WO2021120106A1 - Alkali-soluble resin, photosensitive resin composition, photosensitive element, method of forming resist pattern, and method of forming wiring pattern - Google Patents

Alkali-soluble resin, photosensitive resin composition, photosensitive element, method of forming resist pattern, and method of forming wiring pattern Download PDF

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Publication number
WO2021120106A1
WO2021120106A1 PCT/CN2019/126633 CN2019126633W WO2021120106A1 WO 2021120106 A1 WO2021120106 A1 WO 2021120106A1 CN 2019126633 W CN2019126633 W CN 2019126633W WO 2021120106 A1 WO2021120106 A1 WO 2021120106A1
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group
meth
alkali
photosensitive
forming
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PCT/CN2019/126633
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French (fr)
Inventor
Akitoshi Tanimoto
Sadaaki Kato
Yasuharu Murakami
Xuesong Jiang
Xiao-dong MA
Original Assignee
Showa Denko Materials Co., Ltd.
Shanghai Jiao Tong University
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Application filed by Showa Denko Materials Co., Ltd., Shanghai Jiao Tong University filed Critical Showa Denko Materials Co., Ltd.
Priority to PCT/CN2019/126633 priority Critical patent/WO2021120106A1/en
Priority to JP2022535935A priority patent/JP7507862B2/en
Priority to CN201980103561.5A priority patent/CN115087929A/en
Publication of WO2021120106A1 publication Critical patent/WO2021120106A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen

Definitions

  • the present invention relates to an alkali-soluble resin, a photosensitive resin composition, a photosensitive element, a method of forming a resist pattern, and a method of forming a wiring pattern.
  • a photosensitive resin composition and a photosensitive element comprising a layer (hereinafter, also referred to as ′′photosensitive layer′′ ) formed by using a photosensitive resin composition on a support film are widely used as a resist material used for etching treatment or plating treatment.
  • the printed wiring board is manufactured by the following procedure, for example, by using the photosensitive element. That is, the photosensitive layer of the photosensitive element is laminated on a circuit forming substrate such as a copper clad laminate. The photosensitive layer is exposed through a mask film or the like to form a photocured part. At this time, the support film is stripped before or after exposure. Thereafter, regions other than the photocured part of the photosensitive layer are removed with a developer to form a resist pattern. Using the resist pattern as a resist, etching treatment or plating treatment is performed to form a conductor pattern, and finally a photocured part (resist pattern) of the photosensitive layer is stripped (removed) .
  • an aqueous stripping solution has been used instead of the conventionally used amine stripping solution for stripping the resist pattern (for example, refer to Patent Literature 1) .
  • Patent Literature 1 JP 2013-061556 A
  • the photosensitive resin composition is not only required to form a resist pattern having a high developability in an unexposed part and having excellent resolution, but also required to have excellent stripping characteristics in the photocured part in order to strip and remove the resist pattern.
  • the stripping time of the resist pattern is longer than that of the amine stripping solution, and the stripped pieces tend to be hard to be small.
  • it is conceivable to increase the hydrophilicity of the binder resin contained in the photosensitive layer but the exposed part of the photosensitive layer easily swells during development, resulting in a reduction in resolution.
  • the hydrophobicity of the binder resin is attempted to be increased, not only the developability of the unexposed part is reduced, but also the shorter stripping time of the resist pattern and the smaller stripped pieces are unachievable.
  • An object of the present invention is to provide an alkali-soluble resin used in a photosensitive resin composition having excellent developability, resolution, and stripping characteristics; a photosensitive resin composition including the alkali-soluble resin; photosensitive element; the method of forming a resist pattern; and the method of forming a wiring pattern.
  • One aspect of the present invention relates to an alkali-soluble resin comprising a structural unit having a polarity converting group and a structural unit having a carboxy group, wherein the polar conversion group has a group being not eliminated under weak alkaline conditions but being eliminated under strong alkaline conditions.
  • the present invention relates to a photosensitive resin composition
  • a photosensitive resin composition comprising a binder resin comprising the above alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.
