WO2024085254A1 - Composition de résine photosensible, corps multicouche de résine photosensible et procédé de formation de motif de réserve - Google Patents

Composition de résine photosensible, corps multicouche de résine photosensible et procédé de formation de motif de réserve Download PDF

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Publication number
WO2024085254A1
WO2024085254A1 PCT/JP2023/038065 JP2023038065W WO2024085254A1 WO 2024085254 A1 WO2024085254 A1 WO 2024085254A1 JP 2023038065 W JP2023038065 W JP 2023038065W WO 2024085254 A1 WO2024085254 A1 WO 2024085254A1
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photosensitive resin
component
compound
resin composition
mass
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PCT/JP2023/038065
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English (en)
Japanese (ja)
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奈央 亀山
秀昭 西本
克久 松本
裕樹 松尾
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旭化成株式会社
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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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern.
  • Printed wiring boards are generally produced by photolithography.
  • a photosensitive resin layer (a layer formed of a photosensitive resin composition) is first formed on a substrate. Then, the photosensitive resin layer is exposed to light and developed to form a photosensitive resin pattern (resist pattern). Next, a conductor pattern is formed through etching or plating, and the resist pattern is then removed to form a desired wiring pattern on the substrate.
  • the method of forming a photosensitive resin layer on a substrate is generally as follows: A method of applying a solution of a photosensitive resin composition onto a substrate and drying the applied solution; or A method of laminating a photosensitive resin layer of a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin layer) onto a substrate; In the manufacturing process of a printed wiring board, among the above, a method using a photosensitive resin laminate is often adopted. In the method using a photosensitive resin laminate, good sensitivity of the photosensitive resin layer and flexibility of the resist pattern are likely to be factors that affect the productivity and resolution of the wiring pattern.
  • Patent Document 1 discloses an example in which triphenylbutyl borate is used as a chain transfer agent.
  • Patent Document 2 discloses an example in which borate salts having various cations are used as co-initiators in an initiator system containing an amine and hexaarylbisimidazole (HABI).
  • Patent Document 3 discloses an example in which an organoboron compound of a specific structure is used as a radical generator.
  • Printed wiring boards are generally produced by photolithography.
  • a photosensitive resin layer (a layer containing a photosensitive resin composition) is first formed on a substrate.
  • the photosensitive resin layer is then exposed to light and developed to form a resin pattern (resist pattern).
  • a conductor pattern is then formed by etching or plating, and the resist pattern is then removed to form a desired wiring pattern on the substrate.
  • the method of forming a photosensitive resin layer on a substrate is as follows: A method of applying a solution of a photosensitive resin composition onto a substrate and drying the applied solution; or A method of laminating a photosensitive resin layer of a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin layer) onto a substrate;
  • a method of applying a solution of a photosensitive resin composition onto a substrate and drying the applied solution or
  • a method of laminating a photosensitive resin layer of a dry film resist (a photosensitive resin laminate having a support and a photosensitive resin layer) onto a substrate
  • the method using a photosensitive resin laminate is often adopted.
  • Patent Document 4 describes a photosensitive resin composition that contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and an anthracene-based sensitizer, in which the binder polymer contains polymer (a), and the polymer (a) contains hydroxyalkyl (meth)acrylate units and 40 mass% or more of styrene or styrene derivative units.
  • Patent Document 4 also describes a photosensitive resin laminate that includes a support and a photosensitive resin layer formed using the photosensitive resin composition.
  • Japanese Patent No. 4156069 Japanese Patent No. 3674336 Japanese Patent Application Laid-Open No. 4-271352 International Publication No. 2021/193232
  • the inventors therefore focused on boron compounds that have absorption for light of a specific exposure wavelength, and discovered that such compounds can be incorporated into a photosensitive resin composition.
  • the object of the present invention is to provide a photosensitive resin laminate that achieves both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern by using a boron compound that absorbs light of a specific exposure wavelength and causing the boron compound to absorb the light of the exposure wavelength, as well as a photosensitive resin composition that can realize such a photosensitive resin laminate, and a method for forming a resist pattern.
  • the photosensitive resin composition described in Patent Document 1 contains 40 mass% or more of styrene or styrene derivative units.
  • the photosensitive resin composition described in Patent Document 1 and the photosensitive resin laminate having a photosensitive resin layer obtained by using the same have room for further study from the viewpoints of developability and flexibility of the cured film.
  • the object of the present invention is to provide a photosensitive resin composition that is excellent in all of the following: resolution, adhesion, developability, and flexibility of the cured film.
  • the object of the present invention is to provide a photosensitive resin laminate obtained using such a photosensitive resin composition, a method for forming a resist pattern, and a method for forming a wiring board.
  • a photosensitive resin composition comprising: [2] Ingredients below: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; and (C) a polymerization initiator; A photosensitive resin composition comprising: The component (D) contains a boron compound having absorption for h-line and/or i-line, The component (B) is a photosensitive resin composition containing a bifunctional compound having two ethylenically unsaturated bonds in one molecule.
  • the component (D) is represented by the following general formula: R 2 -B(OH) 2 ; R 3 -B(OR 1 ) 2 ; R 4 -B(NR 5 2 ) 2 ; and R 6 -B(OH)(OR 7 ); (In the formula, R 1 to R 7 are monovalent organic groups, and multiple R 1 s and R 5 s that may be present in one molecule may be the same or different.)
  • the term "having absorption for h-line and/or i-line” refers to the following method: (1) Prepare
  • the read value is treated as the absorbance (A1); (2) The absorbance of toluene alone is measured by the same method as in (1) above, and the obtained absorbance value is read every 1 nm. The read value is treated as the absorbance (A2); and (3) The absorbance (A2) at the same wavelength is subtracted from the absorbance (A1) to obtain the subtracted value (A1-A2) every 1 nm. This subtracted value (A1-A2) is treated as the absorbance (A3) at 5 ppm in the toluene solution; 5.
  • the photosensitive resin composition according to any one of items 1 to 4, wherein there is a wavelength in the range of 400 to 410 nm and/or 350 to 370 nm at which the absorbance (A3) is 0.008 or more as measured by a method according to any one of items 1 to 4.
  • the term "having absorption for h-line and/or i-line” refers to the following method: (4) Prepare a toluene solution of the compound to be measured at a concentration of 5 ppm, measure the absorbance with a spectrophotometer using a double-transparent quartz cell with an optical path length of 10 mm, and read the obtained absorbance value every 1 nm.
  • the read value is treated as the absorbance (A1); (5) The absorbance of toluene alone is measured by the same method as in (1) above, and the obtained absorbance value is read every 1 nm. The read value is treated as absorbance (A2); and (6) The absorbance (A2) at the same wavelength is subtracted from the absorbance (A1) to obtain the subtracted value (A1-A2) every 1 nm. This subtracted value (A1-A2) is treated as the absorbance (A3) at 5 ppm in the toluene solution; 6.
  • the component (D) is represented by the following general formula: R 2 -B(OH) 2 ; and R 3 -B(OR 1 ) 2 ; (In the formula, R 1 to R 3 represent monovalent organic groups, and multiple R 1s that may be present in one molecule may be the same or different.)
  • the component (D) includes a compound having an anthracene skeleton.
  • the component (D) includes a compound having a pyrazoline skeleton.
  • the component (D) is 11.
  • the photosensitive resin composition according to any one of items 1 to 10 comprising a compound having at least one skeleton selected from the group consisting of pyrene, coumarin, triarylamine, benzophenone, oxazole, and chrysene.
  • the component (D) is a compound having a boron atom directly bonded to an anthracene skeleton.
  • the component (D) comprises 10-phenyl-9-anthraceneboronic acid.
  • the photosensitive resin composition according to item 2 wherein the component (B) contains a compound having a bisphenol A skeleton as the bifunctional compound.
  • the component (A) contains hydroxyethyl (meth)acrylate as a comonomer component.
  • the component (B) further contains a hindered amine compound in addition to the bifunctional compound.
  • the component (A) 10 to 90 mass %
  • the component (B) 5 to 70 mass %
  • the component (C) 0.01 to 20% by mass
  • the component (D) 0.01 to 20% by mass 17.
  • a photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from the photosensitive resin composition according to any one of items 1 to 18.
  • the photosensitive resin laminate further includes a protective layer on the opposite side of the photosensitive resin layer from the support, 20.
  • the photosensitive resin laminate according to item 19, wherein the protective layer is a polyethylene terephthalate film or a biaxially oriented polypropylene film. [21] 21.
  • a method for forming a resist pattern comprising: an exposure step of exposing a photosensitive resin layer of the photosensitive resin laminate; and a development step of removing an unexposed portion of the photosensitive resin layer.
  • the component (D) is a compound having absorption at h-line, 23.
  • the component (D) is a compound having absorption at i-line, 23.
  • a method for forming a wiring board comprising:
  • a photosensitive resin composition comprising: The component (A) contains a copolymer (A-1), The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and (a3) hydroxyalkyl (meth)acrylates; having a structural unit derived from the proportion of structural units derived from the component (a1) is 15 to 26% by mass, the proportion of structural units derived from the component (a2) is 30 to 70 mass %, The proportion of structural units derived from the component (a3) is 15 to 35 mass %, and The glass transition temperature (Tg) calculated based on the Fox formula is 100° C.
  • Tg glass transition temperature
  • Photosensitive resin composition [2A] The photosensitive resin composition according to Item 1A, wherein the proportion of structural units derived from the component (a1) in the copolymer (A-1) is 25 mass% or less. [3A] The photosensitive resin composition according to item 1A or 2A, wherein the copolymer (A-1) contains a structural unit derived from methacrylic acid as the component (a1). [4A] Item 3A. The photosensitive resin composition according to Item 3A, wherein the proportion of structural units derived from methacrylic acid in the copolymer (A-1) is 15 to 25% by mass.
  • the copolymer (A-1) further comprises the following components: (a4) A compound represented by the following general formula (I): (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 3 or more carbon atoms.) An alkyl (meth)acrylate represented by the formula: having a structural unit derived from In the copolymer (A-1), The proportion of structural units derived from the component (a2) is 30 to 60 mass %, and The photosensitive resin composition according to any one of items 1A to 5A, wherein the proportion of structural units derived from the component (a4) is 1% by mass to 15% by mass.
  • Item 6B The photosensitive resin composition according to Item 6A, wherein R 2 represents an alkyl group having 3 to 12 carbon atoms.
  • R 2 represents an alkyl group having 3 to 12 carbon atoms.
  • the photosensitive resin composition according to Item 12A wherein the di(meth)acrylate having a bisphenol A skeleton is contained in an amount of 20 mass% or more based on the total solid content of the photosensitive resin composition.
  • the sensitizer comprises a compound having at least one skeleton selected from the group consisting of skeletons derived from pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, and oxazole derivatives.
  • Item 17B The photosensitive resin composition according to Item 17A, wherein the sensitizer includes a compound having a skeleton derived from an anthracene derivative.
  • Item 17A or 18A the photosensitive resin composition according to Item 17A or 18A, wherein the sensitizer comprises at least one compound selected from the group consisting of 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid.
  • the sensitizer comprises at least one compound selected from the group consisting of 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid.
  • a photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from the photosensitive resin composition according to any one of Items 1A to 5A and 6A to 19A.
  • [21A] The following method: (1) After the photosensitive resin layer is formed on a flexible substrate, exposure is performed with an energy amount that results in 15 remaining steps on a Stouffer Industries 41-step step tablet, with a size of 1 inch width and 250 mm length, to obtain a cured film on the substrate. (2) The exposed substrate is developed using a 1% by weight Na 2 CO 3 aqueous solution at 30° C. for a time twice as long as the shortest development time. (3) After development, the substrate is washed with water for twice the minimum development time. (4) After washing with water, the substrate is cut into a 1.2 inch wide piece so that the 1 inch wide cured photosensitive resin layer is located in the center in the width direction, thereby obtaining a sample.
  • Cylindrical Mandrel Method A mandrel test in accordance with JIS K5600-5-1 is carried out on the sample. (6) The smallest mandrel diameter at which no cracks are observed in the cured film, or the smallest mandrel diameter at which no peeling of the cured film from the substrate is observed, is determined. 20B.
  • the photosensitive resin laminate according to 20A wherein the smallest mandrel diameter, as determined by: [22A] the photosensitive resin laminate includes a protective layer on the opposite side of the photosensitive resin layer to the support,
  • PET polyethylene terephthalate
  • OPP biaxially oriented polypropylene
  • the method for forming a resist pattern comprises the steps of: [25A] A step of forming a resist pattern on a substrate using the photosensitive resin laminate according to any one of Items 20A to 23A; forming a conductor pattern by etching or plating the substrate on which the resist pattern has been formed; peeling the resist pattern from the substrate; A method for forming a wiring board comprising:
  • a photosensitive resin composition capable of forming a photosensitive resin layer (resist) that is excellent in all of resolution, adhesion, developability, and flexibility of the cured film.
  • a photosensitive resin laminate having the photosensitive resin layer, a method for forming a resist pattern, and a method for forming a wiring board.
  • FIG. 2 is a plan view showing a configuration of a drawing pattern related to the present embodiment.
  • FIG. 2 is a plan view showing a configuration of a drawing pattern related to the present embodiment.
  • the structures when a plurality of structures represented by the same symbol are present in the same formula, the structures may be independently selected and may be the same or different from each other, unless otherwise specified. When a plurality of structures represented by the same symbol are present in different formulas, the structures may be independently selected and may be the same or different from each other, unless otherwise specified.
  • various measurements are performed based on the methods described in the Examples, unless otherwise specified.
