flame retardants, and the like.
  • An agent may be contained as appropriate, and in such a case, the content is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) to (D). It is preferably contained in an amount of 0.02 to 15 parts by mass, and more preferably 0.03 to 10 parts by mass. These are used alone or in combination of two or more.
  • the photoresist film of the present invention includes a photosensitive resin composition layer comprising a photosensitive resin composition and a support layer.
  • the support layer used here is preferably a transparent layer that transmits light emitted from the exposure light source.
  • a support layer for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. Among these, a polyethylene terephthalate film is preferable. These films can be stretched if necessary.
  • the haze of the support layer is preferably 5 or less.
  • a thinner support layer is advantageous in terms of image formation and economy, but a thickness of 10 to 30 ⁇ m is preferably used in order to maintain strength.
  • the thickness of the photosensitive resin composition layer in the photoresist film varies depending on the application, but is preferably 5 to 100 ⁇ m, more preferably 7 to 60 ⁇ m, and particularly preferably 10 to 50 ⁇ m. If the photosensitive resin composition layer is too thin, the film strength tends to be too low, and if it is too thick, the adhesion, sensitivity, and resolution tend to decrease.
  • the photoresist film of the present invention may have a protective layer on the surface opposite to the support layer side of the photosensitive resin composition layer, if necessary.
  • a protective layer is required to be sufficiently smaller than the protective layer.
  • the protective layer for example, a polyethylene film or a polypropylene film can be preferably used.
  • the thickness of the protective layer is preferably 10 to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
  • a coating solution containing the photosensitive resin composition of the present invention is applied to one side of a support layer, dried, and if necessary, the coated surface is coated with a protective layer.
  • a coating liquid containing the photosensitive resin composition of the present invention is uniformly applied to one side of the support layer by a roll coater method, a bar coater method, or the like, and the temperature is gradually increased from 50 to 120 ° C. or higher. It can be manufactured by drying in an oven to form a photosensitive resin composition layer and then pressure laminating a protective layer on the upper surface of the layer.
  • a resist pattern using the photoresist film of the present invention can be formed by a process including a lamination process, an exposure process, and a development process.
  • An example of a specific method is shown below.
  • the substrate to be processed include a copper-clad laminate for the purpose of producing a printed wiring board, and a glass substrate (for example, a substrate for plasma display panel or surface electrolysis for the purpose of producing an uneven substrate). Display substrate), silicone wafers having through-holes, and ceramic substrates.
  • the plasma display panel substrate is a substrate in which an electrode is formed on a glass substrate, a dielectric layer is formed, a partition wall glass paste is applied, and a partition wall glass paste portion is subjected to sandblasting to form a partition wall. It is a material.
  • a lamination process is performed using a laminator.
  • the protective layer is peeled off, and then the photosensitive resin composition layer is heat-pressed and laminated on the surface of the substrate to be processed with a laminator.
  • the photosensitive resin composition layer may be laminated only on one side of the substrate surface, or may be laminated on both sides.
  • the heating temperature at this time is generally 40 to 160 ° C.
  • an exposure process is performed using an exposure machine. If necessary, the support layer is peeled off and exposed to active light through a photomask.
  • the exposure amount is determined by the light source illuminance and the exposure time, but may be measured using a light meter.
  • a direct drawing exposure method may be used.
  • the direct drawing exposure method is a method in which exposure is performed by directly drawing on a substrate without using a photomask.
  • the light source for example, a semiconductor laser having a wavelength of 350 to 410 nm or an ultrahigh pressure mercury lamp is used.
  • the drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.
  • the photosensitive resin composition of the present invention is a dilute alkali development type, a 0.1 to 5% by weight alkaline aqueous solution containing an alkali compound such as sodium carbonate, potassium carbonate or tetramethylammonium hydroxide is used for development. Do it.
  • the pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer.
  • the resist pattern is obtained by the above-described steps, in some cases, a heating step at 100 to 300 ° C. or a UV curing step can be performed. By carrying out these steps, further chemical resistance can be improved.
  • the conductor pattern forming method of the present invention is performed by performing the following steps after performing the above-described resist pattern formation using a circuit-forming substrate such as a copper-clad laminate or a flexible substrate as a base material. First, a conductor pattern is formed on the surface of the substrate exposed by development using a known method such as plating or etching.
  • plating methods used for plating include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel such as nickel sulfamate Examples thereof include gold plating such as plating, hard gold plating, and soft gold plating.
  • a plating pretreatment agent such as a degreasing agent or a soft etching agent.
  • Etching is usually performed according to a conventional method using an acidic etching solution such as a cupric chloride-hydrochloric acid aqueous solution or a ferric chloride-hydrochloric acid aqueous solution.
  • an ammonia-based alkaline etching solution is also used.
  • an alkali stripping solution composed of an alkaline aqueous solution having a concentration of about 0.1 to 10% by weight containing an alkali compound such as sodium hydroxide or potassium hydroxide, or an organic amine-based stripping of a 3 to 15% by weight aqueous solution.
  • the resist pattern is stripped and removed using a liquid (particularly, one containing monoethanolamine as a main component).
  • a conductor film may be laminated on the resist pattern without removing the resist pattern.
  • flash etching is then performed.
  • the photoresist film in an Example and a comparative example was produced as follows.
  • the solution of the photosensitive resin composition shown in Table 1 was adjusted so that the solid content was 55% by weight, stirred and mixed well, and an applicator was used on a 16 ⁇ m thick polyethylene terephthalate (PET) film as a support film.
  • PET polyethylene terephthalate
  • the coating film thickness after drying was 25 ⁇ m. It dried for 2 minutes each in 60 degreeC and 90 degreeC oven, and also it coat
  • the obtained photoresist film was evaluated as follows.
  • the PET film After exposure, after 15 minutes, the PET film is peeled off and sprayed with a 0.7 wt% sodium carbonate aqueous solution at 27 ° C. for a development time that is twice the breakpoint (time for complete dissolution of the unexposed area). Unexposed portions were dissolved and removed to obtain a cured resist image. From each exposure amount and the number of steps remaining after development, an exposure amount (mJ / cm 2 ) at which the number of remaining step steps after development of the stove 21-step tablet was 6 steps was examined.
  • Adhesion As a mask film at the time of exposure, using a line pattern mask of an exposed portion alone, the exposure was performed with an exposure amount that the number of steps of the step tablet was six, and developed.
  • the minimum mask width ( ⁇ m) at which the cured resist pattern was normally formed was defined as the adhesion value.
  • the photosensitive resin compositions of Examples 1 to 7 are excellent in resolution and adhesion. Furthermore, since the width of the cured resist is small, it is difficult for troubles to occur during subsequent etching or plating. Moreover, since the peelability is also good, stable productivity can be secured.
  • the photosensitive resin compositions of Comparative Examples 1 to 4 were inferior in both resolution and adhesion. Moreover, since the photosensitive resin composition of Comparative Examples 1, 3, and 4 has a large thickness of the cured resist, there is a possibility that troubles may occur during subsequent etching or plating. Furthermore, since the photosensitive resin compositions of Comparative Examples 1 and 2 have poor peelability, it is difficult to obtain a stable throughput.
  • the photosensitive resin composition and the photoresist film of the present invention have the effect that the resolution and adhesion are good, and the cured resist has a very small skirt and a good peelability after development. Therefore, the photosensitive resin composition and the photoresist film of the present invention are suitable as resist materials such as etching resists and plating resists in the fields of production of printed wiring boards, lead frames, semiconductor packages and the like, and precision metal processing. Can be used.

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Abstract

The present invention relates to a photosensitive resin composition comprising a binder polymer, a photopolymerizable monomer containing an amine group, a photopolymerization initiator, and a benzotriazole derivative containing a carboxyl group. The present invention also relates to a photoresist film containing a photosensitive resin composition layer comprising the photosensitive resin composition and a support layer. The photosensitive resin composition and photoresist film provide excellent resolution and adhesion, an extremely small fringe on the cured resist after development, and excellent release properties.

Description

感光性樹脂組成物、これを用いたフォトレジストフィルム、レジストパターンの形成方法及び導体パターンの形成方法Photosensitive resin composition, photoresist film using the same, resist pattern forming method and conductor pattern forming method
　本発明は、アルカリ性水溶液によって現像可能な感光性樹脂組成物、該感光性樹脂組成物からなる感光性樹脂組成物層と支持層を含むフォトレジストフィルム、該フォトレジストフィルムを用いて基材上にレジストパターンを形成する方法、及び該フォトレジストフィルムを用いた導体パターンの形成方法に関する。さらに詳しくは、プリント配線板の製造、フレキシブルプリント配線板の製造、ＩＣチップ搭載用リードフレーム（以下、リードフレームという）の製造、メタルマスク製造などの金属箔精密加工、ＢＧＡ（ボールグリッドアレイ）やＣＳＰ（チップサイズパッケージ）等の半導体パッケージ製造、ＴＡＢ（ＴａｐｅＡｕｔｏｍａｔｅｄＢｏｎｄｉｎｇ）やＣＯＦ（ＣｈｉｐＯｎＦｉｌｍ：半導体ＩＣをフィルム状の微細配線板上に搭載したもの）に代表されるテープ基板の製造、半導体バンプの製造、フラットパネルディスプレイ分野におけるＩＴＯ電極、アドレス電極、または電磁波シールドといった部材の製造に好適なレジストパターンを与える感光性樹脂組成物、及びその関連技術に関するものである。 The present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photoresist film comprising a photosensitive resin composition layer comprising the photosensitive resin composition and a support layer, and a substrate using the photoresist film. The present invention relates to a method for forming a resist pattern and a method for forming a conductor pattern using the photoresist film. More specifically, the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for IC chip mounting (hereinafter referred to as lead frames), metal foil precision processing such as metal mask manufacturing, BGA (ball grid array) Manufacturing of semiconductor packages such as CSP (chip size package), manufacturing of tape substrates represented by TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board), manufacturing of semiconductor bumps, The present invention relates to a photosensitive resin composition that provides a resist pattern suitable for manufacturing a member such as an ITO electrode, an address electrode, or an electromagnetic wave shield in the field of flat panel displays, and a related technique.
　従来、プリント配線板はフォトリソグラフィー法によって製造されている。フォトリソグラフィー法とは、感光性樹脂組成物を基板上に塗布し、パターン露光して該感光性樹脂組成物の露光部を重合硬化させ、未露光部を現像液で除去して基板上にレジストパターンを形成し、エッチング又はめっき処理を施して導体パターンを形成した後、該レジストパターンを該基板上から剥離除去することによって、基板上に導体パターンを形成する方法を言う。
　上記のフォトリソグラフィー法においては、感光性樹脂組成物を基板上に塗布するにあたって、フォトレジスト溶液を基板に塗布して乾燥させる方法、または支持層、感光性樹脂組成物からなる層（以下、「感光性樹脂組成物層」ともいう。）、及び必要によっては保護層、を順次積層したフォトレジストフィルムを用いて、その感光性樹脂組成物層側を基板に積層する方法のいずれかが使用される。そして、プリント配線板の製造においては、後者のフォトレジストフィルムが使用されることが多い。 Conventionally, printed wiring boards are manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate. A method of forming a conductor pattern on a substrate by forming a pattern, forming a conductor pattern by etching or plating, and then peeling and removing the resist pattern from the substrate.
In the photolithography method described above, when the photosensitive resin composition is applied onto the substrate, a method in which a photoresist solution is applied to the substrate and dried, or a support layer, a layer made of the photosensitive resin composition (hereinafter, “ Or a method of laminating the photosensitive resin composition layer side on a substrate using a photoresist film in which a protective layer is laminated in order, if necessary. The In the production of a printed wiring board, the latter photoresist film is often used.
　上記のフォトレジストフィルムを用いてプリント配線板を製造する方法について、以下に簡単に述べる。
　まず、フォトレジストフィルムが保護層、例えば、ポリエチレンフィルムを有する場合には、感光性樹脂組成物層からこれを剥離する。次いで、ラミネーターを用いて基板、例えば、銅張積層板の上に、該基板、感光性樹脂組成物層、支持層の順序になるように感光性樹脂組成物層及び支持層を積層する。次いで、配線パターンを有するフォトマスクを介して、該感光性樹脂組成物層に、超高圧水銀灯が発するｉ線（３６５ｎｍ）を含む紫外線等の活性エネルギー線で露光することによって、露光部分を重合硬化させる。次いで、支持層、例えばポリエチレンテレフタレートフィルムを剥離する。次いで、現像液、例えば、弱アルカリ性を有する水溶液により感光性樹脂組成物層の未露光部分を溶解又は分散除去して、基板上にレジストパターンを形成させる。レジストパターン形成後、回路を形成させるプロセスは大きく２つの方法に分かれる。第一の方法は、レジストパターンによって覆われていない基板の銅面をエッチング除去した後、レジストパターン部分を現像液よりも強いアルカリ水溶液で除去する方法（エッチング工法）である。第二の方法は、基板の銅面に銅、半田、ニッケルを用いためっき処理を行った後、レジストパターン部分を除去し、さらに、現れた基板の銅面をエッチングする方法（めっき工法）である。 A method for producing a printed wiring board using the photoresist film will be briefly described below.