  • the present invention relates to a photosensitive element comprising a support and a photosensitive layer formed on the support, wherein the photosensitive layer comprises the above photosensitive resin composition.
  • the present invention relates to a method for forming a resist pattern comprising: a step of forming a photosensitive layer on the substrate by using the photosensitive resin composition or the photosensitive element; a step of irradiating at least a part of the photosensitive layer with actinic light to form a photocured part; and a step of removing at least a part other than the photocured part of the photosensitive layer from the substrate.
  • the present invention relates to a method of forming a wiring pattern comprising a step of forming a conductor pattern by etching treatment or plating treatment of a substrate having a resist pattern formed thereon by the method of forming a resist pattern.
  • the present invention can provide an alkali-soluble resin used in a photosensitive resin composition having excellent developability, resolution, and stripping characteristics; a photosensitive resin composition including the alkali-soluble resin; photosensitive element; the method of forming a resist pattern; and the method of forming a wiring pattern.
  • Figure 1 is a schematic cross-sectional view showing one embodiment of a photosensitive element.
  • the term ′′step′′ includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step is achieved.
  • the numerical range shown using ′′to′′ shows the range which includes the numerical values described before and after ′′to′′ as the minimum value and the maximum value, respectively.
  • the term ′′layer′′ includes not only a structure of a shape formed on the entire surface but also a structure of a shape formed in part when it is observed as a plan view.
  • ′′(Meth) acrylic acid′′ means at least one of ′′acrylic acid′′ and ′′methacrylic acid′′ corresponding thereto. The same applies to other similar expressions such as (meth) acryloyl.
  • the amount of each component in the photosensitive resin composition means the total amount of the plurality of the substances present in the photosensitive resin composition.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in Examples.
  • the aspect which arbitrarily combines the matters described in this description is also included in this invention.
  • ′′solids′′ refers to non-volatile components excluding volatiles such as water and solvents contained in the photosensitive resin composition. That is, ′′solids′′ refers to components other than the solvent which remains without volatilization in drying of the photosensitive resin composition described below, and also includes liquid, millet jelly-like, and wax components at room temperature (25°C) .
  • the alkali-soluble resin according to the present embodiment comprises a structural unit having a polarity converting group and a structural unit having a carboxy group, wherein the polarity converting group has a group being not eliminated under weak alkaline conditions but being eliminated under strong alkaline conditions.
  • An alkali-soluble resin is a resin that is soluble in an alkaline aqueous solution.
  • the alkaline aqueous solution include a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, a metal carbonate aqueous solution, and an organic amine aqueous solution.
  • TMAH tetramethylammonium hydroxide
  • a varnish obtained by dissolving a resin in an arbitrary solvent is spin-coated on a substrate such as a silicon wafer to form a coating film having 5 ⁇ m thickness.
  • This is immersed in a TMAH aqueous solution, a metal hydroxide aqueous solution, a metal carbonate aqueous solution, or an organic amine aqueous solution at 20 to 25°C.
  • TMAH aqueous solution a metal hydroxide aqueous solution
  • a metal carbonate aqueous solution a metal carbonate aqueous solution
  • organic amine aqueous solution at 20 to 25°C.
  • the ′′polarity converting group′′ means a functional group whose polarity is converted from hydrophobic to hydrophilic.
  • the polarity converting group according to the present embodiment is stable and exhibits hydrophobicity under weak alkaline conditions, but can decompose under strong alkaline conditions to generate hydrophilic groups such as hydroxyl groups and carboxy groups.
  • weak alkaline conditions include development with an alkaline aqueous solution of the photosensitive layer in the formation of a resist pattern described below.
  • Examples of the strong alkali condition include stripping of the formed resist pattern with an alkaline aqueous solution.
  • the polarity conversion group according to the present embodiment is a group that exhibits stable hydrophobicity against the weak alkaline aqueous solution used for developing the photosensitive layer, and can be decomposed by the strong alkaline aqueous solution used for stripping the resist pattern to change a hydrophilic group.
  • the alkali-soluble resin according to the present embodiment can be used as a binder resin of a photosensitive resin composition, and can improve the developability, resolution, and stripping characteristics of a photosensitive layer formed from the photosensitive resin composition.