  • the upper or lower limit value in a numerical range described in stages may be replaced by the upper or lower limit value in a corresponding numerical range described in other stages, and may further be replaced by the corresponding value described in the Examples.
  • (meth)acrylic means “acrylic” and/or “methacrylic
  • (meth)acrylate means “acrylate” and/or “methacrylate”
  • (meth)acryloyl means “acryloyl” and/or “methacryloyl”.
  • a "compound containing a (meth)acryloyl group” is referred to as, for example, a “(meth)acrylate compound”.
  • a “process” is included in this term not only when it is an independent process, but also when it cannot be clearly distinguished from other processes, as long as the function of that process is achieved. In the contents shown in the drawings, the scale, shape, and length may be exaggerated for greater clarity.
  • “derivative” includes not only compounds derived from a parent compound (compounds other than the parent compound) but also the parent compound itself.
  • “styrene derivative” includes not only compounds derived from styrene (compounds other than styrene) but also styrene itself, which is the parent compound.
  • the photosensitive resin composition of the present embodiment is Ingredients below: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) an initiator; and (D) a boron compound having absorption for h-line and/or i-line (hereinafter, may be simply referred to as "boron compound”); including.
  • boron compound a boron compound having absorption for h-line and/or i-line
  • the photosensitive resin composition of the present embodiment comprises: Ingredients below: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; and (C) a polymerization initiator; A photosensitive resin composition comprising: The component (D) contains a boron compound having absorption for h-line and/or i-line, The component (B) contains a bifunctional compound having two ethylenically unsaturated bonds in one molecule.
  • H-line refers to light having a wavelength between 400 and 410 nm, and in one embodiment, light having a wavelength of 405 nm.
  • i-line means light having a wavelength of 350-370 nm, and in one embodiment, light having a wavelength of 365 nm.
  • Having absorption means that the absorbance at 5 ppm in a toluene solution is 0.008 or more. With regard to “having absorption”, the absorbance is measured according to (1) to (5) below. The absorbance is measured at room temperature (25°C). The same measurement can be performed in the examples.
  • the toluene solution is measured for absorbance with a spectrophotometer (U-3010, Hitachi High-Technologies) using a double-transmitting quartz cell (S15-UV-10, Tokyo Glass Instruments) with an optical path length of 10 mm, i.e., an inner dimension of 10 mm in the direction of travel of the irradiated light, and the obtained absorbance value is read every 1 nm.
  • the read value is treated as the absorbance (A1).
  • the "toluene solution having a concentration of 5 ppm" is allowed to be a toluene solution having a concentration of about 5 ppm, specifically, a toluene solution having a concentration of 4.90 to 5.10 ppm.
  • the absorbances (A1) and (A3) at 5 ppm in the toluene solution described below are calculated as values converted to absorbances at a concentration of 5 ppm.
  • the above absorbance (A3) value of 0.008 or more at 405 nm may be treated as "having absorption at h-line,” and the above absorbance (A3) value of 0.008 or more at 365 nm may be treated as "having absorption at i-line.”
  • the photosensitive resin composition of this embodiment contains the above-mentioned component (D) in addition to the above-mentioned components (A) to (C), and the component (D) exhibits a favorable sensitizing function for the specified exposure wavelength (h-line and/or i-line) used in the photolithography method. This makes it possible to reduce the content of other sensitizers that may be an obstacle in terms of achieving good sensitivity of the photosensitive resin layer. Therefore, by using the photosensitive resin composition of this embodiment, a photosensitive resin layer with good sensitivity can be obtained.
  • the photosensitive resin composition of the present embodiment contains the component (D) in addition to the components (A) to (C), so that it is possible to achieve both good sensitivity of the photosensitive resin layer and high flexibility of the resist pattern.
  • Achieving good sensitivity in the photosensitive resin layer is related to shortening the exposure time, and thus to improving the productivity of the wiring pattern. Also, achieving high flexibility in the resist pattern is related to suppressing defects in the resist pattern, and thus to improving the resolution of the wiring pattern. Therefore, by using the photosensitive resin composition of this embodiment, it is possible to meet the expectations for improving the productivity and resolution of the wiring pattern of printed wiring boards produced by photolithography.
  • the photosensitive resin composition of the present embodiment is Component (A): 10 to 90% by mass, (B) component: 5 to 70 mass%, Component (C): 0.01 to 20% by mass, and component (D): 0.01 to 20% by mass According to this, the photosensitive resin composition can easily and suitably exhibit its function, and as a result, the effects of the present invention can be easily achieved.
  • component (A) 10 to 90% by mass
  • component (B) component: 5 to 70 mass%
  • Component (C) 0.01 to 20% by mass
  • component (D) 0.01 to 20% by mass
  • Component (A) Alkali-soluble polymer>
  • the component (A) is an alkali-soluble polymer, i.e., a polymer that is soluble in an alkaline solution.
  • the component (A) is a polymer that is soluble in an alkaline developer.
  • component (A) has a carboxyl group. From the same viewpoint, it is also preferable that component (A) has an acid value of 50 to 600 mgKOH.
  • the acid value of component (A) may be 60 mgKOH or more or 80 mgKOH or more, and may be 500 mgKOH or less or 400 mgKOH or less.
  • the weight average molecular weight (Mw) of the (A) component is preferably 3,000 or more, 5,000 or more, 7,000 or more, 10,000 or more, 12,000 or more, or 15,000 or more, and is preferably 500,000 or less, 200,000 or less, 100,000 or less, 70,000 or less, or 65,000 or less.
  • Mw/Mn which is the ratio of the Mw to the number average molecular weight (Mn) of the (A) component, is preferably 1.0 to 6.0.
  • Mw of component (A) means the Mw of component (A) as a whole, calculated from the mass proportion of each alkali-soluble polymer and the Mw of each alkali-soluble polymer.
  • Mn of the component (A) means the Mn of the component (A) as a whole, calculated from the mass proportion of each alkali-soluble polymer and the Mn of each alkali-soluble polymer.
  • the content of component (A) in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition. The same applies to each component contained below unless otherwise specified) is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 30 to 70 mass%.
  • the content of component (A) is preferably equal to or greater than the above lower limit from the viewpoint of maintaining the alkaline developability of the photosensitive resin layer, and is preferably equal to or less than the above upper limit from the viewpoint of making the resist pattern more flexible.
  • the component (A) is preferably a copolymer containing at least one of the following first monomers as a comonomer component.
  • the component (A) is more preferably a copolymer containing at least one of the following first monomers and at least one of the following second monomers as comonomer components.
  • the component (A), the first monomer, and the second monomer may each be used alone or in combination of two or more kinds.
  • the first monomer is a carboxylic acid or an acid anhydride having a polymerizable unsaturated group in the molecule.
  • the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester.
  • (meth)acrylic acid is preferable, and methacrylic acid is more preferable. Since methacrylic acid has a relatively high hydrophobicity, the use of this makes it easier to improve the resolution of the resist pattern in addition to the above.
  • the copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all comonomer components, from the viewpoint of excellent adhesion, resolution, etc. From the same viewpoint, the copolymerization ratio is more preferably 15% by mass or more, even more preferably 20% by mass or more, and more preferably 45% by mass or less, even more preferably 40% by mass or less.
  • the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • Examples of the second monomer include aromatic monomers, (meth)acrylic acid alkyl esters, conjugated diene compounds, polar monomers, and crosslinkable monomers.
  • Aromatic monomers include, for example, benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, divinylbenzene, and styrene derivatives (styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, styrene trimer, etc.).
  • the (meth)acrylic acid alkyl ester is a concept that encompasses both linear alkyl esters and cyclic alkyl esters.
  • Specific examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, and cyclo
  • conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene.
  • polar monomers examples include hydroxy group-containing monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and penteneol; amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide and N-methylol (meth)acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, and ⁇ -cyanoethyl acrylate; and epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate.
  • hydroxy group-containing monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and penteneol
  • cross-linking monomer is trimethylolpropane triacrylate.
  • the second monomer is preferably a monomer having an aromatic hydrocarbon group from the viewpoint of improving the adhesion and resolution of the resist pattern.
  • the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group; and a substituted or unsubstituted aralkyl group.
  • the aralkyl group include a benzyl group.
  • the second monomer is preferably benzyl (meth)acrylate or a styrene derivative, and more preferably styrene.
  • the copolymerization ratio of the monomer having an aromatic hydrocarbon group is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 40% by mass or more, based on the total mass of all comonomer components, and is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less.
  • the second monomer is preferably 2-hydroxyethyl (meth)acrylate, and more preferably 2-hydroxyethyl methacrylate (HEMA).
  • the synthesis method of component (A) may include a step of adding an appropriate amount of a radical polymerization initiator to a solution in which the monomer or monomers described above are diluted with a solvent such as acetone, methyl ethyl ketone, isopropanol, etc., and heating and stirring the solution.
  • the synthesis method may include a step of performing synthesis while dropping a part of the mixture into a reaction liquid.
  • the synthesis method may include a step of adding further solvent after the reaction is completed to adjust the concentration to the desired level.
  • the synthesis method may be a bulk polymerization, suspension polymerization, or emulsion polymerization method in addition to a solution polymerization method.
  • Component (B) Compound Having an Ethylenically Unsaturated Bond>
  • the component (B) is a compound having an ethylenically unsaturated bond in its structure. Such a component (B) is polymerizable.
  • the component (B) may be used alone or in combination of two or more kinds.
  • the (B) component preferably contains a compound (bifunctional compound) having two ethylenically unsaturated bonds in one molecule.
  • the bifunctional compound is easier to suppress intermolecular entanglement than a compound (polyfunctional compound) having three or more ethylenically unsaturated bonds in one molecule. Therefore, by including a bifunctional compound as the (B) component, the photosensitive resin composition can be given the desired fluidity. In this case, a photosensitive resin laminate having a support and a photosensitive resin layer with high flatness can be obtained, which is likely to be effective in suppressing defects in the wiring pattern. In addition, by using a photosensitive resin composition containing a bifunctional compound as component (B), it is easy to impart appropriate flexibility to the photosensitive resin layer.
  • a photosensitive resin layer having appropriate flexibility has good conformability to a substrate, and therefore is less likely to produce gaps between the photosensitive resin layer and the substrate during lamination.
  • bifunctional compounds have a superior crosslinking efficiency in the exposure step compared to compounds having one ethylenically unsaturated bond in one molecule (monofunctional compounds).
  • bifunctional compounds can suppress excessive crosslinking in the exposure step compared to polyfunctional compounds, and can impart appropriate flexibility to the photosensitive resin layer after exposure. Therefore, the above components (A) to (D) can ensure the flexibility of the resist pattern and meet the expectation of improved resolution of the wiring pattern.
  • Component (B) may include compounds having one ethylenically unsaturated bond in one molecule; compounds having three; compounds having four; compounds having five; and compounds having six or more ethylenically unsaturated bonds in one molecule. That is, component (B) may include a monofunctional compound and/or a polyfunctional compound. In component (B), the total mass of the bifunctional compounds may be greater than the total mass of the monofunctional compound and the polyfunctional compound.
  • the bifunctional compound is preferably a compound having a bisphenol A structure and/or a hydrogenated bisphenol A structure, and more preferably a compound having a bisphenol A structure. This makes it easier to achieve the effects of the present invention.
  • the compound may be contained in an amount of 5% by mass or more, or 10% by mass or more, and may be contained in an amount of 60% by mass or less, 55% by mass or less, or 50% by mass or less, based on the total amount of the photosensitive composition components.
  • the hydrogenated bisphenol A structure is a structure obtained by hydrogenating bisphenol A.
  • component (B) examples include: di(meth)acrylate of polyalkylene glycol in which an average of 1 to 15 moles of alkylene oxide are added to each end of bisphenol A; Tri(meth)acrylate of polyalkylene triol in which an average of 3 to 25 moles of alkylene oxide is added to trimethylolpropane; Glycerin; Trimethylolpropane; Pentaerythritol; Diglycerin; Ditrimethylolpropane; A compound obtained by converting an alcohol obtained by adding a polyalkylene oxide group to an isocyanurate ring or the like or by modifying the alcohol with ⁇ -caprolactone into a (meth)acrylate; A compound obtained by adding a polyalkylene oxide group to an isocyanurate ring or the like, or by modifying the alcohol with ⁇ -caprolactone, and then reacting the resulting alcohol directly with (meth)acrylic acid without modifying the alcohol with an alkylene oxide group or ⁇ -caprol
  • component (B) contains a hindered amine compound. This makes it less likely that residue will be left behind after the resist pattern is stripped off.
  • hindered amine compound refers to, for example, a compound represented by the following general formula: (In the formula, R1 each independently represents an alkyl group having 1 or more carbon atoms, and R2 represents hydrogen or an alkyl group having 1 or more carbon atoms. The number of carbon atoms in R1 and R2 each independently may be 10 or less.)
  • the content of the hindered amine compound may be 1% by mass or more, 3% by mass or more, or 5% by mass or more based on the total amount of the photosensitive composition components, and may be 20% by mass or less, 15% by mass or less, or 10% by mass or less, or may be 0% by mass.
  • the hindered amine compound may be a compound having one ethylenically unsaturated bond.
  • the content of the compound having one ethylenically unsaturated bond (excluding the hindered amine compound when the hindered amine compound is a compound having one ethylenically unsaturated bond) may be 20% by mass or less, 10% by mass or less, 5% by mass or less, or may be 0% by mass, based on the total amount of the photosensitive composition components.