First, when a photoresist film has a protective layer, for example, a polyethylene film, this is peeled from the photosensitive resin composition layer. Next, a photosensitive resin composition layer and a support layer are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin composition layer, and the support layer are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin composition layer with active energy rays such as ultraviolet rays including i rays (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Let Next, the support layer, for example, a polyethylene terephthalate film is peeled off. Next, an unexposed portion of the photosensitive resin composition layer is dissolved or dispersed and removed with a developer, for example, an aqueous solution having weak alkalinity, to form a resist pattern on the substrate. After forming the resist pattern, the process for forming a circuit is roughly divided into two methods. The first method is a method (etching method) in which after removing the copper surface of the substrate not covered with the resist pattern by etching, the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer. The second method is a method (plating method) in which the copper surface of the substrate is plated with copper, solder, and nickel, and then the resist pattern portion is removed and the copper surface of the substrate that appears is etched. is there.
　一方、導体形状が均一で高密度の配線を作成するには、セミアディティブ工法が用いられる。セミアディティブ工法では、まずレジストパターンをシード銅薄膜上に上述の方法で形成する。次いで、レジストパターン間にめっきを施してめっき銅配線を形成し、レジストを剥離したのち、フラッシュエッチングと呼ばれる手法により、該めっき銅配線とシード銅薄膜とを同時にエッチングする。セミアディティブ工法は、上記のめっき工法とは異なりシード銅薄膜が薄く、エッチングによる影響がほとんど無く、矩形かつ高密度の配線を作成することができる。 On the other hand, a semi-additive construction method is used to create a high-density wiring with a uniform conductor shape. In the semi-additive method, a resist pattern is first formed on a seed copper thin film by the above-described method. Next, plating is performed between the resist patterns to form a plated copper wiring, and after the resist is peeled off, the plated copper wiring and the seed copper thin film are simultaneously etched by a technique called flash etching. Unlike the plating method described above, the semi-additive method has a thin seed copper thin film and is hardly affected by etching, and can form rectangular and high-density wiring.
　しかしながら、現像後において硬化レジストと基板との境界部分にスソ（硬化レジストフット部）と呼ばれる半硬化レジストが発生することがある（図１を参照。）。特に高密度のレジストパターン間では、スソによって現像後に表れたシード銅薄膜の表面積が減ることで、めっき法によって形成されためっき銅配線と銅薄膜との接地面積が減少する。したがって、めっき銅配線が剥がれやすくなるという問題につながる。また、スソがめっき銅配線下にあるため、レジスト剥離時にひっかかり、剥離不良の原因ともなる。さらに、エッチング工法においても、スソによって現像後に表れた銅薄膜の表面積が減ることで、エッチング除去が不充分になるおそれがある。このため、現像後の硬化レジストのスソが極めて小さいフォトレジストフィルムが求められている。 However, a semi-cured resist called a soot (cured resist foot) may be generated at the boundary between the cured resist and the substrate after development (see FIG. 1). In particular, between the high-density resist patterns, the surface area of the seed copper thin film that appears after the development due to the soot is reduced, and the ground area of the plated copper wiring formed by the plating method and the copper thin film is reduced. Therefore, it leads to a problem that the plated copper wiring is easily peeled off. Further, since the sushi is under the plated copper wiring, it is caught when the resist is peeled off, which causes a peeling failure. Further, even in the etching method, the surface area of the copper thin film that appears after development due to the soot is reduced, which may result in insufficient etching removal. For this reason, there is a demand for a photoresist film having a very small cured resist skirt after development.
　これらの課題を解決する方法として、例えば、特許文献１では、トリアジン化合物を用いることで、透過光の基材表面でのハレーションを防ぎ、スソの発生を抑制する方法が提案されており、また、特許文献２では、分子内にフルオレン骨格を有する光重合性化合物を用いることで、半硬化レジスト（スソ）の発生を抑制する方法が提案されている。 As a method for solving these problems, for example, Patent Document 1 proposes a method for preventing halation on the substrate surface of transmitted light and suppressing the generation of sedge by using a triazine compound. Patent Document 2 proposes a method of suppressing the generation of a semi-cured resist (soo) by using a photopolymerizable compound having a fluorene skeleton in the molecule.
日本国特開２００７－１１４４５２号公報Japanese Unexamined Patent Publication No. 2007-114452 日本国特開２００９－５３３８８号公報Japanese Unexamined Patent Publication No. 2009-53388
　しかしながら、上記特許文献１に記載されているトリアジン化合物は、スソの低減に対して効果が見られるものの、依然としてまだ充分とは言えず、上記特許文献２に記載されている分子内にフルオレン骨格を有する光重合性化合物は、その強い疎水性によりレジスト剥離性が大きく悪化するという問題があった。 However, although the triazine compound described in Patent Document 1 has an effect on the reduction of soot, it is still not sufficient, and a fluorene skeleton is formed in the molecule described in Patent Document 2. The photopolymerizable compound has a problem that resist releasability is greatly deteriorated due to its strong hydrophobicity.
　そこで、本発明ではこのような背景下において、解像性及び密着性が良好で、かつ現像後の硬化レジストのスソが極めて小さく、剥離性も良好である感光性樹脂組成物、該感光性樹脂組成物からなる感光性樹脂組成物層と支持層を含むフォトレジストフィルム、該フォトレジストフィルムを用いて基材上にレジストパターンを形成する方法、及び該フォトレジストフィルムを用いた導体パターンの形成方法を提供することを目的とする。 Therefore, in the present invention, under such a background, a photosensitive resin composition having good resolution and adhesion, extremely small susceptibility of the cured resist after development, and good peelability, and the photosensitive resin Photoresist film comprising a photosensitive resin composition layer comprising a composition and a support layer, a method for forming a resist pattern on a substrate using the photoresist film, and a method for forming a conductor pattern using the photoresist film The purpose is to provide.
　しかるに、本発明者が上記課題を解決するため鋭意検討した結果、バインダーポリマーを主成分とし、光重合可能なモノマー、光重合開始剤を含有する感光性樹脂組成物において、光重合可能なモノマー成分としてアミノ基を有するモノマーと、剥離性付与成分としてカルボキシル基を有するベンゾトリアゾール誘導体を含有させることにより、高解像性及び高密着性を発現し、かつ現像後の硬化レジストのスソが極めて小さく、剥離性も良好であり、上記目的を達成可能であることを見出し、本発明を完成するに至った。 However, as a result of intensive studies by the present inventor to solve the above problems, a photopolymerizable monomer component in a photosensitive resin composition containing a binder polymer as a main component and containing a photopolymerizable monomer and a photopolymerization initiator. By adding a monomer having an amino group and a benzotriazole derivative having a carboxyl group as a peelability-imparting component, high resolution and high adhesiveness are expressed, and the cured resist has a very small skirt after development. It has been found that the peelability is good and the above object can be achieved, and the present invention has been completed.
　すなわち、本発明の要旨は、（Ａ）バインダーポリマー、（Ｂ）アミノ基を有する光重合可能なモノマー、（Ｃ）光重合開始剤、及び（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体を含有することを特徴とする感光性樹脂組成物に関するものである。 That is, the gist of the present invention includes (A) a binder polymer, (B) a photopolymerizable monomer having an amino group, (C) a photopolymerization initiator, and (D) a benzotriazole derivative having a carboxyl group. It is related with the photosensitive resin composition characterized by these.
　また、本発明は、本発明の感光性樹脂組成物からなる感光性樹脂組成物層と支持層を含むフォトレジストフィルムに関するものである。 The present invention also relates to a photoresist film comprising a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention and a support layer.
　さらに、本発明は、本発明のフォトレジストフィルムを用いて、基材上に感光性樹脂組成物層を形成し、露光し、現像する工程を有するレジストパターンの形成方法に関するものである。 Furthermore, the present invention relates to a method for forming a resist pattern, which includes a step of forming a photosensitive resin composition layer on a substrate using the photoresist film of the present invention, exposing and developing.
　また、本発明は、本発明のフォトレジストフィルムを用いて、回路形成用基板上に感光性樹脂組成物層を形成し、露光し、現像して、レジストパターンを形成する工程と、前記レジストパターンが形成された前記回路形成用基板をエッチングまたはめっきし、前記レジストパターンを剥離する工程を有する導体パターンの形成方法に関するものである。 The present invention also includes a step of forming a photosensitive resin composition layer on a circuit-forming substrate using the photoresist film of the present invention, exposing and developing to form a resist pattern, and the resist pattern It is related with the formation method of the conductor pattern which has the process of etching or plating the said board | substrate for circuit formation in which this was formed, and peeling the said resist pattern.
　本発明は以下の態様を含む。
［１］　（Ａ）バインダーポリマー、（Ｂ）アミノ基を有する光重合可能なモノマー、（Ｃ）光重合開始剤、及び（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体を含有することを特徴とする感光性樹脂組成物。
［２］　（Ｂ）アミノ基を有する光重合可能なモノマーが、下記一般式（Ｉ）で表される光重合可能な不飽和化合物であることを特徴とする［１］に記載の感光性樹脂組成物。
Figure JPOXMLDOC01-appb-C000002
 （但し、式中のＲ１はＨまたはＣＨ３である。Ｒ２及びＲ３はそれぞれ独立して、水素原子、アルキル基、アルコキシ基及びハロゲン基からなる群から選ばれる基を表し、Ｒ２及びＲ３が互いに結合してＮを含む環を形成しても良い。Ｘは炭素数１～１０のアルキレン基、または（Ｃ２Ｈ４Ｏ）ｍまたは（Ｃ３Ｈ６Ｏ）ｎで示され、ｍ、ｎが各々１～１０の整数のポリオキシアルキレン基であり、ポリオキシアルキレン基はランダム重合またはブロック重合である。）
［３］　（Ｂ）アミノ基を有する光重合可能なモノマーを、（Ａ）バインダーポリマー１００重量部に対して、０．０１～３０重量部含有することを特徴とする［１］又は［２］に記載の感光性樹脂組成物。
［４］　（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体を、（Ａ）バインダーポリマー１００重量部に対して、０．０１～２重量部含有することを特徴とする［１］～［３］のいずれかに記載の感光性樹脂組成物。
［５］　（Ａ）バインダーポリマーがカルボキシル基を有しており、その酸価が１００～３００ｍｇＫＯＨ／ｇであることを特徴とする［１］～［４］のいずれかに記載の感光性樹脂組成物。
［６］　［１］～［５］のいずれかに記載の感光性樹脂組成物からなる感光性樹脂組成物層と支持層を含むことを特徴とするフォトレジストフィルム。
［７］　［６］に記載のフォトレジストフィルムを用いて、基材上に感光性樹脂組成物層を形成し、露光し、現像することを含むレジストパターンの形成方法。
［８］　［６］に記載のフォトレジストフィルムを用いて、回路形成用基板上に感光性樹脂組成物層を形成し、露光し、現像して、レジストパターンを形成すること、および前記レジストパターンが形成された前記回路形成用基板をエッチングまたはめっきし、前記レジストパターンを剥離することを含む、導体パターンの形成方法。 The present invention includes the following aspects.
[1] Photosensitivity comprising (A) a binder polymer, (B) a photopolymerizable monomer having an amino group, (C) a photopolymerization initiator, and (D) a benzotriazole derivative having a carboxyl group. Resin composition.
[2] The photosensitive resin according to [1], wherein (B) the photopolymerizable monomer having an amino group is a photopolymerizable unsaturated compound represented by the following general formula (I): Composition.
Figure JPOXMLDOC01-appb-C000002
 (However, R 1 in the formula is independently each .R 2 and R 3 is H or CH 3, represents a hydrogen atom, an alkyl group, a group selected from the group consisting of alkoxy group and a halogen group, R 2 And R 3 may be bonded to each other to form a ring containing N. X represents an alkylene group having 1 to 10 carbon atoms, or (C 2 H 4 O) m or (C 3 H 6 O) n. M and n are each an integer of 1 to 10 polyoxyalkylene groups, and the polyoxyalkylene groups are random polymerization or block polymerization.)
[3] The photopolymerizable monomer having an amino group (B) is contained in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the (A) binder polymer [1] or [2] The photosensitive resin composition as described in 2.
[4] Any of [1] to [3], wherein (D) the benzotriazole derivative having a carboxyl group is contained in an amount of 0.01 to 2 parts by weight with respect to 100 parts by weight of the (A) binder polymer. A photosensitive resin composition according to claim 1.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein (A) the binder polymer has a carboxyl group, and the acid value thereof is 100 to 300 mgKOH / g. object.
[6] A photoresist film comprising a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [5] and a support layer.
[7] A method for forming a resist pattern comprising forming a photosensitive resin composition layer on a substrate using the photoresist film according to [6], exposing and developing.
[8] Using the photoresist film according to [6], a photosensitive resin composition layer is formed on a circuit-forming substrate, exposed and developed to form a resist pattern, and the resist pattern A method for forming a conductor pattern, comprising: etching or plating the circuit forming substrate on which is formed, and peeling the resist pattern.