  • using the alkali-soluble resin according to the present embodiment for a photosensitive resin composition for thick film applications can improve the stripping characteristics while maintaining the resolution.
  • the alkali-soluble resin comprises the structural unit which has a polarity conversion group from the viewpoint of stripping characteristics.
  • the polar conversion group may be a group represented by the following formula (1) .
  • R 2 represents a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, or a trityl group.
  • the group represented by the formula (1) can be converted to ′′-OH′′ by elimination of R 2 under strong alkaline conditions.
  • the structural unit having the above polarity converting group may be a structural unit based on a compound represented by the following formula (2) .
  • R 1 represents a hydrogen atom or a methyl group
  • L 1 represents an alkylene group having 1 to 6 carbon atoms
  • R 2 represents a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, or a trityl group.
  • L 1 is preferable to be an alkylene group having 1 to 4 carbon atoms, more preferable to be an alkylene group having 1 to 3 carbon atoms, and still more preferable to be an alkylene group having 2 or 3 carbon atoms.
  • Examples of the compound represented by the formula (2) include 2- (trimethylsilyloxy) ethyl (meth) acrylate, trimethylsilyl (meth) acrylate, and trityl (meth) acrylate.
  • the alkali-soluble resin according to the present embodiment can be manufactured, for example, by radical polymerization of a monomer having a polarity converting group and a monomer having a carboxy group.
  • the content of the monomer having a polarity converting group may be 1%by mass or more, 2%by mass or more, 3%by mass or more, or 4%by mass or more, based on the total amount of the monomer constituting the alkali-soluble resin. From the viewpoint of further improving developability, the content of the monomer having a polarity converting group may be 35%by mass or less, 30%by mass or less, or 25%by mass or less.
  • the alkali-soluble resin comprises a structural unit having a carboxy group from the viewpoint of alkaline developability.
  • the monomer having a carboxy group include (meth) acrylic acid, ⁇ -bromoacrylic acid, ⁇ -chloroacrylic acid, ⁇ -furyl (meth) acrylic acid, ⁇ -styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, maleic acid monoesters such as monoisopropyl maleate, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.
  • the monomer having a carboxy group may be (meth) acrylic acid or methacrylic acid.
  • the content of the structural unit derived from the monomer having a carboxy group may be 10 to 45%by mass, 15 to 40%by mass, or 20 to 35%by mass, based on the total amount of the monomer constituting the alkali-soluble resin.
  • the content is 10%by mass or more, alkaline developability tends to be improved, and when the content is 45%by mass or less, alkali resistance tends to be excellent.
  • the alkali-soluble resin may have a structural unit based on styrene or a styrene derivative from the viewpoints of adhesion and stripping characteristics.
  • Styrene derivatives are a polymerizable compound such as vinyl toluene and ⁇ -methylstyrene in which ⁇ -position of styrene or a hydrogen atom in an aromatic ring has been replaced.
  • the content of the structural unit based on styrene or styrene derivatives in the alkali-soluble resin may be 10 to 60%by mass, 15 to 55%by mass, or 25 to 50%by mass. When this content is 10%by mass or more, the adhesion tends to be improved, and when this content is 60%by mass or less, an increase in the size of the stripped pieces during development can be suppressed and the longer time required for stripping tends to be suppressed.
  • the alkali-soluble resin may have a structural unit based on (meth) acrylic acid benzyl ester from the viewpoint of resolution and aspect ratio.
  • the content of the structural unit derived from the (meth) acrylic acid benzyl ester in the alkali-soluble resin may be 5 to 50%by mass, 15 to 45%by mass, or 10 to 40%by mass from the viewpoint of improving resolution.
  • the alkali-soluble resin may have a structural unit based on (meth) acrylic acid alkyl ester from the viewpoint of improving plasticity.
  • the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester.
  • the weight average molecular weight (Mw) of the alkali-soluble resin may be 1000 or more, 2000 or more, 3000 or more, or 5000 or more. From the viewpoint of suitable development, Mw of the alkali-soluble resin may be 30000 or less, 28000 or less, 26000 or less, or 24000 or less. Mw can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • the degree of hydrophilicity of the alkali-soluble resin can be calculated by the following formula from the degree of hydrophilicity of the monomer constituting the alkali-soluble resin and the copolymerization ratio of the monomer.