  • one embodiment of the component (B) is, for example, Dimethacrylate of polyethylene glycol having an average of 5 moles of EO added to each end of bisphenol A; Dimethacrylate of polyethylene glycol having an average of 2 moles of EO added to each end of bisphenol A; Tetramethacrylate in which an average of 9 moles of EO is added to pentaerythritol; Tetramethacrylate in which an average of 15 moles of EO is added to pentaerythritol; Hexamethacrylate of polyethylene glycol in which an average of 13 moles of EO is added to dipentaerythritol; Dimethacrylate of polyethylene glycol in which an average of 2 moles of EO are added to each end of hydrogenated bisphenol A; 1,2,2,6,6-Pentamethylpiperidyl methacrylate; etc.
  • the content of component (B) in the photosensitive resin composition is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, and even more preferably 35 to 60% by mass, based on the total amount of the photosensitive composition components.
  • the content of component (B) is preferably equal to or greater than the lower limit above, from the viewpoint of preventing poor curing of the photosensitive resin layer and suppressing delays in development time. Furthermore, the content is preferably equal to or less than the upper limit above, from the viewpoint of improving the removability of the resist pattern.
  • the ratio (B/A) of the total mass of the (B) component to the total mass of the (A) component is preferably 1/3.0 to 1/0.5 (e.g., 0.33 to 2.0). This makes it easier for the photosensitive resin composition to function favorably, and as a result, makes it easier to achieve the effects of the present invention. From the same viewpoint, the ratio (B/A) is more preferably 1/2.5 to 1/0.7 (e.g., 0.40 to 1.4).
  • the component (C) is a compound capable of initiating polymerization of the component (B).
  • the component (C) is preferably a photopolymerization initiator, and more preferably contains a compound that generates radicals when exposed to actinic rays, thereby initiating polymerization of the component (B).
  • component (C) examples include hexaarylbiimidazole compounds, N-aryl- ⁇ -amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, and halogen compounds.
  • hexaarylbiimidazole compound examples include a dimer of a compound having a lophine structure (lophine dimer), that is, a dimer of 2,4,5-triarylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole.
  • lophine dimer a dimer of 2,4,5-triarylimidazole
  • 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole examples include a dimer of a compound having a lophine structure (lophine dimer), that is, a dimer of 2,4,5-triarylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxy
  • lophine dimers include the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,4 -difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4
  • component (C) contains a lophine dimer.
  • component (C) contains 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, or 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and even more preferable that it contains 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.
  • Quinone compounds include, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.
  • aromatic ketone compounds examples include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone.
  • Aromatic ketone compounds may function as photopolymerization initiators when used alone, and may also function as sensitizers when used in combination with other photopolymerization initiators.
  • acetophenone compounds examples include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1.
  • Irgacure series manufactured by BASF: Irgacure-907, Irgacure-369, and Irgacure-379, etc.
  • acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.
  • Commercially available acylphosphine oxide compounds include Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by BASF).
  • benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
  • dialkyl ketal compound examples include benzyl dimethyl ketal and benzyl diethyl ketal.
  • thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
  • dialkylaminobenzoate compound examples include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.
  • oxime ester compounds examples include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime.
  • Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by BASF).
  • acridine compounds examples include 1,7-bis(9,9'-acridinyl)heptane and 9-phenylacridine.
  • halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, 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 diaryliodonium compounds.
  • the content of component (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass. By adjusting the content of component (C) within the above range, it becomes easier to obtain sufficient sensitivity, and therefore easier to achieve high resolution.
  • the (C) component contains a lophine dimer.
  • the content of the lophine dimer is preferably 3.0 to 10 mass%, more preferably 4.0 to 9.0 mass%, and even more preferably 5.0 to 8.0 mass%, based on the total solid content of the photosensitive resin composition.
  • Component (D) Boron compound having absorption for h-rays and/or i-rays>
  • the component (D) contains a boron compound that has absorption for h-rays and/or i-rays.
  • the boron compound as component (D) is excited by h-rays and/or i-rays, causing a negative (negative) electron transfer to component (C). This exerts a sensitizing function.
  • the boron compound that has become a radical cation by the negative electron transfer to component (C) functions as a polymerization initiating species as a result of cleavage of the substituent on the boron.
  • the boron compound as component (D) preferably has a wavelength in the range of 400 to 410 nm or 350 to 370 nm, at which the absorbance (A3) value at 5 ppm in a toluene solution measured by the above method is 0.008 or more.
  • the absorbance (A3) value is equal to or greater than this lower limit, the boron compound is easily excited, and therefore the sensitizing function is easily exerted.
  • the absorbance (A3) value is 0.010 or more, and even more preferable that it is 0.012 or more.
  • the upper limit of the absorbance (A3) value may be 0.500 or less, 0.400 or less, or 0.300 or less. By having the absorbance value be equal to or less than this upper limit, it is easy to ensure the transmittance of the photosensitive resin composition even when the component (D) is contained in an amount sufficient to exert its sensitizing function, and therefore it is unlikely to adversely affect the curing of the photosensitive resin composition during exposure.
  • the absorbance (A3) value at h-line (405 nm) and/or i-line (365 nm) is preferably 0.008 or more, more preferably 0.010 or more, and even more preferably 0.012 or more.
  • the absorbance (A3) has a wavelength of 0.008 or more in the corresponding wavelength range, whereas the absorbance (A3) is not limited in the other wavelength range.
  • the wavelength is such that the absorbance (A3) value is 0.008 or more in the range of 400 to 410 nm. In this case, it is not necessary that the wavelength is such that the absorbance (A3) value is 0.008 or more in the range of 350 to 370 nm.
  • the wavelength when exposed to light having a wavelength near the i-line, it is preferable that the wavelength has a value of 0.008 or more for the absorbance (A3) in the range of 350 to 370 nm. In this case, it is not necessary that the wavelength has a value of 0.008 or more for the absorbance (A3) in the range of 400 to 410 nm.
  • boron is a Lewis acid, so an interaction (a Lewis acid-Lewis base bond) different from a covalent bond occurs between the boron compound and the Lewis base.
  • a Lewis acid-Lewis base bond a Lewis acid-Lewis base bond
  • the boron compound has the following general formula: B-R 1 R 2 R 3 ... (1)
  • R 1 to R 3 By appropriately selecting R 1 to R 3 in the general formula (1), it is easy to appropriately realize a boron compound that has absorption for h-line and/or i-line.
  • R 1 to R 3 in the general formula (1) may each independently be at least one selected from the group consisting of a monovalent organic group, an alkoxy group (-OR 4 ;
  • R 4 is a hydrocarbon group having 1 to 10 carbon atoms), an alkylamino group (-NR 5 R 6 ;
  • R 5 and R 6 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms), a hydroxyl group (-OH), hydrogen, and a halogen, and a plurality of R 1 to R 3 may form a saturated or unsaturated ring.
  • Examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, an alkanoyl group, an arbitrary substituent containing a ring structure having 3 to 20 carbon atoms, and groups in which a hydrogen atom in these groups is substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.
  • Examples of the optional substituent containing a ring structure having 3 to 20 carbon atoms include a benzoyl group and an aryl group having 6 to 20 carbon atoms.
  • R 1 to R 3 in the general formula (1) may each independently be a group having a heterocycle, or may be a group having a saturated or unsaturated ring containing a heteroatom (for example, nitrogen, oxygen, or sulfur). R 1 to R 3 may form a saturated or unsaturated ring, which may contain heteroatoms.
  • the halogen in the monovalent organic group may be, for example, fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). As a result, the effects of the present invention are easily achieved.
  • At least one of R 1 to R 3 is an alkoxy group or a hydroxyl group, since this makes it easier to achieve the effects of the present invention.
  • the R 1 to R 3 that is not an alkoxy group or a hydroxyl group may be hydrogen.
  • Examples of the boron compound represented by the above general formula (1) include boronic acid, boronic acid esters, boric acid esters, boroxines, and boric acid esters.
  • boronic acid, boronic acid esters, and boroxines are preferred from the viewpoint of flexibility of the resist pattern.
  • the boronic acid may be represented in the form R-B(OH) 2 .
  • the boronic ester may be represented in the form R--B(OH)( OR.sup.a ), R--B( OR.sup.a ) 2 , or R-- BO.sub.2Rb .
  • the borate ester may be represented as B(OH) 2 ( ORa ), B(OH)( ORa ) 2 , or B( ORa ) 3 .
  • the borinic ester may be represented in the manner R 2 B-OR a .
  • R and R a may each independently be the monovalent organic group described above, and R b may be a divalent organic group.
  • the multiple Rs may be different from each other, and the multiple Rs may be different from each other.
  • the divalent organic group an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferred.
  • the boron compound may be a compound represented by the formula R-(NR a 2 ) 2 or R-B(OR a )(NR a 2 ) (wherein R and R a may each independently be the monovalent organic group described above).
  • the boron compound is represented by the following general formula: *-B(OH) 2 ; *-B( OR1 ) 2 ; *-B( NR12 ) 2 ; *-B(OH)(OR 1 ); or The following general formula (2): (In the formula, R1 each independently represents the monovalent organic group described above, R2 represents a divalent organic group, and * represents a bonding site to various skeletons.)
  • the boron compound of the present embodiment preferably contains at least one boron moiety selected from the group consisting of:
  • the boron compound of the present embodiment includes compounds in which such a boron moiety is substituted for any hydrogen atom in various skeletons.
  • the boron compound is represented by the following general formula: R2 -B(OH) 2 R 3 -B(OR 1 ) 2 R 4 -B(NR 5 2 ) 2 R 6 -B(OH)(OR 7 ) (wherein R 1 to R 7 are monovalent organic groups, and a plurality of R 1 s and R 5 s that may be present in one molecule may be the same or different); and The following general formula (3): (wherein R 8 is a monovalent organic group and R 9 is a divalent organic group); It is preferred that the composition contains at least one compound selected from the group consisting of:
  • the boron compound may be a compound having a plurality of boron atoms in one molecule.
  • Examples of the compound having a plurality of boron atoms in one molecule include diboronic acid and diboronic acid ester.
  • Diboronic acid may be represented in the manner R(B(OH) 2 ) 2 .
  • the diboronic ester may be represented in the form B 2 (OR a ) 4 or R(B(OR a ) 2 ) 2 .
  • R and R a may each independently be the above-mentioned monovalent organic group. In the formula, when a plurality of R a are present, it goes without saying that the plurality of R a may be different from each other.
  • boron compounds having a hydrocarbon group can be treated as organic boron compounds.
  • boron compounds having a hydrocarbon group in compounds that absorb h-rays and/or i-rays and have a carbon (C)-boron (B) bond, electrons are excited by h-rays and/or i-rays to generate radical cations, and the C-B bond between carbon (C) and boron (B) is cleaved to generate a new polymerization end.
  • compounds that absorb h-rays and/or i-rays and have a carbon (C)-boron (B) bond not only have good sensitizing properties, but also function as a polymerization initiator, making it easier to realize a photosensitive resin layer with better sensitivity.
  • the boron compound can have a specific skeleton.
  • the specific skeleton is preferably a skeleton having an aromatic ring and/or a skeleton having a heteroatom.
  • the boron compound is easily excited by h-rays and/or i-rays, and it is easy to obtain good sensitivity of the photosensitive resin composition.
  • the skeleton that the boron compound may have is preferably derived from at least one selected from the group consisting of pyrazoline, anthracene, naphthalene, triarylamine, oxazole, N-aryl- ⁇ -amino acid, aromatic ketone derivatives, dialkylaminobenzoic acid ester, and chrysene.
  • the boron compound has a skeleton derived from anthracene and/or pyrazoline.
  • boron compounds having the above skeleton include pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, triarylamine derivatives, oxazole derivatives, N-aryl- ⁇ -amino acid derivatives other than oxazole derivatives, aromatic ketone derivatives, dialkylaminobenzoic acid ester derivatives, and chrysene derivatives, and other compounds in which any hydrogen atom in such compounds is substituted with the above boron moiety.
  • the boron compound may include a compound having a plurality of the boron moieties in the skeleton, and the plurality of boron moieties that may be present in the same compound may be the same or different.
  • pyrazoline derivatives include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, di
  • anthracene derivatives include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9-bromo-10-phenylanthracene, 9 -chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenylyl)-10-bromoanthracene, 9
  • Naphthalene derivatives include, for example, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-propoxynaphthalene, 1-butoxynaphthalene, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-bis(n-butoxy)naphthalene, 1,4-bis(i-butoxy)naphthalene, 1,4-bis(n-pentyloxy)naphthalene, 1,4-bis(n-hexyloxy)naphthalene, and 1,4-bis(n-heptyloxy)naphthalene.
  • naphthalene derivative examples include 1,4-bis(n-octyloxy)naphthalene, 1,4-bis(2-ethylhexyloxy)naphthalene, 1,4-bis(n-nonyloxy)naphthalene, 1,4-dibenzyloxynaphthalene, 1,4-diphenethyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,4-bis(2-methylglycidyloxy)naphthalene, 1-naphthol, 2-naphthol, 1-(2-hydroxyethoxy)naphthalene, and 2-(2-hydroxyethoxy)naphthalene. Of these, 1,4-diethoxynaphthalene is preferred as the naphthalene derivative.
  • oxazole derivatives include 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole and 2-[4-(1,3-benzoxazol-2-yl)naphthalen-1-yl]-1,3-benzoxazole.
  • N-aryl- ⁇ -amino acid derivatives include, for example, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N-(n-propyl)-N-phenylglycine, N-(n-butyl)-N-phenylglycine, N-(2-methoxyethyl)-N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N-(n-propyl)-N-phenylalanine, N-(n-butyl)-N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N-(p-tolyl)glycine, N-ethyl-N-(p-tolyl)glycine, N-(n-propyl Examples of such g
  • aromatic ketone derivatives examples include benzophenone derivatives.