　本発明の感光性樹脂組成物及びフォトレジストフィルムは、解像性及び密着性が良好で、かつ現像後の硬化レジストのスソが極めて小さく、剥離性も良好であるという効果を有する。したがって、本発明のフォトレジストフィルムを用いたレジストパターンの形成方法及び導体パターンの形成方法により、レジストパターンの剥離不良や導体パターン（配線）の剥がれが低減するという効果が得られる。 The photosensitive resin composition and the photoresist film of the present invention have the effect that the resolution and adhesion are good, and the cured resist has a very small skirt and a good peelability after development. Therefore, the resist pattern forming method and the conductor pattern forming method using the photoresist film of the present invention can provide an effect that the resist pattern peeling failure and the conductor pattern (wiring) peeling are reduced.
従来のフォトレジストフィルムを用いて、基板（銅薄膜）上に硬化レジストを形成し、めっき（銅配線）を形成した場合において、スソ（硬化レジストフット部）が発生することによる課題を示す模式的な断面図である。Ａは現像後、Ｂはめっき後、Ｃは剥離後の断面図を示す。Schematic showing a problem caused by the occurrence of sushi (cured resist foot) when a conventional photoresist film is used to form a cured resist on a substrate (copper thin film) and plating (copper wiring) is formed. FIG. A shows a cross-sectional view after development, B after plating, and C after peeling.
　以下、本発明について具体的に説明する。
　なお、本明細書において（メタ）アクリルはアクリル又はそれに対応するメタクリルを意味し、（メタ）アクリレートはアクリレート又はそれに対応するメタクリレートを意味し、（メタ）アクリロはアクリロ又はそれに対応するメタクリロを意味する。 Hereinafter, the present invention will be specifically described.
In the present specification, (meth) acryl means acryl or methacryl corresponding thereto, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acrylo means acrylo or methacrylo corresponding thereto. .
　〔感光性樹脂組成物〕
　本発明の感光性樹脂組成物は、（Ａ）バインダーポリマー、（Ｂ）アミノ基を有する光重合可能なモノマー、（Ｃ）光重合開始剤、及び（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体を含有することを特徴とする。 [Photosensitive resin composition]
The photosensitive resin composition of the present invention contains (A) a binder polymer, (B) a photopolymerizable monomer having an amino group, (C) a photopolymerization initiator, and (D) a benzotriazole derivative having a carboxyl group. It is characterized by doing.
　（Ａ）バインダーポリマーとしては、例えば、アクリル系重合体、スチレン系重合体、エポキシ系重合体、アミド系重合体、アミドエポキシ系重合体、アルキド系重合体、フェノール系重合体等が挙げられ、これら重合体のうち１種を単独で又は２種以上を組み合わせて用いることができる。これら重合体の中でも、カルボキシル基含有ポリマーが好ましい。 Examples of the (A) binder polymer include acrylic polymers, styrene polymers, epoxy polymers, amide polymers, amide epoxy polymers, alkyd polymers, phenol polymers, and the like. One of these polymers can be used alone or in combination of two or more. Among these polymers, a carboxyl group-containing polymer is preferable.
　カルボキシル基含有ポリマーとしては、アクリル系重合体、ポリエステル系重合体、ポリアミド系重合体、エポキシ系重合体等が例示され、中でも（メタ）アクリル酸エステルとエチレン性不飽和カルボン酸及び必要に応じてその他の共重合可能なモノマーを共重合させてなるアクリル系重合体を用いることが好ましい。
　上記（メタ）アクリル酸エステルに基づく構成単位の含有量（使用する全重合性単量体に対する（メタ）アクリル酸エステルの割合）は、アルカリ現像性、解像度及び剥離特性を良好にする見地から、１０～７０質量部含むことが好ましく、更には２０～６０質量部含むことが好ましく、特には３０～５０質量部含むことが好ましい。
　また、エチレン性不飽和カルボン酸に基づく構成単位の含有量（使用する全重合性単量体に対するエチレン性不飽和カルボン酸の割合）は、解像性及び密着性、スソ発生抑制、剥離性の観点から、１２～５０質量部であることが好ましく、更には１５～４０質量部であることが好ましく、特には１８～３０質量部であることが好ましい。エチレン性不飽和カルボン酸の含有量が少なすぎるとアルカリ反応性が劣り、現像時間、剥離時間が長くなる傾向があり、多すぎると現像液耐性が低下し、密着性が低下する傾向がある。
　さらに、その他の共重合可能なモノマーに基づく構成単位の含有量（使用する全重合性単量体に対するその他の共重合可能なモノマーの割合）は、１０～８０質量部含むことが好ましく、更には２０～７０質量部含むことが好ましく、特には３０～６０質量部含むことが好ましい。
　これらのカルボキシル基含有ポリマーは、単独で又は２種類以上を組み合わせて使用される。２種類以上を組み合わせて使用する場合のカルボキシル基含有ポリマーとしては、例えば、異なる共重合成分からなる２種類以上のカルボキシル基含有ポリマー、異なる重量平均分子量の２種類以上のカルボキシル基含有ポリマー、異なる分散度の２種類以上のカルボキシル基含有ポリマーなどが挙げられる。
　以下、かかるアクリル系重合体について説明する。但し、本発明で用いられるアクリル系重合体は、以下に限定されるものではない。 Examples of the carboxyl group-containing polymer include acrylic polymers, polyester polymers, polyamide polymers, epoxy polymers and the like. Among them, (meth) acrylic acid esters and ethylenically unsaturated carboxylic acids and as necessary. It is preferable to use an acrylic polymer obtained by copolymerizing other copolymerizable monomers.
The content of the structural unit based on the (meth) acrylic acid ester (ratio of the (meth) acrylic acid ester to the total polymerizable monomer to be used) is from the viewpoint of improving the alkali developability, resolution, and release properties. The content is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass.
In addition, the content of the structural unit based on the ethylenically unsaturated carboxylic acid (ratio of the ethylenically unsaturated carboxylic acid to the total polymerizable monomer used) is high in resolution and adhesion, soot generation suppression, and peelability. From the viewpoint, it is preferably 12 to 50 parts by mass, more preferably 15 to 40 parts by mass, and particularly preferably 18 to 30 parts by mass. If the content of the ethylenically unsaturated carboxylic acid is too small, the alkali reactivity tends to be inferior and the development time and the peeling time tend to be long. If the content is too large, the developer resistance tends to decrease and the adhesion tends to decrease.
Further, the content of structural units based on other copolymerizable monomers (ratio of other copolymerizable monomers to the total polymerizable monomers used) is preferably 10 to 80 parts by mass, It is preferably 20 to 70 parts by mass, particularly preferably 30 to 60 parts by mass.
These carboxyl group-containing polymers are used alone or in combination of two or more. Examples of the carboxyl group-containing polymer used in combination of two or more types include, for example, two or more types of carboxyl group-containing polymers composed of different copolymerization components, two or more types of carboxyl group-containing polymers having different weight average molecular weights, and different dispersions. And two or more kinds of carboxyl group-containing polymers.
Hereinafter, the acrylic polymer will be described. However, the acrylic polymer used in the present invention is not limited to the following.
　上記（メタ）アクリル酸エステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等のアルキル基の炭素数が１～２０、好ましくは１～１０の脂肪族（メタ）アクリレート；ベンジル（メタ）アクリレート等の芳香族（メタ）アクリレート；ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート等のアミノ基含有（メタ）アクリレート；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリレート；グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート等が挙げられ、これらは単独で又は２種以上を組み合わせて用いることができる。 Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Aliphatic (meth) acrylates having an alkyl group such as cyclohexyl (meth) acrylate having 1 to 20, preferably 1 to 10 carbon atoms; Aromatic (meth) acrylates such as benzyl (meth) acrylate; Diethylaminoethyl (meth) acrylate Amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate; hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate Examples include epoxy group-containing (meth) acrylates such as carbonate, 2,2,2-trifluoroethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc., and these are used alone or in combination of two or more. be able to.
　上記エチレン性不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸等のモノカルボン酸が好適に用いられ、マレイン酸、フマル酸、イタコン酸等のジカルボン酸や、それらの無水物やハーフエステルを用いることもでき、これらは単独で又は２種以上を組み合わせて用いることができる。中でも、アクリル酸、メタクリル酸が特に好ましい。 Examples of the ethylenically unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and anhydrides thereof. Half esters can also be used, and these can be used alone or in combination of two or more. Of these, acrylic acid and methacrylic acid are particularly preferable.
　上記その他の共重合可能なモノマーとしては、例えば、（メタ）アクリルアミド、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、アクリルアミド、ジアセトンアクリルアミド、スチレン、α－メチルスチレン、ビニルナフタレン、ビニルシクロヘキサン、ビニルトルエン、酢酸ビニル、アルキルビニルエーテル、（メタ）アクリロニトリル等が挙げられ、これらは単独で又は２種以上を組み合わせて用いることができる。 Examples of the other copolymerizable monomers include (meth) acrylamide, 2,2,3,3-tetrafluoropropyl (meth) acrylate, acrylamide, diacetone acrylamide, styrene, α-methylstyrene, vinylnaphthalene, Examples include vinylcyclohexane, vinyltoluene, vinyl acetate, alkyl vinyl ether, (meth) acrylonitrile and the like, and these can be used alone or in combination of two or more.
　かかるアクリル系重合体については、解像性及び密着性、スソ発生抑制、剥離性の観点から、重量平均分子量は０．５万～２０万が好ましく、更には１万～１０万が好ましく、酸価は１００～３００ｍｇＫＯＨ／ｇが好ましく、更には１２０～２５０ｍｇＫＯＨ／ｇ、特には１４０～１９０ｍｇＫＯＨ／ｇが好ましい。なお、重量平均分子量（Ｍｗ）は、ＧＰＣ（ゲル浸透クロマトグラフィー）装置を用い、乾燥ポリマーのＴＨＦ（テトラヒドロフラン）溶解液をポリスチレン基準で測定した値である。
　かかる酸価は、ポリマー１ｇを中和するのに必要なＫＯＨ（水酸化カリウム）の重量であり、例えば、メタノール等のアルコール類や、アセトン、メチルエチルケトン等のケトン類、または、これらの混合溶媒に溶解させたポリマーを中和滴定することで測定されるものである。 With respect to such an acrylic polymer, the weight average molecular weight is preferably 50,000 to 200,000, more preferably 10,000 to 100,000, from the viewpoints of resolution and adhesion, soot generation suppression, and peelability. The value is preferably 100 to 300 mgKOH / g, more preferably 120 to 250 mgKOH / g, and particularly preferably 140 to 190 mgKOH / g. The weight average molecular weight (Mw) is a value obtained by measuring a THF (tetrahydrofuran) solution of a dry polymer on a polystyrene basis using a GPC (gel permeation chromatography) apparatus.
The acid value is the weight of KOH (potassium hydroxide) necessary to neutralize 1 g of the polymer. For example, the acid value is determined by adding alcohols such as methanol, ketones such as acetone and methyl ethyl ketone, or a mixed solvent thereof. It is measured by neutralizing titrating the dissolved polymer.
　かかる重量平均分子量が小さすぎると硬化後の感光性樹脂組成物が脆くなる傾向にあり、逆に大きすぎると解像性やレジスト剥離性が低下する傾向にある。また、上記酸価が小さすぎると、解像性やレジスト剥離性の低下を抑える効果が弱くなる傾向にあり、逆に大きすぎると硬化レジストの細線密着性の低下を抑える効果が弱くなる傾向にある。 If the weight average molecular weight is too small, the cured photosensitive resin composition tends to be brittle, whereas if it is too large, the resolution and resist peelability tend to decrease. In addition, if the acid value is too small, the effect of suppressing a decrease in resolution and resist peelability tends to be weakened. On the other hand, if the acid value is too large, the effect of suppressing a decrease in fine line adhesion of the cured resist tends to be weakened. is there.
　上記アクリル系重合体のガラス転移温度（Ｔｇ）は３０～１５０℃の範囲が好ましく、更には６０～１２０℃の範囲が好ましい。ガラス転移温度が低すぎると感光性樹脂組成物が流動し易く、フォトレジストフィルムとしてロール状とする時にエッジフュージョンを引き起す傾向にあり、一方、ガラス転移温度が高すぎるとフォトレジストフィルムとして用いた時の基材表面の凹凸への追従性が低下する傾向にある。 The glass transition temperature (Tg) of the acrylic polymer is preferably in the range of 30 to 150 ° C, more preferably in the range of 60 to 120 ° C. If the glass transition temperature is too low, the photosensitive resin composition tends to flow and tends to cause edge fusion when it is rolled into a photoresist film. On the other hand, if the glass transition temperature is too high, it is used as a photoresist film. There is a tendency that the followability to the unevenness of the substrate surface at the time is lowered.
　かかるガラス転移温度（Ｔｇ）は、ＤＳＣ（Ｄｉｆｆｅｒｅｎｔｉａｌ　Ｓｃａｎｎｉｎｇ　Ｃａｌｏｒｉｍｅｔｒｙ）で測定したり、バインダーポリマーの共重合モノマーのホモポリマーのガラス転移温度が既知の場合、Ｆｏｘの式を用いて算出したりすることができる。本発明においては、Ｆｏｘの式により算出されたものである。 The glass transition temperature (Tg) may be measured by DSC (Differential Scanning Colorimetry) or may be calculated using the Fox equation when the glass transition temperature of the homopolymer of the copolymer monomer of the binder polymer is known. it can. In the present invention, it is calculated by the Fox equation.