  • the degree of hydrophilicity of the monomer is the amount of water (%by mass) included in the monomer as measured by the Karl Fischer method after adding ion-exchanged water to the monomer and leaving at 23°C for 12 hours.
  • Degree of hydrophilicity of alkali-soluble resin monomer copolymerization ratio (%by mass) ⁇ degree of hydrophilicity of monomer
  • the hydrophilicity of the alkali-soluble resin before the polarity converting group is decomposed may be 80 to 120, 82 to 115, or 84 to 110 from the viewpoint of alkali resistance during development of the exposed part.
  • the degree of the hydrophilicity of the alkali-soluble resin after the polarity conversing group has been decomposed may be 95 to 120, 98 to 115, or 100 to 110 from the viewpoint of the stripping characteristics.
  • the rate of increase in the degree of hydrophilicity after polarity conversion may be 3 to 45%, 5 to 40%, or 10 to 35%.
  • the photosensitive resin composition according to the present embodiment contains (A) binder resin (hereinafter sometimes referred to as ′′component (A) ′′) ; (B) a photopolymerizable compound (hereinafter sometimes referred to as ′′component (B) ′′ ) ; and (C) photopolymerization initiator (hereinafter sometimes referred to as ′′component (C) ′′ ) .
  • A binder resin
  • B a photopolymerizable compound
  • C photopolymerization initiator
  • the binder resin as the component (A) includes an alkali-soluble resin according to the present embodiment (hereinafter sometimes referred to as ′′component (A1) ′′ ) . Containing the component (A1) improves the alkali resistance during development of the exposed part, allowing a resist pattern having excellent resolution to be formed. The resist pattern can be stripped with a strong alkaline aqueous solution.
  • the component (A1) may be composed of only one resin, or may be composed of two or more resins.
  • the component (A) may further include an alkali-soluble resin other than the component (A1) .
  • the alkali-soluble resin may be a resin having a phenolic hydroxyl group.
  • the resin having a phenolic hydroxyl group include polyhydroxystyrene, hydroxystyrene-based resins such as copolymers including hydroxystyrene as a monomer unit, phenolic resins, polybenzoxazole precursors such as poly (hydroxyamide) , poly (hydroxyphenylene) ether, and polynaphthol.
  • the content of the component (A) may be 30 to 90 parts by mass, 40 to 85 parts by mass, or 50 to 80 parts by mass with respect to 100 parts by mass of total amounts of the component (A) and the component (B) .
  • the content of the component (A) is within this range, the strength of the photocured part of the photosensitive layer becomes better.
  • the component (B) is a compound having a functional group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenyl ethynyl group, a maleimide group, a nadimide group, and a (meth) acryloyl group as a functional group which exhibits photopolymerization.
  • the component (B) is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups.
  • a (meth) acryloyl group is preferable.
  • the component (B) may be used singly or in combination of two or more.
  • Examples of the photopolymerizable compound having one ethylenically unsaturated group include (meth) acrylic acids, alkyl (meth) acrylates, and phthalic acid-based (meth) acrylate compounds.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and hydroxylethyl (meth) acrylate.
  • the component (B) may include a phthalic acid-based compound.
  • the phthalic acid-based compound include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ ′- (meth) acryloyloxyethyl-o-phthalate (aka: 3-chloro-2-hydroxypropyl-2- (meth) acryloyloxyethylphthalate) , ⁇ -hydroxyethyl- ⁇ ′- (meth) acryloyloxyethyl-o-phthalate, and ⁇ -hydroxypropyl- ⁇ ′- (meth) acryloyloxyethyl-o-phthalate.
  • Examples of the photopolymerizable compound having two ethylenically unsaturated groups include polyethylene glycol di(meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2, 2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane, bisphenol A diglycidyl ether di (meth) acrylate, and alkylene oxide-modified bisphenol A di (meth) acrylate.