  • Alkyl benzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, and 4-methylbenzophenone;
  • Benzophenone compounds having a halogen atom such as 2-chlorobenzophenone, 4-chlorobenzophenone, and 4-bromobenzophenone;
  • benzophenone compounds substituted with a carboxy group or an alkoxycarbonyl group such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester; and the like.
  • aromatic ketone derivatives include benzophenone derivatives substituted with an alkylamino group.
  • bis(dialkylamino)benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(dihydroxyethylamino)benzophenone, among which 4,4'-bis(dialkylamino)benzophenone compounds are preferred; 4-methoxy-4'-dimethylaminobenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, and the like; Examples include:
  • the boron compound is preferably a compound having the following skeleton in addition to or in addition to the above skeleton.
  • the skeleton may be, for example, at least one skeleton selected from the group consisting of at least one skeleton selected from the group consisting of pyrene, coumarin, and triarylamine. This is advantageous in terms of sensitivity.
  • the component (D) is 10-phenyl-9-anthraceneboronic acid, 4,4,5,5-tetramethyl-2-(10-phenylanthracen-9-yl)-1,3,2-dioxaborolane, [10-[4-(naphthalen-1-yl)phenyl]anthracen-9-yl]boronic acid, and 2-ethyl-4-methylimidazolium tetraphenylborate, etc. are examples.
  • the component (D) is a boron compound that has absorption for h-rays and/or i-rays. That is, the component (D) is Boron compounds that have absorption for h-lines but no absorption for i-lines, A boron compound that has no absorption for h-line but has absorption for i-line, and a boron compound that has absorption for h-line and also has absorption for i-line, However, it is preferable that the boron compound of the component (D) has absorption at least for h-rays.
  • the content of component (D) is preferably 0.01 to 2.0 mass%, more preferably 0.3 to 1.5 mass%, based on the total mass of component (A).
  • the (D) component may be used alone or in combination of two or more types.
  • the (D) component may contain other boron compounds (boron compounds other than the boron compounds described in this embodiment).
  • boron compounds may be 20% by mass or less, 10% by mass or more, 1% by mass or less, or 0% by mass, based on the total mass of component (D).
  • the photosensitive resin composition may contain components other than the above components (A) to (D) as desired.
  • the other components include colorants, leuco dyes, base dyes (dyes other than leuco dyes), colorants, antioxidants, stabilizers, plasticizers, and other sensitizers (sensitizers other than the above component (D)).
  • the other components may be used alone or in combination of two or more.
  • Colorants include fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (e.g., Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20, diamond green (e.g., Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis(4-methylphenylamino)-9,10-anthraquinone (e.g., OPLAS GREEN 533 manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis(butylamino)anthraquinone (e.g., OIL BLUE 2N manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis(isopropylamino)-9,10-anthraquinone (e.g., OIL BLUE
  • the content of the colorant is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.5 to 2 mass%, based on the total mass of the photosensitive resin composition.
  • Leuco dyes include, for example, leuco crystal violet (tris[4-(dimethylamino)phenyl]methane) and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide.
  • the content of the leuco dye is preferably 0.01 to 2 mass %, more preferably 0.1 to 1.5 mass %, based on the total mass of the photosensitive resin composition.
  • base dyes examples include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], and Basic Yellow 2 [2465-27-2].
  • Basic Green 1 CAS number (hereinafter the same): 633-03-4]
  • Fuchsin 632-99-5]
  • Methyl Violet 603-47-4
  • Methyl Green [82-94-0] Victoria Blue B [2580-56-5]
  • Basic Blue 7 [2390-60-5]
  • the content of the base dye is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the total mass of the photosensitive resin composition.
  • antioxidants examples include triphenyl phosphite (e.g., ADEKA Corporation, product name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., ADEKA Corporation, product name: 2112), tris(mononylphenyl) phosphite (e.g., ADEKA Corporation, product name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., ADEKA Corporation, product name: 329K).
  • TPP triphenyl phosphite
  • tris(2,4-di-tert-butylphenyl) phosphite e.g., ADEKA Corporation, product name: 2112
  • tris(mononylphenyl) phosphite e.g., ADEKA Corporation, product name: 1178
  • the content of the antioxidant is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, based on the total mass of the photosensitive resin composition.
  • the stabilizer may be, for example, at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group.
  • Radical polymerization inhibitors include, for example, 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), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxylamine aluminum salt (for example, aluminum salt with 3 moles of nitrosophenylhydroxylamine added), diphenylnitroso Amines, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid
  • alkylene oxide compounds having a glycidyl group examples include neopentyl glycol diglycidyl ether (e.g., Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolight 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolight 1600 manufactured by Kyoeisha Chemical Co., Ltd.).
  • neopentyl glycol diglycidyl ether e.g., Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.
  • nonaethylene glycol diglycidyl ether e.g., Epolight 400E manufactured by Ky
  • the total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group is preferably 0.001 to 3 mass %, more preferably 0.05 to 1 mass %, based on the total mass of the photosensitive resin composition.
  • the other sensitizers include sensitizers other than the component (D) above.
  • the other sensitizers do not contain, for example, the boron moiety.
  • Examples of other sensitizers (sensitizers other than the above component (D)) in the photosensitive resin composition include pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, triarylamine derivatives, oxazole derivatives, N-aryl- ⁇ -amino acid derivatives other than oxazole derivatives, aromatic ketone derivatives substituted with an alkylamino group, dialkylaminobenzoic acid ester derivatives, and chrysene derivatives.
  • sensitizers include 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, and coumarin (e.g., coumarin 102).
  • the content of the other sensitizer is preferably 2 mass% or less, more preferably 1.5 mass% or less, based on the total mass of the photosensitive resin composition. It is preferably 0.8 mass% or less, more preferably 0.3 mass% or less. The content of the other sensitizer may be 0 mass%.
  • the content (mass%) of the other sensitizer is preferably 2 times or less, more preferably 1.7 times or less, of the content of the above component (D).
  • carboxylbenzotriazoles include carboxylbenzotriazoles.
  • the content of carboxylbenzotriazoles is, for example, 0.01% by mass or more and 5% by mass or less based on the total mass of the photosensitive resin composition.
  • Photosensitive resin composition One aspect of this embodiment is a photosensitive resin composition.
  • a photosensitive resin composition is Ingredients below: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated bond; and (C) a polymerization initiator;
  • a photosensitive resin composition comprising: The component (A) contains a copolymer (A-1), The copolymer (A-1) contains at least the following components: (a1) (meth)acrylic acid; (a2) styrene derivatives; and (a3) hydroxyalkyl (meth)acrylates; having a structural unit derived from the proportion of structural units derived from the component (a1) is 15 to 26% by mass, the proportion of structural units derived from the component (a2) is 30 to 70 mass %, The proportion of structural units derived from the component (a3) is 15 to 35 mass %, and
  • the glass transition temperature (Tg) calculated based on the Fox formula is 100° C.
  • the photosensitive resin composition can form a photosensitive resin layer (resist) that is excellent in all of resolution, adhesion, developability, and flexibility of the cured film.
  • the photosensitive resin composition can provide a photosensitive resin laminate having the photosensitive resin layer, and a method for forming a resist pattern.
  • a photosensitive resin composition can be obtained that can form a photosensitive resin layer (resist) that is excellent in all of the following: resolution, adhesion, developability, and flexibility of the cured film.
  • the photosensitive resin layer is cured in the exposure step, and the cured photosensitive resin layer (cured film) is required to have a certain degree of flexibility.
  • One aspect of the present invention can provide a photosensitive resin layer (resist) that is also excellent in the balance of the flexibility of the cured film itself (balance between hardening and flexibility).
  • components (A) to (C) may be simply referred to as “component (A)” to “component (C)".
  • component (A) to “component (C)
  • Each component and the raw material of each component may be used alone or in combination of two or more.
  • the "solid content" of the photosensitive resin composition means the components of the photosensitive resin composition other than the solvent. Each component will be described below.
  • the component (A) is a polymer that is soluble in an alkaline aqueous solution, and such a polymer is, for example, a vinyl polymer that contains a carboxyl group. It is preferable that the (A) component contains a carboxyl group and has an acid equivalent of 100 to 600.
  • the acid equivalent refers to the mass in grams of an alkali-soluble polymer having one equivalent of a carboxyl group. Adjusting the acid equivalent to 100 or more is preferable from the viewpoint of excellent resolution and adhesion. Adjusting the acid equivalent to 600 or less is preferable from the viewpoint of excellent developability and peelability.
  • the acid equivalent may be measured by potentiometric titration using a titration device (for example, Hiranuma Automatic Titration Device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.) and 0.1 mol/L sodium hydroxide.
  • a titration device for example, Hiranuma Automatic Titration Device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.
  • COM-555 Hiranuma Automatic Titration Device manufactured by Hiranuma Sangyo Co., Ltd.
  • the acid equivalent of the (A) component is more preferably 250 to 450.
  • the weight average molecular weight (Mw) of the (A) component is preferably 5,000 to 500,000. Adjusting the weight average molecular weight (Mw) to 5,000 or more is preferable from the viewpoint of excellent performance such as adhesion, flexibility of the cured film, and edge fuse property. Adjusting the weight average molecular weight (Mw) to 500,000 or less is preferable from the viewpoint of easily preventing polymer aggregates from becoming large due to the developer, and thus from the viewpoint of easily preventing a decrease in yield that may occur due to such aggregates during the formation of a circuit board, etc.
  • edge fuse property means the performance of suppressing the phenomenon in which the photosensitive resin layer protrudes from the end surface of the roll when the photosensitive resin laminate is wound into a roll.
  • the weight average molecular weight (Mw) of the (A) component is more preferably 20,000 to 70,000, even more preferably 30,000 to 50,000, and particularly preferably 35,000 to 45,000.
  • the polydispersity of component (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.
  • the (A) component preferably has a monomer component consisting of a first monomer described below, and more preferably has a monomer component consisting of at least one type of the first monomer and at least one type of the second monomer described below.
  • the first monomer is an acidic monomer having a polymerizable unsaturated group in the molecule, for example, a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule.
  • the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Of these, (meth)acrylic acid is preferred.
  • the content of the first monomer is preferably 10 to 50 mass% based on the total mass of all monomer components. Adjusting the content of the first monomer to 10 mass% or more is preferable from the viewpoint of excellent adhesion and resolution, and 15 mass% or more, 18 mass% or more, 21 mass% or more is more preferable, 23 mass% or more is even more preferable, and 25 mass% or more is particularly preferable. Adjusting the content of the first monomer to 50 mass% or less is preferable from the viewpoint of excellent adhesion and resolution, and 35 mass% or less, more preferably 30 mass% or less, more preferably 29 mass% or less, and particularly preferably 27 mass% or less. When two or more types of first monomers are used, it is preferable that the total content of each is within the above range.
  • the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • the second monomer include styrene derivatives, (meth)acrylate compounds having a hydroxyl group, alkyl (meth)acrylates, (meth)acrylate compounds having an alicyclic or aromatic ring, vinyl alcohol, vinyl acetate, and esters of (meth)acrylonitrile.
  • styrene derivatives include styrene, oxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene.
  • Examples of (meth)acrylate compounds having a hydroxy group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and glycerin mono(meth)acrylate.
  • alkyl (meth)acrylates examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
  • Examples of (meth)acrylate compounds having an alicyclic or aromatic ring include benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and ethyl carbitol (meth)acrylate.
  • the (A) component may be used alone or in combination of two or more types.
  • the molecular weights and polydispersity of the monomers in the multiple (A) components are selected so that the weighted average value, when the content ratio is treated as the weight, falls within the above range.
  • the synthesis of component (A) is preferably carried out by mixing an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile with a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring the solution. In some cases, the synthesis is carried out while dropping a portion of the mixture into the reaction solution. In other cases, the desired concentration is adjusted by adding more solvent after the reaction is completed. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization. In some cases, the synthesis is carried out by living radical polymerization.
  • a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile
  • the content of component (A) may be 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass or more, based on the total solid content of the photosensitive resin composition. From the viewpoint of optimally exerting the effects of the present invention, the content of component (A) is preferably 50% by mass or more, and more preferably 55% by mass or more, based on the total solid content of the photosensitive resin composition. In addition, the content is 70% by mass or less, may be 65% by mass or less, or may be 60% by mass or less.
  • A/B can be controlled by adjusting the charge ratio of the (A) component to the (B) component when preparing the photosensitive resin composition.
  • A/B can be analyzed from the photosensitive resin layer by a predetermined method, and the value obtained thereby is based on the above charge ratio when preparing the photosensitive resin composition.
  • the analysis of the A/B value can be carried out, for example, by the following steps: (1) After dissolving the photosensitive resin layer in a good solvent, a poor solvent for only the component (A) is added dropwise to separate the component (A) by reprecipitation, and the mass of the component (A) obtained by reprecipitation is measured. (2) The amounts of other components such as the initiator are individually quantified using GC-MS or the like, and the amounts of components other than component (A) and component (B) are measured to indirectly determine the mass of component (B), and the value of A/B is calculated based on this. This can be done by:
  • the photosensitive resin composition of this embodiment can easily provide a photosensitive resin layer that satisfies high standards of developability, resolution, adhesion, and flexibility of the cured film by controlling the A/B value to 1.30 or more.
  • the A/B value is more preferably 1.40 or more, and even more preferably 1.50 or more.
  • the upper limit of the A/B value may be, for example, 2.50 or less.