Figure JPOXMLDOC01-appb-M000003
 （Ｔｇは、共重合体のガラス転移温度を表す。Ｗａ、Ｗｂ、・・・は、ａ成分、ｂ成分、・・・の重量分率を示す。Ｔａ、Ｔｂ、・・・は、ａ成分、ｂ成分、・・・のホモポリマーのガラス転移温度を表す。）
Figure JPOXMLDOC01-appb-M000003
 (Tg represents the glass transition temperature of the copolymer. Wa, Wb,... Represent the weight fraction of the a component, b component,... Ta, Tb,. , B represents the glass transition temperature of the homopolymer of component.
　（Ｂ）アミノ基を有する光重合可能なモノマーとしては、例えば、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミド、ノルマルプロピル（メタ）アクリルアミド、イソプロピル（メタ）アクリルアミド、Ｎ－（メタ）アクリロイルモルホリンなどの他、下記一般式（Ｉ）で表される群から選ばれる少なくとも一種の光重合可能な不飽和化合物も挙げられる。中でも、スソ低減効果の点で、下記一般式（Ｉ）で表される光重合可能な不飽和化合物を用いることが好ましい。 (B) Examples of the photopolymerizable monomer having an amino group include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth). In addition to acrylamide, normal propyl (meth) acrylamide, isopropyl (meth) acrylamide, N- (meth) acryloylmorpholine, at least one photopolymerizable unsaturated compound selected from the group represented by the following general formula (I) Also mentioned. Among them, it is preferable to use a photopolymerizable unsaturated compound represented by the following general formula (I) from the viewpoint of the effect of reducing the soot.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（但し、式中のＲ１はＨまたはＣＨ３である。Ｒ２及びＲ３はそれぞれ独立して水素原子、アルキル基、アルコキシ基及びハロゲン基からなる群から選ばれる基を表し、Ｒ２及びＲ３が互いに結合してＮを含む環を形成しても良い。Ｘは炭素数１～１０のアルキレン基、または（Ｃ２Ｈ４Ｏ）ｍまたは（Ｃ３Ｈ６Ｏ）ｎで示され、ｍ、ｎが各々１～１０の整数のポリオキシアルキレン基であり、ポリオキシアルキレン基はランダム重合またはブロック重合である。） (However, R 1 in the formula represents H or CH 3 a is .R 2 and R 3 are each independently a hydrogen atom, an alkyl group, a group selected from the group consisting of alkoxy group and a halogen group, R 2 and R 3 may be bonded to each other to form a ring containing N. X represents an alkylene group having 1 to 10 carbon atoms, or (C 2 H 4 O) m or (C 3 H 6 O) n. , M and n are each an integer of 1 to 10 polyoxyalkylene groups, and the polyoxyalkylene groups are random polymerization or block polymerization.)
　上記一般式（Ｉ）において、式中のＲ１はＨまたはＣＨ３である。Ｒ２及びＲ３はそれぞれ独立して水素原子、アルキル基、アルコキシ基及びハロゲン基からなる群から選ばれる基を表し、Ｒ２及びＲ３が互いに結合してＮを含む環を形成しても良い。アルキル基及びアルコキシ基の炭素数は、通常、１～１０、好ましくは１～６である。Ｘは炭素数１～１０、好ましくは１～６のアルキレン基、または（Ｃ２Ｈ４Ｏ）ｍまたは（Ｃ３Ｈ６Ｏ）ｎで示され、ｍ、ｎが各々１～１０の整数のポリオキシアルキレン基である。ポリオキシアルキレン基はランダム重合であっても、ブロック重合であってもよい。 In the general formula (I), R 1 in the formula is H or CH 3 . R 2 and R 3 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen group, and R 2 and R 3 may be bonded to each other to form a ring containing N. good. The alkyl group and alkoxy group usually have 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. X is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or (C 2 H 4 O) m or (C 3 H 6 O) n, and m and n are each an integer of 1 to 10 It is a polyoxyalkylene group. The polyoxyalkylene group may be random polymerization or block polymerization.
　上記一般式（Ｉ）で表される化合物としては、具体的には、例えば、Ｎ，Ｎ－ジメチルアミノメチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノブチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノペンチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノヘキシル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノヘプチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノオクチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノノニル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノデシル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノメチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノブチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノペンチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノヘキシル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノヘプチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノオクチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノノニル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノデシル（メタ）アクリレート、などのジアルキルアミノアルキル（メタ）アクリレート；Ｎ－ｎ－プロピルアミノエチル（メタ）アクリレート、Ｎ－ｉｓｏ－プロピルアミノエチル（メタ）アクリレート、Ｎ－ｔｅｒｔ－ブチルアミノエチル（メタ）アクリレート、Ｎ－ｎ－ブチルアミノエチル（メタ）アクリレート、などのモノアルキルアミノアルキル（メタ）アクリレート；Ｎ，Ｎ－ジメチルアミノポリエチレングリコール（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノポリエチレングリコール（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノポリプロピレングリコール（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノポリプロピレングリコール（メタ）アクリレート、などのジアルキルアミノポリエーテル（メタ）アクリレート；モルホリノエチル（メタ）アクリレートなどの環状アミノアルキル（メタ）アクリレートが挙げられる。中でも、ジアルキルアミノアルキル（メタ）アクリレートが好ましく、特にはジエチルアミノアルキル（メタ）アクリレートが用いられる。 Specific examples of the compound represented by the general formula (I) include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethyl. Aminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-dimethylaminopentyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-dimethylaminoheptyl (Meth) acrylate, N, N-dimethylaminooctyl (meth) acrylate, N, N-dimethylaminononyl (meth) acrylate, N, N-dimethylaminodecyl (meth) acrylate, N, N-diethylaminomethyl (meth) Acrylate, N, N-diethylaminoethyl (meth) acryl N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-diethylaminopentyl (meth) acrylate, N, N-diethylaminohexyl (meth) acrylate, N, N Dialkylaminoalkyl (meth) acrylates such as diethylaminoheptyl (meth) acrylate, N, N-diethylaminooctyl (meth) acrylate, N, N-diethylaminononyl (meth) acrylate, N, N-diethylaminodecyl (meth) acrylate, etc. Nn-propylaminoethyl (meth) acrylate, N-iso-propylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, Nn-butylaminoethyl (meth) acrylate Monoalkylaminoalkyl (meth) acrylates such as rate; N, N-dimethylaminopolyethylene glycol (meth) acrylate, N, N-diethylaminopolyethylene glycol (meth) acrylate, N, N-dimethylaminopolypropylene glycol (meth) acrylate And dialkylamino polyether (meth) acrylates such as N, N-diethylaminopolypropylene glycol (meth) acrylate; and cyclic aminoalkyl (meth) acrylates such as morpholinoethyl (meth) acrylate. Among them, dialkylaminoalkyl (meth) acrylate is preferable, and diethylaminoalkyl (meth) acrylate is particularly used.
　なお、入手の容易さから、上記一般式においてＲ１がＣＨ３であり、Ｒ２及びＲ３がいずれもＣ２Ｈ５であり、ＸがＣ２Ｈ５である化合物、即ちＮ，Ｎ－ジエチルアミノエチルメタクリレート〔例えば、共栄社化学（株）製、商品名：ライトエステルＤＥ〕が最も好ましい。 From the viewpoint of availability, a compound in which R 1 is CH 3 , R 2 and R 3 are both C 2 H 5 and X is C 2 H 5 in the above general formula, that is, N, N— Most preferred is diethylaminoethyl methacrylate [for example, trade name: Light Ester DE, manufactured by Kyoeisha Chemical Co., Ltd.].
　ここで、硬化レジストのスソの発生は、硬化の弱い半硬化レジストの酸性基が現像液と一部反応し、除去されずに、現像後の乾燥時に半硬化レジストがレジスト下部に移動し再付着するためと推察されている。（Ｂ）の光重合可能なモノマーのアミノ基では、感光性樹脂組成物中で（Ａ）バインダーポリマー中の酸性基と中和反応を起こし、（Ａ）バインダーポリマーの酸性基がカバーされるので耐現像液性が向上し、半硬化レジストの再付着が減少、つまりスソが小さくなると考え得る。また、（Ｂ）のモノマーが光重合可能な構造を有しているため硬化度が上がり、密着性の向上も期待できる。したがって、（Ｂ）のモノマーとしては、アミノ基を有しており、且つ光重合可能な構造であれば同様の効果が期待できる。 Here, the occurrence of scum in the cured resist is due to the partial reaction of the acidic groups of the semi-cured resist, which is weakly cured, with the developer, and the semi-cured resist moves to the bottom of the resist during drying after development without being removed. It is presumed to be. The amino group of the photopolymerizable monomer (B) causes a neutralization reaction with the acidic group in the binder polymer (A) in the photosensitive resin composition, and (A) the acidic group of the binder polymer is covered. It can be considered that the developer resistance is improved and the reattachment of the semi-cured resist is reduced, that is, the sash is reduced. In addition, since the monomer (B) has a photopolymerizable structure, the degree of cure is increased and an improvement in adhesion can be expected. Therefore, the monomer (B) can have the same effect as long as it has an amino group and can be photopolymerized.
　なお、フォトレジストフィルムの用途に用いるような感光性樹脂組成物において、光重合可能なモノマー成分として（Ｂ）アミノ基を有する光重合可能なモノマーを用いることは、めっき浴やエッチング液などの酸性溶液への汚染といった不具合が発生することが懸念されるとの考えから、従来は行なわれなかった。しかし、本発明においては、アミノ基を有するモノマーを敢えて用いたところ、意外にもかかる不具合も生じることなく、本発明の目的を達成することができたのである。 In addition, in a photosensitive resin composition used for a photoresist film, the use of (B) a photopolymerizable monomer having an amino group as a photopolymerizable monomer component is an acidity such as a plating bath or an etching solution. In the past, it was not performed because of the concern that problems such as contamination of the solution would occur. However, in the present invention, when the monomer having an amino group was used, the object of the present invention could be achieved without any unexpected problems.
　本発明において、上記の（Ｂ）アミノ基を有する光重合可能なモノマーの含有量は、（Ａ）バインダーポリマー１００重量部に対して、好ましくは０．０１～３０重量部、より好ましくは０．１～２５重量部、更に好ましくは０．５～２０重量部、特に好ましくは１～１５重量部である。かかる含有量が少なすぎるとスソ低減の効果が不十分となる傾向があり、多すぎると解像性が低下する傾向がある。 In the present invention, the content of the photopolymerizable monomer (B) having an amino group is preferably 0.01 to 30 parts by weight, more preferably 0.8 parts per 100 parts by weight of the (A) binder polymer. The amount is 1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, and particularly preferably 1 to 15 parts by weight. When the content is too small, the effect of reducing the soot tends to be insufficient, and when the content is too large, the resolution tends to decrease.
　（Ｂ）アミノ基を有する光重合可能なモノマーと共に、下記に示される光重合可能なモノマーも用いることができる。例えば、重合性不飽和基を１個有する単量体として、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－フェノキシ－２－ヒドロキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシ－２－ヒドロキシプロピルフタレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルアシッドホスフェート、フタル酸誘導体のハーフ（メタ）アクリレート等が挙げられ、これらは単独で又は２種以上を組み合わせて用いることができる。 (B) The photopolymerizable monomer shown below can be used together with the photopolymerizable monomer having an amino group. For example, as a monomer having one polymerizable unsaturated group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxy Propyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate , Half (meth) acrylates of phthalic acid derivatives, and the like, and these can be used alone or in combination of two or more.
　また、重合性不飽和基を２個有する単量体として、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ポリエチレングリコール・ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、オキシエチレン基含有ビスフェノールＡ型ジ（メタ）アクリレート、オキシプロピレン基含有ビスフェノールＡ型ジ（メタ）アクリレート、オキシエチレン基・オキシプロピレン基含有ビスフェノールＡ型ジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、エチレングリコールジグリシジルエーテルジ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、フタル酸ジグリシジルエステルジ（メタ）アクリレート、ヒドロキシピバリン酸変性ネオペンチルグリコールジ（メタ）アクリレート等が挙げられ、これらは単独で又は２種以上を組み合わせて用いることができる。中でも特に、オキシエチレン基含有ビスフェノールＡ型ジ（メタ）アクリレート、ポリエチレングリコール・ポリプロピレングリコールジ（メタ）アクリレートが好ましく用いられる。 Examples of the monomer having two polymerizable unsaturated groups include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol / polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, oxyethylene group-containing bisphenol A Type di (meth) acrylate, oxypropylene group-containing bisphenol A type di (meth) acrylate, oxyethylene / oxypropylene group-containing bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether Examples include di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, and hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, which can be used alone or in combination of two or more. Of these, oxyethylene group-containing bisphenol A di (meth) acrylate and polyethylene glycol / polypropylene glycol di (meth) acrylate are preferably used.
　さらに、重合性不飽和基を３個以上有する単量体として、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリ（メタ）アクリロイルオキシエトキシトリメチロールプロパン、グリセリンポリグリシジルエーテルポリ（メタ）アクリレート等が挙げられ、これらは単独で又は２種以上を組み合わせて用いることができる。 Furthermore, as a monomer having three or more polymerizable unsaturated groups, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyl Examples thereof include oxyethoxytrimethylolpropane and glycerin polyglycidyl ether poly (meth) acrylate, and these can be used alone or in combination of two or more.