  • the component (B) may include an alkylene oxide-modified bisphenol A di (meth) acrylate.
  • alkylene oxide modified bisphenol A di (meth) acrylate examples include 2, 2-bis (4- ( (meth) acryloxypolyethoxy) phenyl) propane (for example: 2, 2-bis (4- ( (meth) acryloxypentaethoxy) phenyl) propane) , 2, 2-bis (4- ( (meth) acryloxypolypropoxy) phenyl) propane, 2, 2-bis (4- ( (meth) acryloxypolybutoxy) phenyl) propane, and 2, 2-bis (4- ( (meth) acryloxypolyethoxypolypropoxy) phenyl) propane.
  • Examples of the photopolymerizable compound having 3 or more ethylenically unsaturated groups include (meth) acrylate having a skeleton derived from trimethylolpropane such as trimethylolpropane tri (meth) acrylate; (meth) acrylate having a skeleton derived from tetramethylolmethane such as tetramethylolmethane tri (meth) acrylate and tetramethylolmethane tetra (meth) acrylate; (meth) acrylate having a skeleton derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate; (meth) acrylate having a skeleton derived from dipentaerythritol such as dipentaerythritol penta (meth) acrylate and dipentaeryth
  • (meth) acrylate compounds having a skeleton derived from dipentaerythritol are preferable and dipentaerythritol penta (meth) acrylate is more preferable.
  • the component (B) may include a photopolymerizable compound having an ethylenically unsaturated group and an acid-modified group.
  • the acidic group to be modified include a carboxy group, a sulfo group, and a phenolic hydroxyl group, and among them, the carboxy group is preferable.
  • Examples of the photopolymerizable compound having an ethylenically unsaturated group and an acidic group include styrene-maleic acid-based resin and acid-modified epoxy derivative containing a vinyl group.
  • the styrene-maleic acid-based resin is a hydroxyethyl (meth) acrylate modified product of a styrene-maleic anhydride copolymer.
  • the acid-modified epoxy derivative containing a vinyl group is a compound obtained by reacting a compound having epoxy resin modified with vinyl group-containing organic acid with saturated or unsaturated group-containing polybasic acid anhydride.
  • the epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups.
  • the epoxy resin include a glycidyl ether type epoxy resin, a glycidylamine type epoxy resin, and a glycidyl ester type epoxy resin. Among them, from the viewpoint of reliability in mounting semiconductor chips, a bisphenol novolac type epoxy resin is preferable and a bisphenol F novolac type epoxy resin is more preferable.
  • the vinyl group-containing organic acid is not particularly limited, and may be a vinyl group-containing monocarboxylic acid.
  • the vinyl group-containing monocarboxylic acid include acrylic acid derivatives such as acrylic acid, a dimer of acrylic acid, methacrylic acid, ⁇ -furfurylacrylic acid, ⁇ -styrylacrylic acid, cinnamic acid, crotonic acid, and ⁇ -cyanocinnamic acid; a half ester compound which is a reaction product of a hydroxyl group-containing acrylate and a dibasic acid anhydride; and a half ester compound which is a reaction product of a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride.
  • the ethylenically unsaturated bond is not particularly limited as long as photopolymerization is possible.
  • Examples of the ethylenically unsaturated bond include an ⁇ , ⁇ -unsaturated carbonyl group such as a (meth) acryloyl group.
  • Examples of the photopolymerizable compound having an ⁇ , ⁇ -unsaturated carbonyl group include ⁇ , ⁇ -unsaturated carboxylic acid ester of polyhydric alcohol, bisphenol type (meth) acrylate, ⁇ , ⁇ -unsaturated carboxylic acid adduct of a glycidyl group-containing compound, (meth) acrylate having a urethane bond, nonylphenoxypolyethyleneoxyacrylate, and (meth) acrylic acid alkyl ester.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester of a polyhydric alcohol include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, polyethylene/polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, and a (meth) acrylate compound having
  • the component (B) may include polyalkylene glycol di (meth) acrylate from the viewpoint of improving the flexibility of the resist pattern.