  • the photosensitive resin composition containing the (A) component is likely to have excellent resolution and adhesion.
  • the content of the (A) component in a photosensitive resin composition containing a copolymer containing a large amount of styrene as a monomer component is increased (for example, A/B is 1.30 or more)
  • the cured film and resist pattern tend to become hard and brittle. Therefore, it is generally recognized that it becomes difficult to form a thin resist pattern and that adhesion is likely to deteriorate.
  • a photosensitive resin layer (resist) that is excellent in the flexibility of the cured film itself while using a photosensitive resin composition containing a copolymer containing a large amount of styrene as a monomer component. It is precisely because of this photosensitive resin composition that the value of A/B is controlled to 1.30 or more, it becomes easy to provide a photosensitive resin layer that satisfies high levels of developability, resolution, adhesion, and flexibility of the cured film.
  • the glass transition temperature Tg of component (A) is expressed as the weight average value Tg total .
  • Tg total is more preferably 99° C. or less, and even more preferably 95° C. or less. From the viewpoint of easy control of edge fusing property, Tg total is preferably 50° C. or more, more preferably 70° C. or more, even more preferably 80° C., and particularly preferably 85° C. or more.
  • the component (A) contains a copolymer (A-1),
  • the copolymer (A-1) is At least the following ingredients: (a1) (meth)acrylic acid; (a2) styrene derivatives; and (a3) hydroxyalkyl (meth)acrylates; having a structural unit derived from the proportion of structural units derived from the component (a1) is 15 to 26% by mass, the proportion of structural units derived from the component (a2) is 30 to 70 mass %, The proportion of structural units derived from the component (a3) is 15 to 35 mass %, and
  • the glass transition temperature (Tg) calculated based on the Fox equation is 100° C. or lower.
  • the weight average molecular weight (Mw) of the copolymer (A-1) is preferably 20,000 to 70,000, more preferably 30,000 to 50,000, and even more preferably 35,000 to 45,000, from the viewpoint of excellent flexibility of the cured film.
  • the content of copolymer (A-1) is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 45% by mass or more, based on the total solid content of the photosensitive resin composition.
  • the content of copolymer (A-1) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, based on the entire component (A).
  • Tg Glass transition temperature
  • the glass transition temperature (Tg) of the copolymer (A-1), calculated based on the Fox formula, is 100° C. or less from the viewpoint of excellent developability and flexibility of the cured film. From the same viewpoint as above, Tg is preferably 99° C. or less, and more preferably 95° C. or less. From the viewpoint of easy control of edge fusing property, Tg is preferably 50° C. or more, more preferably 70° C. or more, even more preferably 80° C., and particularly preferably 85° C. or more.
  • Tg is the temperature at which the proportion of free volume in the total volume of the polymer begins to increase rapidly. At temperatures above Tg, it is believed that the free volume increases in proportion to the temperature difference from the Tg. Therefore, under the same temperature conditions, the higher the Tg of a polymer, the smaller the free volume tends to be, and conversely, the lower the Tg, the larger the free volume tends to be. For this reason, it is believed that cured films of photosensitive resin layers obtained from photosensitive resin compositions with high Tg tend to have low flexibility, while cured films of photosensitive resin layers obtained from photosensitive resin compositions with low Tg tend to have high flexibility.
  • Tg i K (K: Kelvin)
  • c i the copolymerization ratio of each monomer
  • Tg i glass transition temperature
  • the mechanism by which the present embodiment can favorably exhibit all of the performance characteristics with regard to resolution, developability, adhesion, and flexibility of the cured film is presumed to be as follows.
  • the (A) component contains a copolymer containing a relatively large amount (30 to 70% by mass) of structural units derived from the (a2) component
  • the resulting photosensitive resin composition is likely to have excellent resolution and adhesion.
  • the (a2) component is highly hydrophobic, it is necessary to improve the developability of the resulting photosensitive resin composition.
  • the photosensitive resin layer obtained using the photosensitive resin composition containing the copolymer is likely to become a hard and brittle cured film after exposure, so it is necessary to improve the flexibility of the cured film.
  • the photosensitive resin layer obtained from the photosensitive resin composition containing the copolymer containing a large amount of the (a1) component still tends to become a hard cured film after exposure. That is, from the viewpoint of the flexibility of the cured film, it is better to have a small content of the (a1) component in the copolymer.
  • the (a3) component has a hydroxyl group, so it shows high hydrophilicity.
  • a copolymer in which the copolymerization ratio of the (a3) component is adjusted to a large amount of 15 mass% or more in the photosensitive resin composition even if the copolymerization ratio of the (a1) component in the copolymer is 26 mass% or less, a photosensitive resin composition capable of forming a photosensitive resin layer having excellent developability can be obtained.
  • the photosensitive resin composition by adjusting the contents of the components (a1) to (a3) within the ranges specified in the present application and further adjusting the Tg of the copolymer to 100° C. or less, a photosensitive resin layer capable of forming a cured film having excellent flexibility can be obtained.
  • the component (a1) may contain only one of methacrylic acid and acrylic acid, may consist of only one of them, may contain both, or may consist of only both.
  • the copolymerization ratio of the component (a1) is determined by the sum of the copolymerization ratio of methacrylic acid and the copolymerization ratio of acrylic acid.
  • the proportion of the structural units derived from component (a1) is 15 to 26% by mass based on the total mass of all structural units of copolymer (A-1). Adjusting this proportion to 15% by mass or more is preferable from the viewpoint of excellent developability and resolution. Adjusting this proportion to 26% by mass or less is preferable from the viewpoint of controlling the glass transition temperature (Tg) of the photosensitive resin layer within an appropriate range and from the viewpoint of flexibility of the cured film.
  • Tg glass transition temperature
  • the proportion is more preferably 17 to 25% by mass, and even more preferably 18 to 23% by mass.
  • the (a1) component contains methacrylic acid.
  • the copolymerization ratio of methacrylic acid is preferably 50 mass% or more, more preferably 75 mass% or more, and even more preferably 90 mass% or more, and may be 100 mass% based on the entire (a1) component.
  • the copolymerization ratio of methacrylic acid is preferably 15 to 25 mass%, and more preferably 17 to 23 mass%.
  • Component (a2) >>> Examples of the component (a2) include styrene, oxystyrene, hydroxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene. Of these, it is preferable that the component (a2) contains styrene.
  • the proportion of the structural units derived from component (a2) is 30 to 70% by mass based on the total mass of all structural units of copolymer (A-1). Adjusting this proportion to 30% by mass or more is preferable from the viewpoint of excellent resolution and adhesion. Adjusting this proportion to 70% by mass or less is preferable from the viewpoint of excellent developability and flexibility of the cured film.
  • the proportion is preferably 30 to 60% by mass, and more preferably 35 to 50% by mass.
  • the (a2) component may consist of only one type of compound, or may contain two or more types of compounds.
  • the copolymerization ratio of the (a2) component is determined by the sum of the copolymerization ratios of the respective compounds.
  • the component (a3) is a compound in which the hydrogen atom of the alkyl group of an alkyl (meth)acrylate is substituted with a hydroxy group.
  • examples of such compounds include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.
  • the component (a3) preferably contains hydroxyethyl (meth)acrylate from the viewpoint of excellent developability.
  • the proportion of the structural units derived from component (a3) is 15 to 35% by mass based on the total mass of all structural units of copolymer (A-1). Adjusting this proportion to 15% by mass or more is preferable from the viewpoint of achieving both developability and flexibility of the cured film. Adjusting this proportion to 35% by mass or less is preferable from the viewpoint of achieving excellent resolution and adhesion.
  • the proportion is preferably 20 to 30% by mass, and more preferably 23 to 27% by mass.
  • the (a3) component may consist of only one type of compound, or may contain two or more types of compounds.
  • the copolymerization ratio of the (a3) component is determined by the sum of the copolymerization ratios of the respective compounds.
  • the copolymer (A-1) may further contain, in addition to the structural units derived from the above components (a1) to (a3), a structural unit derived from the following component (a4) which is different from the above components (a1) to (a3).
  • Examples of the component (a4) include: (a4) A compound represented by the following general formula (I): (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 3 or more carbon atoms.) Preferred is an alkyl (meth)acrylate represented by the following formula:
  • the glass transition temperature Tg of a homopolymer of the component (a4) is lower than the glass transition temperature Tg of a homopolymer of the component (a1), the component (a2), or the component (a3). Therefore, by using such a component (a4), it is easy to adjust the glass transition temperature Tg of the copolymer (A-1) to a low value.
  • a compound represented by the above general formula (I) in which R 2 is an alkyl group having 3 to 12 carbon atoms is preferred.
  • examples of such compounds include propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and nonyl (meth)acrylate.
  • a compound represented by the above general formula (I) in which R 2 is an alkyl group having 4 to 10 carbon atoms is more preferred, and a compound represented by the above general formula (I) in which R 2 is an alkyl group having 6 to 9 carbon atoms is even more preferred.
  • 2-ethylhexyl (meth)acrylate is particularly preferred.
  • the proportion of the structural units derived from the (a4) component is preferably 1 to 15% by mass based on the total mass of all structural units of the copolymer (A-1). From the viewpoint of easily lowering the Tg of the copolymer (A-1) and of excellent flexibility of the cured film, the proportion is preferably 1% by mass or more.
  • the (a4) component has an unsaturated hydrocarbon group that does not have a hydrophilic group, and is therefore highly hydrophobic.
  • the (a4) component does not have an aromatic ring, it is preferable to balance it with the (a2) component that has an aromatic ring component incorporated into the polymer main chain. In this case, from the viewpoint of excellent various properties (for example, resolution, adhesion, developability, etc.), the proportion is preferably 15% by mass or less.
  • the proportion is more preferably 5 to 13% by mass, and even more preferably 8 to 12% by mass.
  • Copolymer (A-1) may contain a monomer other than components (a1) to (a4) as a copolymerization component.
  • the monomer other than components (a1) to (a4) is a first monomer other than (a1) and a second monomer other than components (a2) to (a4), and examples of such a monomer include compounds that do not fall under the above components (a1) to (a4) among the compounds exemplified as the first monomer and the compounds exemplified as the second monomer.
  • the copolymer (A-1) has a first monomer other than the component (a1)
  • the copolymerization ratio of the entire first monomer (including the above component (a1)) is preferably 26 mass% or less, and more preferably 25 mass% or less.
  • the copolymerization ratio of the first monomer other than the component (a1) may be 0 mass%.
  • the copolymer (A-1) has a second monomer other than the components (a2) to (a4)
  • the copolymerization ratio of the monomer component is preferably 20% by mass or less, and more preferably 10% by mass or less.
  • the copolymerization ratio of the second monomer other than the components (a2) to (a4) may be 0% by mass.
  • the (B) component is a compound having an ethylenically unsaturated bond.
  • the (B) component can have at least one ethylenically unsaturated bond in one molecule.
  • the (B) component preferably contains a compound having two ethylenically unsaturated bonds in one molecule.
  • the (B) component may further contain a compound having three ethylenically unsaturated bonds in one molecule, or may further contain a compound having four, five or six ethylenically unsaturated bonds in one molecule.
  • the content of the compound having two ethylenically unsaturated bonds in one molecule in component (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the entire component (B).
  • the content may be 100% by mass or less than 100% by mass based on the entire component (B).
  • component (B) contains a compound having three or more ethylenically unsaturated bonds in one molecule
  • the content of the compound having three or more ethylenically unsaturated bonds in one molecule is preferably 30% by mass or less, and may be 20% by mass or less, based on the entire component (B).
  • the content may be 1% by mass or more, and may be 5% by mass or more, based on the entire component (B).
  • the (B) component preferably contains a (meth)acrylate compound, and from the viewpoint of obtaining a photosensitive resin layer having appropriate flexibility, it is more preferable that the (B) component contains a bifunctional or higher (meth)acrylate compound (a compound having two or more (meth)acryloyl groups in one molecule).
  • a (meth)acrylate compound having n (meth)acryloyl groups in one molecule is referred to as, for example, "n-functionality.”
  • n-functionality For example, having 1, 2, 3, 4, 5, or 6 ethylenically unsaturated bonds in one molecule is referred to as "monofunctional (or monofunctional)", “bifunctional”, “trifunctional”, “tetrafunctional”, “pentafunctional”, or “hexafunctional”, respectively.
  • the (B) component contains a (meth)acrylate compound, from the viewpoint of excellent crosslinking efficiency in the exposure step, it may contain only a bifunctional (meth)acrylate compound, or it may contain a bifunctional (meth)acrylate compound and a trifunctional or higher functional (meth)acrylate compound.
  • the (B) component may contain, for example, a tetrafunctional, pentafunctional, or hexafunctional (meth)acrylate compound together with or separately from the bifunctional (meth)acrylate compound and/or the trifunctional or higher functional (meth)acrylate compound.
  • the content of the bifunctional (meth)acrylate compound is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the entire (B) component, from the viewpoint of excellent resolution and flexibility of the cured film. Furthermore, the content may be 100% by mass or less, based on the entire (B) component.
  • the content of the trifunctional or higher (meth)acrylate compound is preferably 30% by mass or less, and may be 20% by mass or less, based on the entire (B) component. Moreover, the content may be 1% by mass or more, and may be 5% by mass or more, based on the entire (B) component.
  • bifunctional (meth)acrylate compounds include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyalkylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, di(meth)acrylate with a bisphenol A structure, di(meth)acrylate with a hydrogenated bisphenol A structure, etc.