　また、ウレタン（メタ）アクリレートも挙げられる。ウレタン（メタ）アクリレートとしては、例えば、ヘキサメチレンジイソシアネート、トリレンジイソシアネート等のジイソシアネートと、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、オリゴプロピレングリコールモノメタクリレート等の一分子中にヒドロキシル基と（メタ）アクリル基を有する水酸基含有（メタ）アクリレート、必要に応じて、ポリオールとを反応させて得られる化合物が挙げられる。これらは単独で使用しても、２種類以上を併用しても構わない。 Also, urethane (meth) acrylate may be mentioned. Examples of urethane (meth) acrylates include diisocyanates such as hexamethylene diisocyanate and tolylene diisocyanate, and hydroxyl groups in one molecule such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and oligopropylene glycol monomethacrylate. Examples thereof include a hydroxyl group-containing (meth) acrylate having a (meth) acryl group and, if necessary, a compound obtained by reacting with a polyol. These may be used alone or in combination of two or more.
　本発明において、（Ｂ）アミノ基を有する光重合可能なモノマー及び（Ｂ）以外の光重合可能なモノマーの合計量については、（Ａ）バインダーポリマー１００重量部に対して、１０～２００重量部であることが好ましく、特には３０～１６０重量部、更には５０～１２０重量部、殊には６０～１００重量部であることが好ましい。かかる含有量が少なすぎると硬化が不十分となる傾向があり、多すぎるとコールドフローが発生しやすくなる傾向がある。 In the present invention, the total amount of the photopolymerizable monomer (B) having an amino group and the photopolymerizable monomer other than (B) is 10 to 200 parts by weight with respect to 100 parts by weight of the (A) binder polymer. It is preferably 30 to 160 parts by weight, more preferably 50 to 120 parts by weight, and particularly preferably 60 to 100 parts by weight. When the content is too small, curing tends to be insufficient, and when the content is too large, cold flow tends to occur.
　（Ｃ）光重合開始剤としては、例えば、（Ｃ１）ヘキサアリールビスイミダゾール誘導体、（Ｃ２）アルキルアミノベンゾフェノン誘導体、Ｎ－アリールグリシン誘導体、アクリジン誘導体、ジアミノアントラキノン等のアントラキノン誘導体、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラアリールベンジジン誘導体、三酢酸リボフラビン、ベンゾフェノン、ベンジルジメチルケタール、チオキサントン誘導体、アルキルアミノ安息香酸アルキルエステル、トリアジン誘導体、クマリン６等のクマリン誘導体、トリフェニルホスフィン、トリトリルホスフィン、トリキシリルホスフィン、トリビフェニルホスフィン、トリナフチルホスフィン、トリアントリルホスフィン、トリフェナントリルホスフィン等のトリアリールホスフィン等が挙げられ、これらは単独で又は２種以上を組み合わせて用いることができる。 Examples of (C) photopolymerization initiators include (C1) hexaarylbisimidazole derivatives, (C2) alkylaminobenzophenone derivatives, N-arylglycine derivatives, acridine derivatives, anthraquinone derivatives such as diaminoanthraquinone, N, N, N ', N'-tetraarylbenzidine derivatives, riboflavin triacetate, benzophenone, benzyldimethyl ketal, thioxanthone derivatives, alkylaminobenzoic acid alkyl esters, triazine derivatives, coumarin derivatives such as coumarin 6, triphenylphosphine, tolylphosphine, trixylyl And triarylphosphine such as phosphine, tribiphenylphosphine, trinaphthylphosphine, trianthrylphosphine, triphenanthrylphosphine, etc. It can be used alone or in combination of two or more.
　（Ｃ１）ヘキサアリールビスイミダゾール誘導体としては、例えば、２，２′－ビス（２，３－ジクロロフェニル）－４，４′，５，５′－テトラキス（３－メトキシフェニル）ビスイミダゾール、２，２′－ビス（２，３－ジクロロフェニル）－４，４′，５，５′－テトラキス（４－メトキシフェニル）ビスイミダゾール、２，２′－ビス（２，４－ジクロロフェニル）－４，４′，５，５′－テトラキス（３－メトキシフェニル）フェニルビスイミダゾール、２，２′－ビス（２，５－ジクロロフェニル）－４，４′，５，５′－テトラキス（３－メトキシフェニル）ビスイミダゾール、２，２′－ビス（２，６－ジクロロフェニル）－４，４′，５，５′－テトラキス（３－メトキシフェニル）ビスイミダゾール、２，２′，４，４′－テトラキス（２－クロロフェニル）－５，５′－ビス（３－メトキシフェニル）ビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４，４′，５，５′－テトラフェニルビスイミダゾール、２，２′，４，４′－テトラキス（２－クロロフェニル）－５，５′－ビス（４－メトキシフェニル）ビスイミダゾール、２，２′，４，４′－テトラキス（２－クロロフェニル）－５，５′－ビス（２，３－ジメトキシフェニル）ビスイミダゾール、２，２′，４，４′－テトラキス（２－クロロフェニル）－５，５′－ビス（３，４－ジメトキシフェニル）ビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４，４′，５，５′－テトラキス（４－メトキシフェニル）ビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４，４′，５，５′－テトラキス（３，４－ジメトキシフェニル）ビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４，４′，５，５′－テトラキス（３，４，５－トリメトキシフェニル）ビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４，５－ビス（３－メトキシフェニル）－４′，５′－ジフェニルビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４，５－ビス（３，４－ジメトキシフェニル）－４′，５′－ジフェニルビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４－（３，４－ジメトキシフェニル）－４′，５，５′－トリフェニルビスイミダゾール等が挙げられ、中でも２，２′，４，４′－テトラキス（２－クロロフェニル）－５，５′－ビス（３－メトキシフェニル）ビスイミダゾール、２，２′，４，４′－テトラキス（２－クロロフェニル）－５，５′－ビス（２，３－ジメトキシフェニル）ビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４－（３，４－ジメトキシフェニル）－４′，５，５′－トリフェニルビスイミダゾール、２，２′－ビス（２－クロロフェニル）－４，４′，５，５′－テトラフェニルビスイミダゾールが好適であり、これらは単独で又は２種以上を組み合わせて用いることができる。 Examples of (C1) hexaarylbisimidazole derivatives include 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (3-methoxyphenyl) bisimidazole, 2,2 '-Bis (2,3-dichlorophenyl) -4,4', 5,5'-tetrakis (4-methoxyphenyl) bisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5′-tetrakis (3-methoxyphenyl) phenylbisimidazole, 2,2′-bis (2,5-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2', 4 '-Tetrakis (2-chlorophenyl) -5,5'-bis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole 2,2 ', 4,4'-tetrakis (2-chlorophenyl) -5,5'-bis (4-methoxyphenyl) bisimidazole, 2,2', 4,4'-tetrakis (2-chlorophenyl)- 5,5'-bis (2,3-dimethoxyphenyl) bisimidazole, 2,2 ', 4,4'-tetrakis (2-chlorophenyl) -5,5'-bis (3,4-dimethoxyphenyl) bisimidazole 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-methoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) Nyl) -4,4 ′, 5,5′-tetrakis (3,4-dimethoxyphenyl) bisimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3 , 4,5-trimethoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,5-bis (3-methoxyphenyl) -4 ', 5'-diphenylbisimidazole, 2,2' -Bis (2-chlorophenyl) -4,5-bis (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4- (3,4 -Dimethoxyphenyl) -4 ', 5,5'-triphenylbisimidazole and the like, among others, 2,2', 4,4'-tetrakis (2-chlorophenyl) -5,5'-bis (3-methoxy Phenyl) bisimidazole, 2,2 ', 4,4'-tetrakis (2-chlorophenyl) -5,5'-bis (2,3-dimethoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5,5'-triphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbis Imidazole is preferred, and these can be used alone or in combination of two or more.
　（Ｃ２）アルキルアミノベンゾフェノン誘導体としては、例えば、４，４′－ビス（ジエチルアミノ）ベンゾフェノン、３，３′－ジメチル－４－メトキシベンゾフェノン、４，４′－ビス（ジメチルアミノ）ベンゾフェノン等が挙げられ、中でも４，４′－ビス（ジエチルアミノ）ベンゾフェノンが特に好ましく、これらは単独で又は２種以上を組み合わせて用いることができる。 Examples of (C2) alkylaminobenzophenone derivatives include 4,4′-bis (diethylamino) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bis (dimethylamino) benzophenone, and the like. Among these, 4,4′-bis (diethylamino) benzophenone is particularly preferable, and these can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物は、高感度化の観点から、光重合開始剤（Ｃ）として、少なくとも（Ｃ１）ヘキサアリールビスイミダゾール誘導体を含有することが好ましく、特には（Ｃ１）ヘキサアリールビスイミダゾール誘導体及び他の光重合開始剤を含有することが好ましく、更には（Ｃ１）ヘキサアリールビスイミダゾール誘導体及び（Ｃ２）アルキルアミノベンゾフェノン誘導体を含有することが好ましい。 The photosensitive resin composition of the present invention preferably contains at least (C1) hexaarylbisimidazole derivative as the photopolymerization initiator (C) from the viewpoint of increasing sensitivity, and in particular, (C1) hexaarylbis. It preferably contains an imidazole derivative and another photopolymerization initiator, and further preferably contains a (C1) hexaarylbisimidazole derivative and (C2) an alkylaminobenzophenone derivative.
　（Ｃ）光重合開始剤の含有量は、（Ａ）バインダーポリマー１００重量部に対して、１～２０重量部であることが好ましく、特には２～１６重量部、更には３～１２重量部であることが好ましい。（Ｃ）光重合開始剤の含有量が少なすぎると必要な感度、解像性、及び密着性が得られない傾向にあり、また多すぎると感光性樹脂組成物中に不溶解物を生じる傾向にある。 The content of the (C) photopolymerization initiator is preferably 1 to 20 parts by weight, particularly 2 to 16 parts by weight, more preferably 3 to 12 parts by weight with respect to 100 parts by weight of the (A) binder polymer. It is preferable that (C) If the content of the photopolymerization initiator is too small, the required sensitivity, resolution, and adhesion tend to be not obtained, and if too large, insoluble matter tends to be generated in the photosensitive resin composition. It is in.
　（Ｃ１）ヘキサアリールビスイミダゾール誘導体及び他の光重合開始剤を併用する場合、例えば（Ｃ１）ヘキサアリールビスイミダゾール誘導体及び（Ｃ２）アルキルアミノベンゾフェノン誘導体を併用する場合は、（Ａ）バインダーポリマー１００重量部に対して、（Ｃ１）ヘキサアリールビスイミダゾール誘導体が１～１６重量部、特には２～１３重量部、更には３～１０重量部であることが好ましく、（Ｃ２）アルキルアミノベンゾフェノン誘導体が０．０１～４重量部、特には０．０２～３重量部、更には０．０６～２重量部であることが好ましい。 When (C1) a hexaarylbisimidazole derivative and another photopolymerization initiator are used in combination, for example, when (C1) a hexaarylbisimidazole derivative and (C2) an alkylaminobenzophenone derivative are used in combination, (A) 100 weight of binder polymer The amount of (C1) hexaarylbisimidazole derivative is preferably 1 to 16 parts by weight, particularly 2 to 13 parts by weight, more preferably 3 to 10 parts by weight, and (C2) the alkylaminobenzophenone derivative is 0 parts by weight. It is preferably 0.01 to 4 parts by weight, particularly 0.02 to 3 parts by weight, and more preferably 0.06 to 2 parts by weight.
　（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体としては、例えば、４－カルボキシベンゾトリアゾール、５－カルボキシベンゾトリアゾール、１－（１′，２′－ジカルボキシエチル）ベンゾトリアゾール、１－（２′，３′－ジカルボキシプロピル）ベンゾトリアゾール、１－（（ビス（２－エチルヘキシル）アミノ）メチル）－１Ｈ－ベンゾトリアゾールカルボン酸が好適に用いられ、これらは単独で又は２種以上を組み合わせて用いることができる。なお、入手の容易さから、４－カルボキシベンゾトリアゾールや、５－カルボキシベンゾトリアゾールが特に好ましい。 Examples of (D) benzotriazole derivatives having a carboxyl group include 4-carboxybenzotriazole, 5-carboxybenzotriazole, 1- (1 ′, 2′-dicarboxyethyl) benzotriazole, 1- (2 ′, 3 '-Dicarboxypropyl) benzotriazole, 1-((bis (2-ethylhexyl) amino) methyl) -1H-benzotriazolecarboxylic acid is preferably used, and these may be used alone or in combination of two or more. it can. Note that 4-carboxybenzotriazole and 5-carboxybenzotriazole are particularly preferable because of their availability.
　ベンゾトリアゾール誘導体は、銅金属と親和性が良いことが知られており、銅基材上にフォトレジストフィルムをラミネートした後にベンゾトリアゾール誘導体が銅基材上に配位していると考えられる。カルボキシル基を有するベンゾトリアゾール誘導体では、剥離時の強いアルカリ水溶液と該カルボキシル基が中和反応を起こすため、レジストを銅基材の界面から容易に剥離できると推察される。 The benzotriazole derivative is known to have good affinity with copper metal, and it is considered that the benzotriazole derivative is coordinated on the copper substrate after laminating a photoresist film on the copper substrate. In the case of a benzotriazole derivative having a carboxyl group, the strong alkaline aqueous solution at the time of stripping and the carboxyl group cause a neutralization reaction, so that the resist can be easily stripped from the interface of the copper substrate.