  • the polyalkylene glycol di (meth) acrylate may have at least one of an EO group and a PO group, or may have both an EO group and a PO group.
  • each of the EO group and the PO group may be continuously present in block or may be present randomly.
  • the PO group may be either an oxy-n-propylene group or an oxyisopropylene group.
  • the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.
  • Examples of commercially available products of polyalkylene glycol di (meth) acrylate include FA-023M (manufactured by Hitachi Chemical Co., Ltd. ) , FA-024M (manufactured by Hitachi Chemical Co., Ltd. ) , and NK ester HEMA-9P (manufactured by Shin-Nakamura Chemical Co., Ltd. ) .
  • the component (B) may include (meth) acrylate having urethane bond from the viewpoint of improving the flexibility of the resist pattern.
  • the (meth) acrylate having urethane bond include an addition reaction product of (meth) acrylic monomer having OH group at ⁇ -position and diisocyanate (such as isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, and 1, 6-hexamethylene diisocyanate) , tris ( (meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO-and PO-modified urethane di (meth) acrylate.
  • Examples of commercially available EO-modified urethane di (meth) acrylates include ′′UA-11′′ and ′′UA-21EB′′ (manufactured by Shin-Nakamura Chemical Co., Ltd. ) .
  • Examples of commercially available EO-and PO-modified urethane di (meth) acrylates include ′′UA-13′′ (manufactured by Shin-Nakamura Chemical Co., Ltd. ) .
  • the component (B) may include a (meth) acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol, from the viewpoint of easily forming a thick resist pattern and improving the resolution and adhesion in a balanced manner.
  • the (meth) acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol is preferable to have four or more (meth) acryloyl groups, and may be dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate.
  • the component (B) may include bisphenol (meth) acrylate, and may include bisphenol A (meth) acrylate among bisphenol (meth) acrylates.
  • the bisphenol A (meth) acrylate include 2, 2-bis (4- ( (meth) acryloxypolyethoxy) phenyl) propane, 2, 2-bis (4- ( (meth) acryloxypolypropoxy) phenyl) propane, 2, 2-bis (4- ( (meth) acryloxypolybutoxy) phenyl) propane, and 2, 2-bis (4- ( (meth) acryloxypolyethoxypolypropoxy) phenyl) propane.
  • 2, 2-bis (4- ( (meth) acryloxypolyethoxy) phenyl) propane is preferable from the viewpoint of further improving the resolution and the patterning ability.
  • examples of 2, 2-bis (4- ( (meth) acryloxydipropoxy) phenyl) propane include BPE-200 (Shin-Nakamura Chemical Co., Ltd. )
  • examples of 2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane include BPE-500 (Shin-Nakamura Chemical Co., Ltd. ) and FA-321M (Hitachi Chemical Co., Ltd. ) .
  • nonylphenoxypolyethyleneoxyacrylate examples include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.
  • the component (C) is not particularly limited as long as it is a component capable of polymerizing the component (B) , and can be appropriately selected from commonly used photopolymerization initiators.
  • the component (C) can be used singly or in combination of two or more.
  • component (C) examples include photopolymerization initiators such as acylphosphine oxide, oxime ester, aromatic ketone, quinone, alkylphenone, imidazole, acridine, phenylglycine, and coumarin.
  • photopolymerization initiators such as acylphosphine oxide, oxime ester, aromatic ketone, quinone, alkylphenone, imidazole, acridine, phenylglycine, and coumarin.
  • the component (C) may include an acridine photopolymerization initiator, a phenylglycine photopolymerization initiator, or an imidazole photopolymerization initiator, from the viewpoint of improving sensitivity and resolution in a balanced manner.