  • the polyalkylene glycol di(meth)acrylate may be a compound represented by the following general formula (II):
  • R 1 's are each independently a hydrogen atom or a methyl group
  • X 1 O and Y 1 O are each independently an oxyalkylene group having 2 to 4 carbon atoms
  • m1, m2, and n1 are each independently an integer of 0 to 40, m1+m2 is 1 to 40, and n1 is 0 to 20.
  • Examples of the compound include compounds represented by the following formula:
  • the di(meth)acrylate having a bisphenol A structure includes a di(meth)acrylate represented by the following general formula (III):
  • each R 2 is independently a hydrogen atom or a methyl group
  • each X 2 O and Y 2 O is independently an oxyethylene group or an oxypropylene group
  • each m3, m4, n2, and n3 is independently an integer of 0 to 40
  • m3+m4 is 1 to 40
  • n2+n3 is 0 to 20.
  • the number of structural units of oxyethylene groups or oxypropylene groups is an integer value in a single molecule, and is a rational number that is an average value in an aggregate of a plurality of molecules.
  • Di(meth)acrylates having a hydrogenated bisphenol A structure include compounds in which hydrogen is added to the aromatic ring of the compound represented by formula (III) above.
  • the component (B) preferably contains, as a bifunctional (meth)acrylate compound, a di(meth)acrylate having a bisphenol A structure and/or a di(meth)acrylate having a hydrogenated bisphenol A structure.
  • the compound is preferably contained in an amount of 20 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, and particularly preferably 70 mass% or more, based on the total amount of the component (B).
  • the compound is preferably contained in an amount of 10 mass % or more, more preferably 15 mass % or more, even more preferably 20 mass % or more, and particularly preferably 25 mass % or more, based on the total solid content of the photosensitive resin composition.
  • bifunctional (meth)acrylate compounds include, for example, NK Ester (registered trademark) A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, and AB.
  • NK Ester registered trademark
  • A-HD-N A-NOD-N
  • A-DOD-N A-NPG
  • 701A A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, and AB.
  • trifunctional or higher (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, diglycerin (tetra)(meth)acrylate, ditrimethylolpropane (tetra/penta/hexa)(meth)acrylate, triglycerin (penta)(meth)acrylate, dipentaerythritol (tetra/penta/hexa)(meth)acrylate, etc.
  • the tri- or higher functional (meth)acrylate compound may be a compound obtained by forming a (meth)acrylate from an alcohol having a central skeleton with three or more groups to which an alkylene oxide group can be added within the molecule and having an alkylene oxide group (e.g., an ethylene oxide group, a propylene oxide group, or a butylene oxide group) added thereto, and (meth)acrylic acid.
  • an alkylene oxide group e.g., an ethylene oxide group, a propylene oxide group, or a butylene oxide group
  • Examples of such compounds include alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, alkylene oxide-modified tri(meth)acrylate of glycerin, alkylene oxide-modified isocyanuric acid tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri/tetra)(meth)acrylate, alkylene oxide-modified tetra(meth)acrylate of diglycerin, alkylene oxide-modified ditrimethylolpropane (tetra/penta/hexa)(meth)acrylate, alkylene oxide-modified penta(meth)acrylate of triglycerin, and alkylene oxide-modified dipentaerythritol (tetra/penta/hexa)(meth)acrylate.
  • the tri- or higher functional (meth)acrylate compound preferably contains alkylene oxide-modified pentaerythritol (tri/tetra)(meth)acrylate and/or alkylene oxide-modified dipentaerythritol (tri/tetra)(meth)acrylate.
  • Specific embodiments of the compound include: Tetramethacrylate in which an average of 9 moles of ethylene oxide groups are added to pentaerythritol; Tetramethacrylate in which an average of 15 moles of ethylene oxide groups are added to pentaerythritol; Hexamethacrylate of polyethylene glycol in which an average of 13 moles of ethylene oxide groups are added to dipentaerythritol; etc.
  • NK Ester registered trademark
  • A-TMPT A-TMPT-9EO
  • AT-20E A-GLY-3E
  • A-GLY-9E A-GLY-20E
  • A-9300 A-9200YN
  • A-TMM-3 A-TMM-3L
  • A-TMM-3LM-N A-TMMT
  • ATM-35E AD-TMP, A-DPH, and A-955.
  • the component (B) may contain a hindered amine compound. This makes it difficult for residues to be generated after stripping the resist pattern.
  • the hindered amine compound include those represented by the following general formula (IV): (In the formula, each R 1 independently represents an alkyl group having 1 or more carbon atoms, R 2 independently represents hydrogen or an alkyl group having 1 or more carbon atoms, and the number of carbon atoms in R 1 and R 2 independently is 10 or less.)
  • An example of the compound represented by the general formula (IV) is 1,2,2,6,6-pentamethylpiperidyl methacrylate.
  • the content of the hindered amine compound may be 1 mass% or more, 3 mass% or more, or 5 mass% or more based on the total solid content of the photosensitive resin composition, and may be 20 mass% or less, 15 mass% or less, 10 mass% or less, or 0 mass%.
  • the hindered amine compound may be a compound having one ethylenically unsaturated bond.
  • the content of the compound having one ethylenically unsaturated bond (excluding the hindered amine compound when the hindered amine compound is a compound having one ethylenically unsaturated bond) may be 20 mass% or less, 10 mass% or less, 5 mass% or less, or 0 mass% based on the total solid content of the photosensitive resin composition.
  • the content of component (B) is preferably 10 to 50% by mass based on the total solid content of the photosensitive resin composition.
  • the content is preferably 10% by mass or more from the viewpoint of preventing poor curing of the photosensitive resin layer and suppressing delays in development time.
  • the content is preferably 50% by mass or less. From the same viewpoint, the content is more preferably 20 to 45% by mass, and even more preferably 25 to 40% by mass.
  • the total content of the (A) component and the (B) component is preferably 85% by mass or more, and more preferably 90% by mass or more, based on the total solid content of the photosensitive resin composition.
  • the total content of the components (A) and (B) may be 99% by mass or less, or may be 95% by mass or less.
  • the component (C) is a polymerization initiator.
  • the component (C) is preferably a photopolymerization initiator that generates radicals by actinic rays and thereby initiates polymerization of the component (B).
  • the component (C) preferably contains a compound having a biimidazole structure.
  • component (C) examples include hexaarylbiimidazole compounds, N-aryl- ⁇ -amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, and halogen compounds.
  • hexaarylbiimidazole compound examples include a dimer of a compound having a lophine structure (lophine dimer), that is, a dimer of 2,4,5-triarylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole.
  • lophine dimer a dimer of 2,4,5-triarylimidazole
  • 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole examples include a dimer of a compound having a lophine structure (lophine dimer), that is, a dimer of 2,4,5-triarylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxy
  • lophine dimer examples include a dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-( 2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-( 2,4-difluorophenyl)-4,4
  • component (C) contains a lophine dimer.
  • component (C) contains 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, or 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and even more preferable that it contains 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.
  • Quinone compounds include, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.
  • Aromatic ketone compounds include, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone.
  • Aromatic ketone compounds function as photopolymerization initiators when used alone, but may also function as sensitizers when used in combination with other photopolymerization initiators.
  • acetophenone compounds examples include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1.
  • Irgacure series manufactured by BASF: Irgacure-907, Irgacure-369, and Irgacure-379, etc.
  • acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.
  • Commercially available acylphosphine oxide compounds include Lucirin TPO (both manufactured by BASF) and Irgacure-819 (both manufactured by BASF).
  • benzoin compounds and benzoin ether compounds examples include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
  • Dialkyl ketal compounds include, for example, benzyl dimethyl ketal and benzyl diethyl ketal.
  • thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
  • dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.
  • Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime.
  • Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by BASF).
  • Examples of the acridine compound include 1,7-bis(9,9'-acridinyl)heptane and 9-phenylacridine.
  • halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, 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 diaryliodonium compounds.
  • the content of component (C) is preferably 0.01 to 20 mass%, more preferably 0.5 to 10 mass%, based on the total solid content of the photosensitive resin composition.
  • the content of the lophine dimer is preferably 3.0 to 10 mass%, more preferably 4.0 to 9.0 mass%, and even more preferably 5.0 to 8.0 mass%, based on the total solid content of the photosensitive resin composition.
  • the photosensitive resin composition preferably further contains a sensitizer (D).
  • the component (D) accelerates the photopolymerization reaction by transferring the energy obtained by absorbing light to the initiator.
  • the "component (D)” referred to in this embodiment may be different from the “component (D)” referred to in the above [embodiment of the "first invention”].
  • component (D) examples include pyrazoline derivatives, anthracene derivatives, naphthalene derivatives, oxazole derivatives, N-aryl- ⁇ -amino acid derivatives, and aromatic ketone derivatives substituted with an alkylamino group. Of these, it is preferable that component (D) contains a pyrazoline derivative or an anthracene derivative.
  • pyrazoline derivatives include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxy phenyl)-pyrazoline,
  • anthracene derivatives include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethyl-9,10-dibutoxyanthracene, 9-bromo-10-phenylanthracene, 9- Examples of the anthracene derivatives include chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenylyl)-10-bro
  • Naphthalene derivatives include, for example, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-propoxynaphthalene, 1-butoxynaphthalene, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-bis(n-butoxy)naphthalene, 1,4-bis(i-butoxy)naphthalene, 1,4-bis(n-pentyloxy)naphthalene, 1,4-bis(n-hexyloxy)naphthalene, and 1,4-bis(n-heptyloxy)naphthalene.
  • naphthalene derivative examples include 1,4-bis(n-octyloxy)naphthalene, 1,4-bis(2-ethylhexyloxy)naphthalene, 1,4-bis(n-nonyloxy)naphthalene, 1,4-dibenzyloxynaphthalene, 1,4-diphenethyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,4-bis(2-methylglycidyloxy)naphthalene, 1-naphthol, 2-naphthol, 1-(2-hydroxyethoxy)naphthalene, and 2-(2-hydroxyethoxy)naphthalene. Of these, 1,4-diethoxynaphthalene is preferred as the naphthalene derivative.
  • oxazole derivatives include 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole and 2-[4-(1,3-benzoxazol-2-yl)naphthalen-1-yl]-1,3-benzoxazole.
  • N-aryl- ⁇ -amino acid derivatives include, for example, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N-(n-propyl)-N-phenylglycine, N-(n-butyl)-N-phenylglycine, N-(2-methoxyethyl)-N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N-(n-propyl)-N-phenylalanine, N-(n-butyl)-N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N-(p-tolyl)glycine, N-ethyl-N-(p-tolyl)glycine, N-(n-propyl Examples of such g
  • aromatic ketone derivatives substituted with an alkylamino group examples include benzophenone derivatives.
  • Alkyl benzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, and 4-methylbenzophenone;
  • Benzophenone compounds having a halogen atom such as 2-chlorobenzophenone, 4-chlorobenzophenone, and 4-bromobenzophenone;
  • Benzophenone compounds substituted with a carboxy group or an alkoxycarbonyl group such as 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or its tetramethyl ester;
  • bis(dialkylamino)benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone,
  • the component (D) may contain a compound having the following skeleton in addition to or in addition to the above skeleton.
  • the skeleton may be, for example, at least one skeleton selected from the group consisting of pyrene, coumarin, triarylamine, oxazole, and chrysene. This is likely to be advantageous in terms of sensitivity.
  • the component (D) may contain a boron compound having absorption at h-line and/or i-line.
  • the boron compound having absorption at h-line and/or i-line is at least one compound selected from the group consisting of pyrazoline derivatives, anthracene derivatives, oxazole derivatives, N-aryl- ⁇ -amino acid derivatives, and aromatic ketone derivatives substituted with an alkylamino group, and is preferably a compound represented by the following general formula: * -BH2 *-B(OH) 2 *-B( OR1 ) 2 *-B(OH)(OR 1 ) (In the formula, each R1 independently represents a monovalent organic group, and * represents a bonding site to each of the skeletons.)
  • the compound is selected from the group consisting of: Examples of this type of compound include boronic acids having a pyrazoline skeleton, an anthracene skeleton, and an oxazole skeleton
  • the content of component (D) is preferably 0.01 to 2.0 mass%, more preferably 0.3 to 1.5 mass%, based on the total mass of component (A).
  • the photosensitive resin composition may contain components other than the above components (A) to (D) (component (E): other components) as desired.
  • component (E) include colorants, leuco dyes, base dyes (dyes other than leuco dyes), antioxidants, and stabilizers.
  • colorants include fuchsine, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green ⁇ e.g., Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd. ⁇ , basic blue 20, diamond green ⁇ e.g., Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd. ⁇ , 1,4-bis(4-methylphenylamino)-9,10-anthraquinone (e.g., OPLAS GREEN 533 manufactured by Orient Chemical Industry Co., Ltd.), 1,4-bis(butylamino)anthraquinone (e.g., OIL BLUE 2N manufactured by Orient Chemical Industry Co., Ltd.), and 1,4-bis(isopropylamino)-9,10-anthraquinone
  • the content of the colorant is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.5 to 2 mass %, based on the total solid content of the photosensitive resin composition.
  • Leuco dyes include, for example, leuco crystal violet ("tris[4-(dimethylamino)phenyl]methane"), and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide.
  • the content of the leuco dye is preferably 0.01 to 2 mass %, more preferably 0.1 to 1.5 mass %, based on the total solid content of the photosensitive resin composition.
  • Base dye examples include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd., Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], and Basic Yellow 2 [2465-27-2].
  • Basic Green 1 CAS number (hereinafter the same): 633-03-4]
  • Fuchsin 632-99-5]
  • Methyl Violet 603-47-4
  • Methyl Green [82-94-0] Victoria Blue B [2580-56-5]
  • Basic Blue 7 e.g., Ai
  • the content of the base dye is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the total solid content of the photosensitive resin composition.