　（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体の含有量は、（Ａ）バインダーポリマー１００重量部に対して、０．０１～２重量部であることが好ましく、特には０．０４～１．６重量部、更には０．０８～１重量部であることが好ましい。（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体の含有量が少なすぎると、剥離性が低下する傾向にあり、また多すぎると密着性が低下し、スソも大きくなる傾向にある。 The content of the (D) carboxyl group-containing benzotriazole derivative is preferably 0.01 to 2 parts by weight, particularly 0.04 to 1.6 parts by weight, based on 100 parts by weight of the (A) binder polymer. Part, more preferably 0.08 to 1 part by weight. (D) When there is too little content of the benzotriazole derivative which has a carboxyl group, there exists a tendency for peelability to fall, and when too large, there exists a tendency for adhesiveness to fall and for a soot to become large.
　また、本発明においては、スソの低減、及び剥離性を両立するという観点から、前記（Ｂ）成分と前記（Ｄ）成分を併用することが重要であり、前記（Ｂ）成分と前記（Ｄ）成分の重量比率（Ｂ）／（Ｄ）が１以上５００以下の範囲であることが好ましい。特には重量比率（Ｂ）／（Ｄ）が３以上２００以下の範囲であることが好ましく、更には重量比率（Ｂ）／（Ｄ）が５以上５０以下の範囲であることが好ましい。かかる比率が低すぎると剥離は容易にできるがスソが大きくなる傾向があり、高すぎるとスソの発生は抑制できるものの剥離が困難となる傾向がある。 Further, in the present invention, it is important to use the component (B) and the component (D) in combination from the viewpoint of achieving both reduction of sword and peelability, and the component (B) and the component (D). The weight ratio (B) / (D) of the component is preferably in the range of 1 to 500. In particular, the weight ratio (B) / (D) is preferably in the range of 3 to 200, and the weight ratio (B) / (D) is preferably in the range of 5 to 50. If the ratio is too low, peeling can be easily performed, but the soot tends to increase. If the ratio is too high, the generation of soot can be suppressed, but the peeling tends to be difficult.
　本発明の感光性樹脂組成物には、上記の（Ａ）～（Ｄ）の化合物に加えて、更に染料を含有させることも好ましく、さらにかかる染料としては、例えば、クリスタルバイオレット、マラカイトグリーン、マラカイトグリーンレイク、ブリリアントグリーン、ダイヤモンドグリーン、パテントブルー、チルバイオレット、ビクトリアブルー、ビクトリアピュアブルー、オイルブルー、ベイシックブルー２０、ローズアニリン、パラフクシン、エチレンバイオレット等の着色染料、トリス（４－ジメチルアミノ－２－メチルフェニル）メタン［ロイコクリスタルバイオレット］、トリス（４－ジメチルアミノ－２－メチルフェニル）メタン［ロイコマラカイトグリ－ン］、フルオラン染料等のロイコ染料等が挙げられる。 In addition to the compounds (A) to (D) described above, the photosensitive resin composition of the present invention preferably further contains a dye. Examples of such dyes include crystal violet, malachite green, and malachite. Green Lake, Brilliant Green, Diamond Green, Patent Blue, Chill Violet, Victoria Blue, Victoria Pure Blue, Oil Blue, Basic Blue 20, Rose Aniline, Parafuchsin, Ethylene Violet and other Coloring Dyes, Tris (4-Dimethylamino-2- And leuco dyes such as methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye.
　また、本発明の感光性樹脂組成物には、ハロゲン化合物を含有させても良い。ハロゲン化合物としては、例えば、臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンジル、臭化メチレン、トリブロモメチルフェニルスルフォン、四臭化炭素、トリス（２，３－ジブロモプロピル）ホスフェート、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、１，１，１－トリクロロ－２，２－ビス（ｐ－クロロフェニル）エタン、クロル化トリアジン化合物等が挙げられる。 Further, the photosensitive resin composition of the present invention may contain a halogen compound. Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like.
　更に、本発明の感光性樹脂組成物には、必要に応じて、可塑剤などの添加剤を含有させても良い。このような添加剤としては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシプロピレンポリオキシエチレンエーテル、ポリオキシエチレンモノメチルエーテル、ポリオキシプロピレンモノメチルエーテル、ポリオキシエチレンポリオキシプロピレンモノメチルエーテル、ポリオキシエチレンモノエチルエーテル、ポリオキシプロピレンモノエチルエーテル、ポリオキシエチレンポリオキシプロピレンモノエチルエーテル等のグリコール・エステル類、ジエチルフタレート等のフタル酸エステル類、ｏ－トルエンスルフォン酸アミド、ｐ－トルエンスルフォン酸アミド、クエン酸トリブチル、クエン酸トリエチル、アセチルクエン酸トリエチル、アセチルクエン酸トリ－ｎ－プロピル、アセチルクエン酸トリ－ｎ－ブチル等が挙げられる。 Furthermore, the photosensitive resin composition of the present invention may contain an additive such as a plasticizer, if necessary. Examples of such additives include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl Glycol esters such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, citric acid Tributyl, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, tri-n-acetyl citrate Chill, and the like.
　本発明の感光性樹脂組成物の熱安定性、保存安定性を向上させるために、感光性樹脂組成物にラジカル重合禁止剤を含有させることも可能である。ラジカル重合禁止剤としては、例えば、ｐ－メトキシフェノール、ハイドロキノン、ピロガロール、ナフチルアミン、ｔｅｒｔ－ブチルカテコール、塩化第一銅、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、２，２′－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２′－メチレンビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）、ニトロソフェニルヒドロキシアミンアルミニウム塩、及びジフェニルニトロソアミン等が挙げられる。 In order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, it is also possible to contain a radical polymerization inhibitor in the photosensitive resin composition. Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis. (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.
　本発明の感光性樹脂組成物は、必要に応じて、メタノール、エタノール、アセトン、メチルエチルケトン、メチルセロソルブ、エチルセロソルブ、トルエン、Ｎ，Ｎ－ジメチルホルムアミド、プロピレングリコールモノメチルエーテル等の溶剤又はこれらの混合溶剤に溶解して、固形分３０～６０重量％程度の溶液としても良い。この溶液を、後述するフォトレジストフィルムの感光性樹脂組成物層を形成するための塗布液として、使用することができる。なお、この塗布液を回路形成用基板などの基板上に塗布し、乾燥させて、感光性樹脂組成物層を形成することも可能ではあるが、作業効率等の観点から、後述のフォトレジストフィルムの感光性樹脂組成物層を形成するために用いるのが好ましい。 The photosensitive resin composition of the present invention is optionally mixed with a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. It is good also as a solution with a solid content of about 30 to 60% by weight. This solution can be used as a coating solution for forming a photosensitive resin composition layer of a photoresist film described later. Although it is possible to form a photosensitive resin composition layer by applying this coating solution on a substrate such as a circuit-forming substrate and drying it, from the viewpoint of work efficiency and the like, a photoresist film described later It is preferably used for forming a photosensitive resin composition layer.
　さらに、本発明の感光性樹脂組成物には、密着性付与剤、酸化防止剤、熱重合禁止剤、表面張力改質剤、安定剤、連鎖移動剤、消泡剤、難燃剤、等の添加剤を適宜含有させても良く、含有させる場合には、かかる含有量は、（Ａ）～（Ｄ）成分の固形分総量１００質量部に対して各々０．０１～２０質量部含有することが好ましく、更には０．０２～１５質量部含有することが好ましく、特には０．０３～１０質量部含有することが好ましい。これらは、単独で又は２種類以上を組み合わせて使用される。 Furthermore, the photosensitive resin composition of the present invention includes adhesion promoters, antioxidants, thermal polymerization inhibitors, surface tension modifiers, stabilizers, chain transfer agents, antifoaming agents, flame retardants, and the like. An agent may be contained as appropriate, and in such a case, the content is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) to (D). It is preferably contained in an amount of 0.02 to 15 parts by mass, and more preferably 0.03 to 10 parts by mass. These are used alone or in combination of two or more.
　〔フォトレジストフィルム〕
　本発明のフォトレジストフィルムは、感光性樹脂組成物からなる感光性樹脂組成物層と支持層を含む。ここで用いられる支持層としては、露光光源から放射される光を透過する透明なものが望ましい。 [Photoresist film]
The photoresist film of the present invention includes a photosensitive resin composition layer comprising a photosensitive resin composition and a support layer. The support layer used here is preferably a transparent layer that transmits light emitted from the exposure light source.
　このような支持層としては、例えば、ポリエチレンテレフタレートフィルム、ポリビニルアルコールフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリ塩化ビニリデンフィルム、塩化ビニリデン共重合フィルム、ポリメタクリル酸メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロニトリルフィルム、スチレン共重合体フィルム、ポリアミドフィルム、セルロース誘導体フィルム等が挙げられ、中でもポリエチレンテレフタレートフィルムが好適である。これらのフィルムは、必要に応じて延伸されたものも使用可能である。 As such a support layer, for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. Among these, a polyethylene terephthalate film is preferable. These films can be stretched if necessary.
　支持層のヘーズは５以下のものが好ましい。支持層の厚みは、薄い方が画像形成性及び経済性の面で有利であるが、強度を維持する必要から１０～３０μｍのものが好ましく用いられる。フォトレジストフィルムにおける感光性樹脂組成物層の厚みは、用途において異なるが、好ましくは５～１００μｍ、より好ましくは７～６０μｍ、特に好ましくは１０～５０μｍである。感光性樹脂組成物層が薄すぎると膜強度が低くなりすぎる傾向にあり、厚すぎると密着性、感度、解像性が低下する傾向にある。 The haze of the support layer is preferably 5 or less. A thinner support layer is advantageous in terms of image formation and economy, but a thickness of 10 to 30 μm is preferably used in order to maintain strength. The thickness of the photosensitive resin composition layer in the photoresist film varies depending on the application, but is preferably 5 to 100 μm, more preferably 7 to 60 μm, and particularly preferably 10 to 50 μm. If the photosensitive resin composition layer is too thin, the film strength tends to be too low, and if it is too thick, the adhesion, sensitivity, and resolution tend to decrease.
　本発明のフォトレジストフィルムは、必要により、感光性樹脂組成物層の支持層側とは反対側の表面に保護層を有しても良い。フォトレジストフィルムに用いられる保護層の重要な特性の１つは、使用時に感光性樹脂組成物層から容易に剥離できることであり、そのためには、感光性樹脂組成物層との密着力について支持層よりも保護層の方が充分小さいことが求められる。保護層としては、例えば、ポリエチレンフィルム、ポリプロピレンフィルムが好ましく使用できる。保護層の膜厚は１０～１００μｍが好ましく、１０～５０μｍがより好ましい。 The photoresist film of the present invention may have a protective layer on the surface opposite to the support layer side of the photosensitive resin composition layer, if necessary. One of the important characteristics of the protective layer used in the photoresist film is that it can be easily peeled off from the photosensitive resin composition layer at the time of use. For this purpose, the support layer is used for adhesion with the photosensitive resin composition layer. The protective layer is required to be sufficiently smaller than the protective layer. As the protective layer, for example, a polyethylene film or a polypropylene film can be preferably used. The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.
　本発明のフォトレジストフィルムは、本発明の感光性樹脂組成物を含有する塗布液を支持層の片面に塗工し、乾燥して、さらに必要に応じて、その塗工面を保護層で被覆することにより製造することができる。より具体的には、支持層の片面に、ロールコーター法やバーコーター法等で本発明の感光性樹脂組成物を含有する塗布液を均一に塗布し、５０～１２０℃、もしくは順次温度の高くなるオーブンで乾燥して感光性樹脂組成物層を形成し、次いで、該層の上面に保護層を加圧積層することにより製造することができる。 In the photoresist film of the present invention, a coating solution containing the photosensitive resin composition of the present invention is applied to one side of a support layer, dried, and if necessary, the coated surface is coated with a protective layer. Can be manufactured. More specifically, a coating liquid containing the photosensitive resin composition of the present invention is uniformly applied to one side of the support layer by a roll coater method, a bar coater method, or the like, and the temperature is gradually increased from 50 to 120 ° C. or higher. It can be manufactured by drying in an oven to form a photosensitive resin composition layer and then pressure laminating a protective layer on the upper surface of the layer.
　〔レジストパターンの形成方法〕
　本発明のフォトレジストフィルムを用いて、基材上にレジストパターンを形成するための各工程について説明する。
　本発明のフォトレジストフィルムを用いたレジストパターンは、積層工程、露光工程、及び現像工程を含む工程によって形成することができる。下記に具体的な方法の一例を示す。
　被加工基材としては、プリント配線板製造目的の場合には銅張積層板が挙げられ、また凹凸基材の製造目的の場合にはガラス基材（例えば、プラズマディスプレイパネル用基材や表面電解ディスプレイ基材）、貫通孔を形成したシリコーンウエハー及びセラミック基材などが挙げられる。プラズマディスプレイパネル用基材とは、ガラス基材上に電極を形成後、誘電体層を形成し、次いで隔壁用ガラスペーストを塗布し、隔壁用ガラスペースト部分にサンドブラスト加工を施し隔壁を形成した基材である。 [Method of forming resist pattern]
Each process for forming a resist pattern on a substrate using the photoresist film of the present invention will be described.
A resist pattern using the photoresist film of the present invention can be formed by a process including a lamination process, an exposure process, and a development process. An example of a specific method is shown below.
Examples of the substrate to be processed include a copper-clad laminate for the purpose of producing a printed wiring board, and a glass substrate (for example, a substrate for plasma display panel or surface electrolysis for the purpose of producing an uneven substrate). Display substrate), silicone wafers having through-holes, and ceramic substrates. The plasma display panel substrate is a substrate in which an electrode is formed on a glass substrate, a dielectric layer is formed, a partition wall glass paste is applied, and a partition wall glass paste portion is subjected to sandblasting to form a partition wall. It is a material.
　まず、ラミネーターを用いて積層工程を行う。フォトレジストフィルムが保護層を有する場合には保護層を剥離した後、ラミネーターで感光性樹脂組成物層を被加工基材表面に加熱圧着し積層する。この場合、感光性樹脂組成物層は基材表面の片面だけに積層しても良いし、両面に積層しても良い。この時の加熱温度は一般的に４０～１６０℃である。 First, a lamination process is performed using a laminator. When the photoresist film has a protective layer, the protective layer is peeled off, and then the photosensitive resin composition layer is heat-pressed and laminated on the surface of the substrate to be processed with a laminator. In this case, the photosensitive resin composition layer may be laminated only on one side of the substrate surface, or may be laminated on both sides. The heating temperature at this time is generally 40 to 160 ° C.
　次に、露光機を用いて露光工程を行う。必要ならば支持層を剥離し、フォトマスクを通して活性光により露光する。露光量は、光源照度及び露光時間により決定されるが、光量計を用いて測定しても良い。
　また露光工程において、直接描画露光方法を用いてもよい。直接描画露光方法はフォトマスクを使用せず、基材上に直接描画して露光する方式である。光源としては、例えば、波長３５０～４１０ｎｍの半導体レーザーや超高圧水銀灯が用いられる。描画パターンはコンピューターによって制御され、この場合の露光量は光源照度および基板の移動速度によって決定される。 Next, an exposure process is performed using an exposure machine. If necessary, the support layer is peeled off and exposed to active light through a photomask. The exposure amount is determined by the light source illuminance and the exposure time, but may be measured using a light meter.
In the exposure process, a direct drawing exposure method may be used. The direct drawing exposure method is a method in which exposure is performed by directly drawing on a substrate without using a photomask. As the light source, for example, a semiconductor laser having a wavelength of 350 to 410 nm or an ultrahigh pressure mercury lamp is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.
　次に、必要に応じて支持層を剥離除去してから現像を行う。本発明の感光性樹脂組成物は希アルカリ現像型であるので、現像には、炭酸ソーダ、炭酸カリウム、水酸化テトラメチルアンモニウム等のアルカリ化合物を含む０．１～５重量％のアルカリ性水溶液を用いて行う。上記アルカリ性水溶液のｐＨは９～１１の範囲とすることが好ましく、その温度は、感光性樹脂組成物層の現像性に合わせて調節される。この現像により、感光性樹脂組成物層のうち未露光部（所望のパターン画像を除く領域）が除去されて、レジストパターンが形成される。なお、上記アルカリ性水溶液中には、界面活性剤、消泡剤や現像を促進させるために少量の有機溶剤等を混入させてもよい。
　上述の工程によってレジストパターンが得られるが、場合によっては、さらに１００～３００℃の加熱工程、若しくはＵＶキュア工程を行うこともできる。これらの工程を実施することにより、更なる耐薬品性向上が可能となる。 Next, development is performed after the support layer is peeled and removed as necessary. Since the photosensitive resin composition of the present invention is a dilute alkali development type, a 0.1 to 5% by weight alkaline aqueous solution containing an alkali compound such as sodium carbonate, potassium carbonate or tetramethylammonium hydroxide is used for development. Do it. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. By this development, an unexposed portion (region excluding a desired pattern image) of the photosensitive resin composition layer is removed, and a resist pattern is formed. Note that a small amount of an organic solvent or the like may be mixed in the alkaline aqueous solution in order to promote a surfactant, an antifoaming agent or development.
Although the resist pattern is obtained by the above-described steps, in some cases, a heating step at 100 to 300 ° C. or a UV curing step can be performed. By carrying out these steps, further chemical resistance can be improved.
　〔導体パターンの形成方法〕
　本発明の導体パターンの形成方法は、基材として銅張積層板やフレキシブル基板などの回路形成用基板を用いて、上述のレジストパターン形成を行なった後、以下の工程を経ることで行われる。まず現像により露出した基板の面にめっき法、またはエッチング法といった既知の方法を用いて導体パターンを形成する。 [Method of forming conductor pattern]
The conductor pattern forming method of the present invention is performed by performing the following steps after performing the above-described resist pattern formation using a circuit-forming substrate such as a copper-clad laminate or a flexible substrate as a base material. First, a conductor pattern is formed on the surface of the substrate exposed by development using a known method such as plating or etching.
　めっきを行う場合のめっき方法としては、例えば、硫酸銅めっき、ピロリン酸銅めっき等の銅めっき、ハイスローはんだめっき等のはんだめっき、ワット浴（硫酸ニッケル－塩化ニッケル）めっき、スルファミン酸ニッケル等のニッケルめっき、ハード金めっき、ソフト金めっき等の金めっきなどが挙げられる。めっきを行うに際しては、脱脂剤、ソフトエッチング剤等のめっき前処理剤を用いて前処理を行うことが好ましい。また、エッチングは、通常、塩化第二銅－塩酸水溶液や、塩化第二鉄－塩酸水溶液等の酸性エッチング液を用いて、常法に従って行う。希に、アンモニア系のアルカリエッチング液も用いられる。 Examples of plating methods used for plating include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel such as nickel sulfamate Examples thereof include gold plating such as plating, hard gold plating, and soft gold plating. In performing plating, it is preferable to perform pretreatment using a plating pretreatment agent such as a degreasing agent or a soft etching agent. Etching is usually performed according to a conventional method using an acidic etching solution such as a cupric chloride-hydrochloric acid aqueous solution or a ferric chloride-hydrochloric acid aqueous solution. In rare cases, an ammonia-based alkaline etching solution is also used.
　めっき又はエッチング終了後、水酸化ナトリウム、水酸化カリウム等のアルカリ化合物を含む０．１～１０重量％程度の濃度のアルカリ水溶液からなるアルカリ剥離液、または３～１５重量％水溶液の有機アミン系剥離液（特にモノエタノールアミンを主成分とするもの）を用いて、レジストパターンの剥離除去を行う。
　なお、レジストパターンを用いてスルーホール内にめっきを充填する等の場合には、レジストパターンを除去せずに、レジストパターン上に導体膜を積層することもある。めっきの場合では、次いでフラッシュエッチングを行う。以上の工程を経て、プリント配線板等の回路基板における導体パターンを形成することができる。 After plating or etching is completed, an alkali stripping solution composed of an alkaline aqueous solution having a concentration of about 0.1 to 10% by weight containing an alkali compound such as sodium hydroxide or potassium hydroxide, or an organic amine-based stripping of a 3 to 15% by weight aqueous solution. The resist pattern is stripped and removed using a liquid (particularly, one containing monoethanolamine as a main component).
In addition, when filling a through hole with a resist pattern, a conductor film may be laminated on the resist pattern without removing the resist pattern. In the case of plating, flash etching is then performed. Through the above steps, a conductor pattern on a circuit board such as a printed wiring board can be formed.
　以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。なお、以下「％」「部」とあるのは、重量基準を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following, “%” and “parts” mean weight basis.
　１）評価用サンプルの作製
　実施例及び比較例におけるフォトレジストフィルムは、次の様にして作製した。表１に示す感光性樹脂組成物の溶液を、固形分量が５５重量％になるように調整し、よく撹拌、混合し、支持フィルムとして１６μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルム上に、アプリケーターを用いて乾燥後の塗工膜厚が２５μｍになるよう塗工した。６０℃、９０℃のオーブンでそれぞれ２分間乾燥して、更にその感光性樹脂組成物層の上から厚さ２１μｍのポリエチレンフィルムで被覆し、フォトレジストフィルムを得た。得られたフォトレジストフィルムについて、以下の項目を下記の如く評価した。 1) Preparation of sample for evaluation The photoresist film in an Example and a comparative example was produced as follows. The solution of the photosensitive resin composition shown in Table 1 was adjusted so that the solid content was 55% by weight, stirred and mixed well, and an applicator was used on a 16 μm thick polyethylene terephthalate (PET) film as a support film. Thus, the coating film thickness after drying was 25 μm. It dried for 2 minutes each in 60 degreeC and 90 degreeC oven, and also it coat | covered with the polyethylene film with a thickness of 21 micrometers from the photosensitive resin composition layer, and obtained the photoresist film. The obtained photoresist film was evaluated as follows.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１中の記号は下記のものを表わす。
　〔（Ａ）バインダーポリマー〕
　・Ｐ－１：メタクリル酸／メタクリル酸メチル／スチレン（重量比２２／３８／４０）を重合させて得られた、重量平均分子量４２，０００の４０％メチルエチルケトン溶液。固形分酸価＝１４３．４ｍｇＫＯＨ／ｇ。ガラス転移温度＝１１３．９℃。
　・Ｐ－２：メタクリル酸／メタクリル酸メチル／スチレン（重量比２８／３２／４０）を重合させて得られた、重量平均分子量３４，０００の４０％メチルエチルケトン溶液。固形分酸価＝１８２．５ｍｇＫＯＨ／ｇ。ガラス転移温度＝１１８．１℃。
　〔光重合可能なモノマー〕
　・Ｍ－１：Ｎ，Ｎ－ジエチルアミノエチルメタクリレート　ＣＨ２＝ＣＨ（ＣＨ３）ＣＯＯＣ２Ｈ５Ｎ（Ｃ２Ｈ５）２　〔共栄社化学社製、商品名：ライトエステルＤＥ〕
　・Ｍ－２：Ｎ－ｔｅｒｔ－ブチルアミノエチルメタクリレート　ＣＨ２＝ＣＨ（ＣＨ３）ＣＯＯＣ２Ｈ５ＮＨ（ｔ－Ｃ４Ｈ９）
　・Ｍ－３：ビスフェノールＡの両側にそれぞれ平均５モルのオキシエチレン基を付加したオキシエチレン基含有ビスフェノールＡ型ジメタクリレート〔新中村化学工業社製、商品名：ＢＰＥ－５００〕
　・Ｍ－４：ノナエチレングリコールジメタクリレート〔新中村化学工業社製、商品名：９Ｇ〕
　〔光重合開始剤〕
　・Ｉ－１：２，２′－ビス（２－クロロフェニル）－４，４′，５，５′－テトラフェニルビスイミダゾール　
　・Ｉ－２：４，４′－ビス（ジエチルアミノ）ベンゾフェノン
　〔染料〕
　・Ｄ－１：マラカイトグリーン
　・Ｄ－２：ロイコクリスタルバイオレット
　〔ベンゾトリアゾール誘導体〕
　・Ｔ－１：４－カルボキシベンゾトリアゾール
　・Ｔ－２：１－（１′，２′－ジカルボキシエチル）ベンゾトリアゾール
　・Ｔ－３：１－（（ビス（２－エチルヘキシル）アミノ）メチル）－１Ｈ－ベンゾトリアゾールカルボン酸
　・Ｔ－４：ベンゾトリアゾール
　〔溶剤〕
　・Ｆ－１：メチルエチルケトン The symbols in Table 1 represent the following.
[(A) Binder polymer]
P-1: 40% methyl ethyl ketone solution having a weight average molecular weight of 42,000, obtained by polymerizing methacrylic acid / methyl methacrylate / styrene (weight ratio 22/38/40). Solid content acid value = 143.4 mg KOH / g. Glass transition temperature = 113.9 ° C.
P-2: A 40% methyl ethyl ketone solution having a weight average molecular weight of 34,000 obtained by polymerizing methacrylic acid / methyl methacrylate / styrene (weight ratio 28/32/40). Solid content acid value = 182.5 mg KOH / g. Glass transition temperature = 118.1 ° C.