  • antioxidant examples include triphenyl phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl)phosphite (e.g., ADEKA Corporation, trade name: 2112), tris(mononylphenyl)phosphite (e.g., ADEKA Corporation, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., Asahi Denka Kogyo Co., Ltd., trade name: 329K).
  • TPP triphenyl phosphite
  • TPP tris(2,4-di-tert-butylphenyl)phosphite
  • ADEKA Corporation tris(mononylphenyl)phosphite
  • 1178 tris(mononylphenyl)phosphite
  • the content of the antioxidant is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, based on the total mass of the photosensitive resin composition.
  • the stabilizer may, for example, be at least one of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group.
  • Radical polymerization inhibitors include, for example, 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), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxylamine aluminum salt (for example, aluminum salt with 3 moles of nitrosophenylhydroxylamine added), di
  • the radical polymerization inhibitor include phenylnitrosamine, hydroquinone, N-nitrosodiphenylamine, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cycl
  • the radical polymerization inhibitors preferably include p-methoxyphenol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, phenothiazine, and triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate].
  • alkylene oxide compounds having a glycidyl group examples include neopentyl glycol diglycidyl ether (e.g., Epolight 1500NP, manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolight 400E, manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolight 3002, manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolight 1600, manufactured by Kyoeisha Chemical Co., Ltd.).
  • Epolight 1500NP manufactured by Kyoeisha Chemical Co., Ltd.
  • nonaethylene glycol diglycidyl ether e.g., Epolight 400E, manufactured by Kyoeisha Chemical Co., Ltd.
  • the total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group is preferably 0.001 to 3 mass %, more preferably 0.05 to 1 mass %, based on the total solid content of the photosensitive resin composition.
  • Examples of other components include carboxylbenzotriazoles.
  • the content of the carboxylbenzotriazoles is, for example, 0.01% by mass or more and 5% by mass or less based on the total solid content of the photosensitive resin composition.
  • a preparation liquid for producing the photosensitive resin composition can be prepared by mixing the photosensitive resin composition with a solvent.
  • the solvent include Ketones such as acetone and methyl ethyl ketone (MEK); Alcohols such as methanol, ethanol, and isopropyl alcohol; It is preferable to mix the photosensitive resin composition with a solvent so that the viscosity of the prepared solution is 500 to 4000 mPa ⁇ sec at 25° C.
  • a photosensitive resin laminate obtained using the photosensitive resin composition of the embodiment of the "first invention” and the embodiment of the “related invention” is also another aspect of the embodiment of the present invention.
  • a photosensitive resin laminate obtained by using a photosensitive resin composition The following method: (1) After the photosensitive resin layer is formed on a flexible substrate, exposure is performed with an energy amount that results in 15 remaining steps on a Stouffer Industries 41-step step tablet, with a size of 1 inch width and 250 mm length, to obtain a cured film on the substrate. (2) The exposed substrate is developed using a 1% by weight Na 2 CO 3 aqueous solution at 30° C. for a time twice as long as the shortest development time. (3) After development, the substrate is washed with water for twice the minimum development time.
  • the substrate is cut into a 1.2 inch wide piece so that the 1 inch wide cured photosensitive resin layer is located in the center in the width direction, thereby obtaining a sample.
  • Cylindrical Mandrel Method A mandrel test in accordance with JIS K5600-5-1 is carried out on the sample.
  • a photosensitive resin laminate that can achieve both adhesion and flexibility of a cured film is likely to have excellent independent thin line formability.
  • the photosensitive resin laminate has, for example, a support and a photosensitive resin layer obtained from a photosensitive resin composition.
  • the photosensitive resin laminate is preferably a dry film resist from the viewpoint of easily achieving the effects of the present invention. It is also understood that the photosensitive resin composition is preferably used for a dry film resist.
  • the support is preferably a transparent film that transmits the light emitted from the exposure light source.
  • the support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as necessary.
  • the support may be one layer or multiple layers.
  • the thickness of the support is related to the transmission distance of the exposure light source. Therefore, a thinner support is more advantageous for image formation and also economically.
  • the thickness is preferably 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
  • the haze of the support is also preferably 5 or less.
  • the thickness of the photosensitive resin layer is preferably 3 to 100 ⁇ m, more preferably 10 to 50 ⁇ m, and even more preferably 15 to 50 ⁇ m.
  • the photosensitive resin laminate may have a protective layer on the side of the photosensitive resin layer opposite to the support.
  • the protective layer include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, and a polyester film. These films may be stretched as necessary.
  • the protective layer may be a single layer or multiple layers.
  • the protective layer has an appropriate adhesive strength.
  • the adhesive strength of the protective layer to the photosensitive resin layer is preferably smaller than the adhesive strength of the support to the photosensitive resin layer, and the protective layer can be easily peeled off from the photosensitive resin laminate.
  • the protective layer is preferably a polyethylene terephthalate (PET) film or a biaxially oriented polypropylene (OPP) film.
  • the thickness of the protective layer is preferably 10 to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
  • the thickness is preferably 5 to 100 ⁇ m, more preferably 8 to 50 ⁇ m, and even more preferably 10 to 30 ⁇ m.
  • the protective layer has a release layer on its surface. This makes it easier to peel the protective film from the photosensitive resin layer.
  • the release layer is classified, for example, into a silicone compound and a non-silicone compound.
  • the release layer may have an antistatic function, that is, it may be an antistatic layer. In this case, since charging between the photosensitive resin layer and the protective film can be prevented, it is easier to peel the protective film from the photosensitive resin layer.
  • the protective layer is preferably a PET film having an antistatic function.
  • silicone compound examples include: A condensation reaction type silicone resin obtained by reacting a polydimethylsiloxane having silanol groups at both ends with a polymethylhydrogensiloxane or a polymethylmethoxysiloxane; an addition reaction type silicone resin obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane; UV-curable or electron beam-curable silicone resins obtained by curing acrylic silicone, epoxy group-containing silicone, or the like with UV rays or electron beams; Modified silicone resins such as epoxy-modified silicone resins (silicone epoxy), polyester-modified silicone resins (silicone polyester), acrylic-modified silicone resins (silicone acrylic), phenol-modified silicone resins (silicone phenol), alkyd-modified silicone resins (silicone alkyd), and melamine-
  • Non-silicone compounds include, for example, alkyd (or alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.
  • the thickness of the release layer is preferably 0.001 to 2 ⁇ m, more preferably 0.005 to 1 ⁇ m, and even more preferably 0.01 to 0.5 ⁇ m. If the thickness is equal to or less than the upper limit, the appearance of the coating film after the protective layer is peeled off is likely to be good, and the coating film is likely to be sufficiently cured. On the other hand, if the thickness is equal to or more than the lower limit, sufficient release properties are likely to be ensured.
  • a photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support.
  • An example of the production method is as follows. First, as described above, a preparation liquid (coating liquid) of a photosensitive resin composition is prepared. Next, the preparation liquid is applied to a support using a bar coater or a roll coater, and dried, thereby producing a photosensitive resin layer on the support. Thereafter, if necessary, a protective layer is laminated on the photosensitive resin layer, thereby producing a photosensitive resin laminate.
  • the embodiment of the "first invention” and the embodiment of the “related invention” each include a method of forming a resist pattern using a photosensitive resin composition.
  • Such a method comprises the following steps: a lamination step of laminating a photosensitive resin layer in the photosensitive resin laminate onto a substrate; a step of exposing the photosensitive resin layer of the laminated photosensitive resin laminate (exposure step); and a step of removing the unexposed portion of the photosensitive resin layer (development step). has.
  • the method for forming a wiring pattern includes a step of performing a plating process, if necessary, on the substrate on which the resist pattern has been formed by the above method, followed by an etching step, and a peeling step.
  • the lamination step specifically, after peeling off the protective film from the photosensitive resin laminate, the resist layer is heated and pressed onto the substrate surface with a laminator, and laminated once or multiple times.
  • the substrate material include copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc., and a copper-clad laminate is preferred.
  • the substrate may be washed with, for example, an aqueous H 2 SO 4 solution having a concentration of about 10% by mass to prepare the substrate surface.
  • the heating temperature during lamination is generally 40 to 160°C, more preferably 80 to 120°C.
  • the heat-pressure bonding can be performed by using a laminator equipped with a roll, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the roll several times.
  • the heat-pressure bonding can be performed under a reduced pressure environment if desired.
  • the heat-pressure bonding can also be performed two or more times, which makes it easier to improve the adhesion of the resulting resist pattern to the substrate.
  • a two-stage laminator equipped with two successive rolls may be used, and the laminate of the substrate and the photosensitive resin layer may be passed repeatedly through the rolls.
  • the resist layer is exposed to an ultraviolet light source or the like through a photomask or reticle having a pattern, or directly, using an exposure machine such as a contact aligner, a mirror projection, or a stepper.
  • the exposure step may be performed after peeling off the support film, or through the support film, as desired.
  • the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using an actinometer.
  • direct imaging exposure may be performed. In direct imaging exposure, exposure is performed directly on the substrate using a drawing device without using a photomask.
  • the light source a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 nm to 410 nm is used.
  • the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.
  • the exposure light in the exposure step has a wavelength near the h-line
  • the exposure light in the exposure step preferably has a wavelength near the i-line.
  • the boron compound is a compound having absorption at h-line
  • the exposure step it is preferable to expose the photosensitive resin layer to light having a wavelength of 400 to 410 nm, and the boron compound is a compound having absorption at i-line, In the exposure step, it is preferable to expose the pre-photosensitive resin layer to light having a wavelength of 350 to 370 nm.
  • the exposure method used in the exposure process is preferably at least one method selected from the projection exposure method, the proximity exposure method, the contact exposure method, the direct imaging exposure method, and the electron beam direct writing method, and is more preferably performed using the projection exposure method or the direct imaging exposure method.
  • a heating step may be provided between the exposure step and the development step.
  • the heating temperature is preferably 30 to 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. By carrying out this heating step, it is possible to improve the resolution and adhesion.
  • a hot air, infrared, or far infrared heating furnace, a thermostatic bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like can be used.
  • the heating time is preferably 1 to 300 seconds, and more preferably 5 to 120 seconds.
  • the time that elapses from the exposure step to the heating step is preferably 10 to 600 seconds, and more preferably 20 to 300 seconds.
  • the time that elapses from the point at which heating is started to the point at which heating is stopped is preferably 1 to 120 seconds, and more preferably 5 to 60 seconds.
  • the unexposed portion of the resist layer after exposure is removed with a developer using a developing device to form a resist pattern. If there is a support film on the resist layer after exposure, the support film is removed. Then, the unexposed portion is developed and removed using a developer consisting of an alkaline aqueous solution to obtain a resist pattern.
  • a development method for developing the resist layer after exposure any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment.
  • the alkaline aqueous solution used as the developer is preferably an aqueous solution of Na 2 CO 3 , K 2 CO 3 or tetramethylammonium hydroxide.
  • the alkaline aqueous solution is selected according to the characteristics of the resist layer, but an aqueous solution of Na 2 CO 3 having a concentration of 0.2% by mass to 2% by mass is generally used.
  • a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, etc. may be added to the alkaline aqueous solution.
  • the temperature of the developer in the development step is preferably kept constant within the range of 20 to 40°C.
  • the development step preferably includes a washing step for removing the developer contained in the resist pattern after development.
  • the washing water may be selected according to the characteristics of the resist layer, such as pure water or industrial water, and may contain a polyvalent metal salt such as MgSO 4 at a concentration of 0.001 to 1% by mass in order to improve the resolution and the shape of the resist pattern.
  • the temperature of the washing water in the washing step is preferably kept constant within the range of 20 to 40°C.
  • a heat treatment can be further carried out at 60 to 300°C for 1 to 120 minutes.
  • the chemical resistance of the resist pattern can be improved.
  • a heating furnace using hot air, infrared rays, or far infrared rays can be used.
  • a conductor pattern formation process may be performed in which the substrate on which the resist pattern has been formed is etched or plated.
  • the conductive pattern forming step is a step of forming a conductive pattern by using a known etching method or plating method on a substrate surface (eg, a copper surface) on which a resist pattern has been formed by development.
  • the method for forming the conductor pattern by plating is, for example, as follows.
  • the substrate after the development step is immersed in an acidic degreasing bath such as a 1 to 50% by weight aqueous sulfuric acid solution for 1 to 60 minutes at 20 to 60° C.
  • the immersed substrate is washed with water, and then immersed in a 1 to 50% by weight aqueous sulfuric acid solution at room temperature for 1 to 60 minutes.
  • An aqueous solution containing 1-15% by mass of copper sulfate, 0.1-30% by mass of sulfuric acid, and 1-1000 ppm of hydrochloric acid is prepared, and then a brightener (in one embodiment, Cupracid HL and Cupracid GS, manufactured by Atotech, Inc.) is added at 0.01-40 ml/l and 1-200 ml/l, respectively, to prepare a copper sulfate plating solution.
  • the prepared copper sulfate plating solution is used for plating with a Haring Cell Uniform Plating Device (manufactured by Yamamoto Plating Tester Co., Ltd.) at an applied current of 0.01-10 A for 1-300 minutes to form a conductor pattern.
  • the thickness of the copper plating film depends on the thickness of the resist pattern, but is preferably 1 ⁇ m or more and the thickness of the resist pattern ( ⁇ m) - 2 ⁇ m or less.
  • the thickness of the resist pattern means the thickness of the resist layer.
  • An example of a method for forming a conductor pattern using an etching method is flash etching.