(Photopolymerizable monomer)
M-1: N, N-diethylaminoethyl methacrylate CH 2 ═CH (CH 3 ) COOC 2 H 5 N (C 2 H 5 ) 2 [Kyoeisha Chemical Co., Ltd., trade name: Light Ester DE]
M-2: N-tert-butylaminoethyl methacrylate CH 2 ═CH (CH 3 ) COOC 2 H 5 NH (tC 4 H 9 )
M-3: An oxyethylene group-containing bisphenol A-type dimethacrylate having an average of 5 moles of oxyethylene groups added to both sides of bisphenol A (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-4: Nonaethylene glycol dimethacrylate [manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: 9G]
(Photopolymerization initiator)
I-1: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole
I-2: 4,4'-bis (diethylamino) benzophenone [dye]
・ D-1: Malachite Green ・ D-2: Leuco Crystal Violet [Benzotriazole Derivative]
T-1: 4-carboxybenzotriazole T-2: 1- (1 ′, 2′-dicarboxyethyl) benzotriazole T-3: 1-((bis (2-ethylhexyl) amino) methyl)- 1H-benzotriazole carboxylic acid T-4: benzotriazole [solvent]
・ F-1: Methyl ethyl ketone
　２）評価方法
　上記フォトレジストフィルムのポリエチレンフィルムを剥離した後、感光性樹脂組成物層面が銅張基板上に接するように、ラミネートロール温度１００℃、同ロール圧０．３ＭＰａ、ラミネート速度１．２ｍ／ｍｉｎにてラミネートした。その後、光透過量が段階的に少なくなるように作られたネガフィルム（ストーファー２１段ステップタブレット）を用いて、超高圧水銀ランプを有する平行露光機（オーク製作所社製、商品名：ＥＸＭ－１２０１）によりストーファー２１段ステップタブレット全面を均一に露光した。露光後、１５分経過してからＰＥＴフィルムを剥離し、２７℃で０．７重量％炭酸ナトリウム水溶液をブレークポイント（未露光部分の完全溶解する時間）の２倍の現像時間でスプレーすることにより未露光部分を溶解除去して硬化レジスト画像を得た。各露光量と現像後に残った段数より、ストーファー２１段ステップタブレットの現像後の残存ステップ段数が６段となる露光量（ｍＪ／ｃｍ２）を調べた。 2) Evaluation method After peeling off the polyethylene film of the above photoresist film, a laminating roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.2 m so that the photosensitive resin composition layer surface is in contact with the copper-clad substrate. Laminate at / min. After that, a parallel exposure machine (trade name: EXM-, manufactured by Oak Manufacturing Co., Ltd.) having an ultra-high pressure mercury lamp using a negative film (Stofer 21-step step tablet) made so that the light transmission amount decreases stepwise. 1201) uniformly exposed the entire surface of a 21-step stove tablet. After exposure, after 15 minutes, the PET film is peeled off and sprayed with a 0.7 wt% sodium carbonate aqueous solution at 27 ° C. for a development time that is twice the breakpoint (time for complete dissolution of the unexposed area). Unexposed portions were dissolved and removed to obtain a cured resist image. From each exposure amount and the number of steps remaining after development, an exposure amount (mJ / cm 2 ) at which the number of remaining step steps after development of the stove 21-step tablet was 6 steps was examined.
　〔解像性〕
　露光時のガラスクロムマスクとして、露光部と未露光部の幅が１：１の比率のラインパターンマスクを用いて、ステップタブレットの段数が６段となる露光量で露光し、現像した。硬化レジストパターンが正常に形成されている最小マスク幅（μｍ）を解像性の値とした。 [Resolution]
As a glass chrome mask at the time of exposure, a line pattern mask having a ratio of 1: 1 between the exposed area and the unexposed area was exposed and developed with an exposure amount of 6 steps of the step tablet. The minimum mask width (μm) in which the cured resist pattern was normally formed was defined as the resolution value.
　〔密着性〕
　露光時のマスクフィルムとして、露光部単独のラインパターンマスクを用いて、ステップタブレットの段数が６段となる露光量で露光し、現像した。硬化レジストパターンが正常に形成されている最小マスク幅（μｍ）を密着性の値とした。 [Adhesion]
As a mask film at the time of exposure, using a line pattern mask of an exposed portion alone, the exposure was performed with an exposure amount that the number of steps of the step tablet was six, and developed. The minimum mask width (μm) at which the cured resist pattern was normally formed was defined as the adhesion value.
　〔現像後の硬化レジストのスソ〕
　基板にラミネートされたフォトレジストフィルムに、クロムガラスマスクを通してステップタブレットの段数が６段となる露光量で露光し、現像した。得られたレジストパターンのライン／スペース＝１０／１０μｍラインのスソを、下記によりランク付けした。スソ引きは、硬化レジストパターンのフット部のスソ幅をＳＥＭ（日本電子社製、商品名：ＪＳＭ－６３９０）により測定した。
　◎：硬化レジストパターンのフット部に、１μｍ以下のスソ引きが認められる。
　○：硬化レジストパターンのフット部に、１μｍを超え３μｍ以下のスソ引きが認められる。
　×：硬化レジストパターンのフット部に、３μｍを越えるスソ引きが認められる。 [Hardened resist after development]
The photoresist film laminated on the substrate was exposed and developed with an exposure amount of 6 step tablet steps through a chrome glass mask. Lines / spaces of the obtained resist patterns = 10/10 μm lines were ranked according to the following. In the sooting, the width of the foot portion of the cured resist pattern was measured by SEM (manufactured by JEOL Ltd., trade name: JSM-6390).
(Double-circle): The soot pull of 1 micrometer or less is recognized by the foot part of a cured resist pattern.
A: Soo pulling exceeding 1 μm and 3 μm or less is observed in the foot portion of the cured resist pattern.
X: Soo pulling exceeding 3 μm is observed in the foot portion of the cured resist pattern.
　〔剥離性〕
　基板にラミネートされたフォトレジストフィルムに、ステップタブレットの段数が６段となる露光量で４ｃｍ×４ｃｍ正方形パターンを露光した。最小現像時間の２倍の現像時間で現像した後、硫酸銅めっきを行った。さらに５０℃、３重量％の苛性ソーダ水溶液にてスプレーして硬化レジストの剥離時間を測定し、硬化レジストの剥離性を以下のようにランク付けした。
　◎：レジスト剥離時間が５０秒以下。
　○：レジスト剥離時間が５０秒を超え６０秒以下。
　×：レジスト剥離時間が６０秒を超える。 [Peelability]
A 4 cm × 4 cm square pattern was exposed on the photoresist film laminated on the substrate with an exposure amount of 6 step tablet steps. After development with a development time twice as long as the minimum development time, copper sulfate plating was performed. Further, spraying was performed with a 3% by weight aqueous caustic soda solution at 50 ° C. to measure the peeling time of the cured resist, and the peelability of the cured resist was ranked as follows.
A: Resist stripping time is 50 seconds or less.
○: Resist peeling time exceeds 50 seconds and is 60 seconds or less.
X: Resist peeling time exceeds 60 seconds.
　３）評価結果
　実施例および比較例の評価結果を表２に示す。 3) Evaluation results Table 2 shows the evaluation results of Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表２に示す如く、実施例１～７の感光性樹脂組成物は、解像性、密着性に優れている。さらに、硬化レジストのスソが小さいため、後工程のエッチングやめっきの際に支障が生じ難いものであった。また、剥離性も良好であるため安定した生産性を確保できる。 As shown in Table 2, the photosensitive resin compositions of Examples 1 to 7 are excellent in resolution and adhesion. Furthermore, since the width of the cured resist is small, it is difficult for troubles to occur during subsequent etching or plating. Moreover, since the peelability is also good, stable productivity can be secured.
　一方、比較例１～４の感光性樹脂組成物は、解像性、密着性ともに劣るものであった。また、比較例１、３、４の感光性樹脂組成物は硬化レジストのスソが大きいため、後工程のエッチングやめっきの際に支障が生じるおそれがある。さらに比較例１、２の感光性樹脂組成物は剥離性も悪いため、安定したスループットを得ることが困難である。 On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 4 were inferior in both resolution and adhesion. Moreover, since the photosensitive resin composition of Comparative Examples 1, 3, and 4 has a large thickness of the cured resist, there is a possibility that troubles may occur during subsequent etching or plating. Furthermore, since the photosensitive resin compositions of Comparative Examples 1 and 2 have poor peelability, it is difficult to obtain a stable throughput.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１１年３月３日出願の日本特許出願（特願２０１１‐０４６３７３）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on March 3, 2011 (Japanese Patent Application No. 2011-046373), the contents of which are incorporated herein by reference.
　本発明の感光性樹脂組成物及びフォトレジストフィルムは、解像性及び密着性が良好で、かつ現像後の硬化レジストのスソが極めて小さく、剥離性も良好であるという効果を有する。したがって、本発明の感光性樹脂組成物及びフォトレジストフィルムは、印刷配線板、リードフレーム、半導体パッケージ等の製造、金属の精密加工等の分野において、エッチングレジスト、めっきレジスト等のレジスト材料として好適に利用することができる。 The photosensitive resin composition and the photoresist film of the present invention have the effect that the resolution and adhesion are good, and the cured resist has a very small skirt and a good peelability after development. Therefore, the photosensitive resin composition and the photoresist film of the present invention are suitable as resist materials such as etching resists and plating resists in the fields of production of printed wiring boards, lead frames, semiconductor packages and the like, and precision metal processing. Can be used.
１　硬化レジスト
２　基板（銅薄膜）
３　スソ
４　めっき（銅配線） 1 Cured resist 2 Substrate (copper thin film)
3 Suseo 4 plating (copper wiring)

Claims (8)

  1. 　（Ａ）バインダーポリマー、（Ｂ）アミノ基を有する光重合可能なモノマー、（Ｃ）光重合開始剤、及び（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体を含有することを特徴とする感光性樹脂組成物。 A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable monomer having an amino group, (C) a photopolymerization initiator, and (D) a benzotriazole derivative having a carboxyl group. object.
  2. 　（Ｂ）アミノ基を有する光重合可能なモノマーが、下記一般式（Ｉ）で表される光重合可能な不飽和化合物であることを特徴とする請求項１に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （但し、式中のＲ１はＨまたはＣＨ３である。Ｒ２及びＲ３はそれぞれ独立して、水素原子、アルキル基、アルコキシ基及びハロゲン基からなる群から選ばれる基を表し、Ｒ２及びＲ３が互いに結合してＮを含む環を形成しても良い。Ｘは炭素数１～１０のアルキレン基、または（Ｃ２Ｈ４Ｏ）ｍまたは（Ｃ３Ｈ６Ｏ）ｎで示され、ｍ、ｎが各々１～１０の整数のポリオキシアルキレン基であり、ポリオキシアルキレン基はランダム重合またはブロック重合である。）     (B) The photopolymerizable monomer which has an amino group is a photopolymerizable unsaturated compound represented by the following general formula (I), The photosensitive resin composition of Claim 1 characterized by the above-mentioned.
    Figure JPOXMLDOC01-appb-C000001
     (However, R 1 in the formula is independently each .R 2 and R 3 is H or CH 3, represents a hydrogen atom, an alkyl group, a group selected from the group consisting of alkoxy group and a halogen group, R 2 And R 3 may be bonded to each other to form a ring containing N. X represents an alkylene group having 1 to 10 carbon atoms, or (C 2 H 4 O) m or (C 3 H 6 O) n. M and n are each an integer of 1 to 10 polyoxyalkylene groups, and the polyoxyalkylene groups are random polymerization or block polymerization.)
  3. 　（Ｂ）アミノ基を有する光重合可能なモノマーを、（Ａ）バインダーポリマー１００重量部に対して、０．０１～３０重量部含有することを特徴とする請求項１又は２に記載の感光性樹脂組成物。 3. The photosensitivity according to claim 1, wherein the photopolymerizable monomer having an amino group is contained in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the binder polymer (A). Resin composition.
  4. 　（Ｄ）カルボキシル基を有するベンゾトリアゾール誘導体を、（Ａ）バインダーポリマー１００重量部に対して、０．０１～２重量部含有することを特徴とする請求項１～３のいずれか一項に記載の感光性樹脂組成物。 The benzotriazole derivative having a carboxyl group (D) is contained in an amount of 0.01 to 2 parts by weight with respect to 100 parts by weight of the (A) binder polymer, according to any one of claims 1 to 3. Photosensitive resin composition.
  5. 　（Ａ）バインダーポリマーがカルボキシル基を有しており、その酸価が１００～３００ｍｇＫＯＨ／ｇであることを特徴とする請求項１～４のいずれか一項に記載の感光性樹脂組成物。 (A) The photosensitive resin composition according to any one of claims 1 to 4, wherein the binder polymer has a carboxyl group, and the acid value thereof is 100 to 300 mgKOH / g.
  6. 　請求項１～５のいずれか一項に記載の感光性樹脂組成物からなる感光性樹脂組成物層と支持層を含むことを特徴とするフォトレジストフィルム。 A photoresist film comprising a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 5 and a support layer.
  7. 　請求項６に記載のフォトレジストフィルムを用いて、基材上に感光性樹脂組成物層を形成し、露光し、現像することを含むレジストパターンの形成方法。 A method for forming a resist pattern, comprising: forming a photosensitive resin composition layer on a substrate using the photoresist film according to claim 6; exposing and developing the layer.
  8. 　請求項６に記載のフォトレジストフィルムを用いて、回路形成用基板上に感光性樹脂組成物層を形成し、露光し、現像して、レジストパターンを形成すること、および
    　前記レジストパターンが形成された前記回路形成用基板をエッチングまたはめっきし、前記レジストパターンを剥離することを含む、導体パターンの形成方法。     A photosensitive resin composition layer is formed on a circuit-forming substrate using the photoresist film according to claim 6, exposed and developed to form a resist pattern, and the resist pattern is formed A method of forming a conductor pattern, comprising etching or plating the circuit forming substrate and peeling off the resist pattern.
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