  • the copper seed layer can be removed using a specific etching solution.
  • etching solutions include, but are not limited to, a mixed etching solution of sulfuric acid and hydrogen peroxide (manufactured by Ebara Densan Co., Ltd.).
  • the method for producing the conductor pattern is carried out, for example, by using a metal plate or a metal-coated insulating plate as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then carrying out a conductor pattern forming step.
  • a peeling step may be performed in which the resist pattern is peeled off from the substrate using an aqueous solution having a stronger alkalinity than the developer.
  • a wiring board in one embodiment, a printed wiring board having a desired wiring pattern can be obtained.
  • the alkaline aqueous solution used for stripping (hereinafter also referred to as the "stripping solution") is not particularly limited, but an aqueous solution of NaOH or KOH with a concentration of 2% by mass to 20% by mass, or an organic amine-based stripping solution is generally used.
  • a small amount of a water-soluble solvent may be added to the stripping solution. Examples of water-soluble solvents include alcohol.
  • the temperature of the stripping solution in the stripping process is preferably within the range of 40 to 70°C, and the immersion time in the stripping solution is preferably 1 to 60 minutes.
  • a method for producing a wiring board using the photosensitive resin laminate according to the above embodiment includes the following steps: a lamination step of laminating a photosensitive resin layer onto a substrate; an exposure step of exposing the photosensitive resin layer to light; a developing step of developing and removing the unexposed portions of the photosensitive resin layer to form a resist pattern; a conductive pattern forming step of forming a conductive pattern by etching or plating the substrate on which the resist pattern has been formed; and a peeling step of peeling the resist pattern from the substrate; including.
  • the steps included in the method for producing a wiring board according to the above embodiment that is, the lamination step, the exposure step, the development step, the conductor pattern formation step, and the peeling step, are the same as those described above.
  • the photosensitive resin laminate in the above embodiment can be used in the manufacture of printed wiring boards; the manufacture of lead frames for mounting IC chips; precision processing of metal foils such as the manufacture of metal masks; the manufacture of packages such as ball grid arrays (BGA) and chip size packages (CSP); the manufacture of tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); the manufacture of semiconductor bumps; and the manufacture of partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields.
  • BGA ball grid arrays
  • CSP chip size packages
  • COF chip-on-film
  • TAB tape automated bonding
  • partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields.
  • evaluation samples were prepared as follows.
  • a 19 ⁇ m thick polyethylene film (manufactured by Tamapoly Co., Ltd., product name "GF-818") was attached as a protective layer to the opposite side of the photosensitive resin layer from the support film to obtain a photosensitive resin laminate.
  • ⁇ Substrate surface preparation> The surface of a copper-clad laminate having a total thickness of 0.4 mm and laminated with 18 ⁇ m rolled copper foil was washed with a 10 mass % H 2 SO 4 aqueous solution. The washed copper-clad laminate was used as a substrate for evaluating image properties (evaluation substrate).
  • the photosensitive resin layer was laminated onto a copper-clad laminate (substrate for evaluation) preheated to 50° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105° C.
  • the air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.
  • ⁇ Exposure> The evaluation substrate 2 hours after lamination was directly exposed to exposure light having a wavelength of 401 nm using a direct imaging (DI) exposure mask pattern with a direct imaging exposure machine (FDi-3 manufactured by Oak Manufacturing Co., Ltd.) The exposure was performed with an exposure amount that resulted in a maximum remaining film step number of 15 steps when exposed using a Stouffer Industries 41-step step tablet as a mask and then developed.
  • DI direct imaging
  • the polyethylene terephthalate film (support film) was peeled off. Then, development was performed by spraying a 1% by mass Na 2 CO 3 aqueous solution at 30° C. onto the photosensitive resin layer for a predetermined time using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine). The spraying time was set to twice the shortest developing time, and the cleaning time after development (water washing by spraying) was set to twice the shortest developing time. At this time, the shortest time required for the photosensitive resin layer in the unexposed part to completely dissolve was treated as the shortest developing time. From the above, a resist pattern was prepared on the evaluation substrate.
  • a commercially available dry film resist (DFR) was laminated on a copper-clad laminate, and the photosensitive resin layer was exposed to light and developed, followed by etching of the copper and peeling off of the DFR to produce a pit substrate in which a circular depression with a diameter of 310 ⁇ m and a depth of about 10 ⁇ m was formed.
  • the photosensitive resin laminates of the examples and comparative examples were laminated on this pit substrate according to the lamination process described above. At that time, if the photosensitive resin layer does not follow sufficiently, a gap will occur between the circular depression and the substrate. The average value of the diameter of 10 points of the gap was calculated and evaluated according to the following criteria. If it was fair or better, it was treated as passing. Excellent: 100um or less Good: Over 100um and under 150um Fair: Over 150um and under 200um Poor: Over 200um
  • the absorbance of each of the above compounds to h-line and i-line was measured according to (1) to (5). The results are shown in the table below.
  • the wavelength absorbance of the boron compound can be treated as the wavelength absorbance of the photosensitive resin composition containing the boron compound.
  • solution (b) 0.5 parts by mass of azobisisobutyronitrile was dissolved in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol to prepare solution (b).
  • 50 g of solution (b) was added dropwise to the solution in the flask over a period of 10 minutes at a constant rate, and the solution was stirred at 80°C for 3 hours.
  • the solution in the flask was further heated to 90°C over a period of 30 minutes, and then kept at 90°C for 2 hours. Stirring was then stopped, and the solution was cooled to room temperature (25°C).
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) and calculated using a calibration curve of standard polystyrene.
  • GPC conditions are as follows: (GPC conditions) Pump: JASCO PU-4580 Degasser: DG-2080-53 Column oven: CO-1560 Columns: 4 in total (Shodex) KF-807 x 1, KF-806M x 2, KF-802.5 x 1 Eluent: tetrahydrofuran Measurement temperature: 40°C Flow rate: 1.00 mL/min Detector: JASCO RI-1530
  • ⁇ Preparation of Photosensitive Resin Laminate> The components shown in the table below (the numbers of each component indicate the amount of solid content (parts by mass)) were mixed with ethanol measured to give a solid content concentration of 60% so that the amount of solid content of each component was the amount shown in the table below, to obtain a preparation liquid for a photosensitive resin composition.
  • a 16 ⁇ m thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., QS71) was used as a support film, and the preparation liquid was applied to its surface using a bar coater, and then dried in a dryer at 95 ° C. for 2.5 minutes. As a result, a photosensitive resin layer having a thickness of 25 ⁇ m was formed on the support film. As a result, a photosensitive resin laminate was obtained.
  • a 19 ⁇ m thick polyethylene film (manufactured by Tamapoly Co., Ltd., product name "GF-818") was attached as a protective layer to the side of the photosensitive resin layer opposite the support film to obtain a laminate.
  • the laminate of the support film, photosensitive resin layer, and protective film was treated as a photosensitive resin laminate.
  • ⁇ Substrate surface preparation> A surface of a copper-clad laminate having a total thickness of 0.4 mm, which was laminated with a rolled copper foil having a thickness of 18 ⁇ m, was prepared. The surface was then washed with a 10 mass% H 2 SO 4 aqueous solution, and then washed with pure water. The copper-clad laminate after washing was preheated to 50° C.
  • the photosensitive resin layer was laminated to a copper-clad laminate preheated to 50° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105° C. so that the photosensitive resin layer was in contact with the surface of the copper-clad laminate. This resulted in a substrate for evaluation.
  • the air pressure during lamination was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.
  • the evaluation substrate which had been laminated for 2 hours, was directly exposed to light using a direct imaging (DI) exposure pattern by a direct imaging exposure machine (FDi-3 manufactured by Oak Manufacturing Co., Ltd.).
  • DI direct imaging
  • FDi-3 manufactured by Oak Manufacturing Co., Ltd.
  • the exposure was performed using a Stouffer Industries 41-step step tablet as a mask, with an exposure amount that resulted in a maximum remaining film step number of 15 steps when developed.
  • the support film was peeled off from the evaluation substrate. Then, using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine), a 1% by mass Na 2 CO 3 aqueous solution at 30° C. was sprayed onto the photosensitive resin layer for a predetermined time to perform development. Then, pure water was sprayed onto the photosensitive resin layer for a predetermined time to perform water washing. As a result, a resist pattern was obtained on the evaluation substrate.
  • an alkali developing machine manufactured by Fuji Kiko Co., Ltd., a dry film developing machine
  • FIG. 1 is a plan view showing an example of the configuration of a drawing pattern.
  • an exposed region is indicated by the reference numeral 10
  • an unexposed region is indicated by the reference numeral 1.
  • the unexposed region 1 has a predetermined width and extends in the X direction, and a plurality of such unexposed regions 1 are arranged in the width direction (Y direction) at predetermined intervals.
  • the unexposed region 1 is removed through a ⁇ development> step, so that it is expected that a resist pattern having an L/S that corresponds to the width of the unexposed region 1 (S: space) and the width of the exposed region 10 (L: line) is theoretically formed by exposing the photosensitive resin layer based on the drawing pattern in FIG. 1.
  • the substrate on which the resist pattern was formed was observed under an optical microscope at a magnification of 200 times and evaluated according to the following criteria. Note that residual resist may occur when unexposed parts of the resist are not sufficiently removed in the above ⁇ Development>.
  • FIG. 2 is a plan view showing an example of the configuration of a drawing pattern.
  • the exposed area is indicated by the reference numeral 10
  • the unexposed area hatchched area
  • the exposed area 10 has a predetermined width and extends in the x direction, and a plurality of such exposed areas 10 are arranged in the width direction (y direction) at predetermined intervals.
  • the unexposed area 1 is removed through the ⁇ development> step, so that, based on the drawing pattern in FIG. 2, it is theoretically expected that a resist pattern having an L/S corresponding to the width of the exposed area 10 (L: line) and the width of the unexposed area 1 (S: space) will be formed.
  • the substrate on which the resist pattern was formed was observed under an optical microscope at a magnification of 100 times and evaluated according to the following criteria.
  • Good (G): No breaks or defects were observed in the resist pattern with L/S 8 ⁇ m/200 ⁇ m (excluding the case of an "Excellent (E)" rating).
  • Acceptable (A): No breaks or defects were observed in the resist pattern with L/S 10 ⁇ m/200 ⁇ m (excluding cases rated as "excellent (E)" or "good (G)”).
  • ⁇ Flexibility of cured film> The above-mentioned ⁇ Lamination> was carried out on a flexible substrate ⁇ Nikkan Industries NIKKAFLEX F-30VC1 25RC11(H) ⁇ cut to a size of 200 mm x 250 mm, and a photosensitive resin layer was formed on the substrate. Next, exposure was carried out with an energy amount that resulted in 15 remaining steps on a Stouffer Industries 41-step step tablet, with a size of 1 inch width and 250 mm length.
  • the prepared samples were subjected to a mandrel test (cylindrical mandrel method; a bending resistance test conforming to JIS K5600-5-1-1999). Thereafter, the smallest mandrel diameter at which no "cracking" or “peeling from the substrate” was observed in the cured film on the sample was determined, and flexibility was evaluated based on this diameter according to the following criteria. The smaller this value, the higher the flexibility. (Evaluation criteria) Excellent (E): The smallest mandrel diameter at which the cured film showed no "cracking" or "peeling from the substrate” was 6 mm or less.
  • the photosensitive resin laminate of the present invention has good sensitivity and excellent flexibility. Therefore, it can be suitably used as a photosensitive resin laminate for use in forming wiring in a printed wiring board or the like.
  • the photosensitive resin composition of the present invention can suitably obtain the above-mentioned photosensitive resin laminate that can be used industrially.
  • the method for forming a resist pattern of the present invention can be used in a process for forming a wiring pattern.
  • the photosensitive resin composition of the present invention can be used to form wiring in a printed wiring board or the like.
  • the photosensitive resin composition of the present invention By using the photosensitive resin composition of the present invention, the above-mentioned photosensitive resin laminate that can be used industrially can be suitably obtained.
  • the method for forming a resist pattern of the present invention can be suitably used in a process for forming a wiring pattern.

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Abstract

La présente invention concerne une composition de résine photosensible, un corps multicouche de résine photosensible et un procédé de formation de motif de réserve. Cette composition de résine photosensible contient les composants suivants : (A) un polymère soluble dans les alcalis ; (B) un composé ayant une double liaison éthyléniquement insaturée ; (C) un initiateur de polymérisation ; et (D) un composé de bore qui absorbe les rayons h et/ou les rayons i.
PCT/JP2023/038065 2022-10-21 2023-10-20 Composition de résine photosensible, corps multicouche de résine photosensible et procédé de formation de motif de réserve WO2024085254A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04172456A (ja) * 1990-11-06 1992-06-19 Toray Ind Inc 湿し水不要平版印刷用原版
WO2022186389A1 (fr) * 2021-03-05 2022-09-09 旭化成株式会社 Corps multicouche de résine photosensible et son procédé de production
JP2022136141A (ja) * 2018-05-17 2022-09-15 東洋インキＳｃホールディングス株式会社 カラーフィルタ用着色組成物及びカラーフィルタ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04172456A (ja) * 1990-11-06 1992-06-19 Toray Ind Inc 湿し水不要平版印刷用原版
JP2022136141A (ja) * 2018-05-17 2022-09-15 東洋インキＳｃホールディングス株式会社 カラーフィルタ用着色組成物及びカラーフィルタ
WO2022186389A1 (fr) * 2021-03-05 2022-09-09 旭化成株式会社 Corps multicouche de résine photosensible et son procédé de production

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