  • acridine photopolymerization initiator examples include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine, 9-pentylaminoacridine, bis (9-acridinyl) alkanes such as 1, 2-bis (9-acridinyl) ethane, 1, 4-bis (9-acridinyl) butane, 1, 6-bis (9-acridinyl) hexane, 1, 8-bis (9-acridinyl) octane, 1, 10-bis (9-acridinyl) decane, 1, 12-bis (9-acridinyl) dodecane, 1,
  • phenylglycine photopolymerization initiator examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
  • imidazole photopolymerization initiator examples include 2- (o-chlorophenyl) -4, 5-diphenylbiimidazole, 2, 2′, 5-tris- (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4′, 5′-diphenylbiim idazole, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylbiimidazole , 2, 4, 5-tris- (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -biimidazole, 2, 2′-bis- (2-fluorophenyl) -4, 4′, 5, 5′-tetrakis- (3-methoxyphenyl) -biimidazo le, 2, 2′-bis
  • the content of the component (C) may be 0.1 to 10 parts by mass, 0.2 to 5 parts by mass, or 0.5 to 4 parts by mass with respect to 100 parts by mass of total amounts of the component (A) and the component (B) .
  • the content of the component (C) is 0.1 parts by mass or more, the photosensitivity, resolution, and adhesion tend to be improved, and when the content is 10 parts by mass or less, the resist patterning ability tends to be excellent.
  • the photosensitive resin composition according to the present embodiment may further include a photosensitizer as the component (D) . Containing the component (D) allows the absorption wavelength of actinic light used for exposure to be effectively used.
  • the component (D) may be used singly or in combination of two or more.
  • Examples of the component (D) include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
  • the component (D) may include a pyrazoline compound or an anthracene compound from the viewpoint of further improving the resolution.
  • Examples of the pyrazoline compound include 1- (4-methoxyphenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1, 5-bis- (4-methoxyphenyl) -3- (4-methoxystyryl) -pyrazoline, 1- (4-isopropylphenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1, 5-bis- (4-isopropylphenyl) -3- (4-isopropylstyryl) -pyrazoline, 1- (4-methoxyphenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline,
  • anthracene compound examples include 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-dipropoxyanthracene, 9, 10-dibutoxyanthracene, and 9, 10-dipentoxyanthracene.
  • the content of the component (D) may be 0.01 to 5 parts by mass, 0.01 to 1 part by mass, or 0.01 to 0.2 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) .
  • the photosensitive resin composition according to the present embodiment may further contain additives such as dyes, photochromic agents, thermochromic inhibitors, plasticizers, pigments, fillers, antifoaming agents, flame retardants, adhesion promoters, leveling agents, stripping accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and polymerization inhibitors.
  • additives such as dyes, photochromic agents, thermochromic inhibitors, plasticizers, pigments, fillers, antifoaming agents, flame retardants, adhesion promoters, leveling agents, stripping accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and polymerization inhibitors.
  • Examples of the dye include malachite green, victoria pure blue, brilliant green, and methyl violet.
  • Examples of the photochromic agent include tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline.
  • Examples of the plasticizer include p-toluenesulfonamide.
  • the photosensitive resin composition is dissolved in a solvent, such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, and propylene glycol monomethyl ether, or a mixed solvent thereof, allowing a solution having a solid content of about 30 to 60%by mass to be prepared.
  • a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, and propylene glycol monomethyl ether, or a mixed solvent thereof, allowing a solution having a solid content of about 30 to 60%by mass to be prepared.
  • the photosensitive element of the present embodiment comprises a support and a photosensitive layer formed on the support, and the photosensitive layer comprises the above photosensitive resin composition.
  • the photosensitive layer is laminated on the substrate and then may be exposed without stripping the support (support film) .
  • the photosensitive element 1 according to the present embodiment is formed by comprising a support 2 and a photosensitive layer 3 derived from the above photosensitive resin composition formed on the support 2, and comprising other layers such as a protective layer 4 provided as required.
  • polyester films such as polyethylene terephthalate (PET) , polybutylene terephthalate (PBT) , and polyethylene-2, 6-naphthalate (PEN) , and polyolefin films such as polypropylene and polyethylene.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene-2, 6-naphthalate
  • polyolefin films such as polypropylene and polyethylene.
  • a PET film may be used from the viewpoint of being easily available and excellent in handling in the manufacturing process (particularly, heat resistance, thermal shrinkage, and breaking strength) .
  • the haze of the support may be 0.01 to 1.0%or 0.01 to 0.5%. When the haze is 0.01%or more, the support itself tends to be easily manufactured, and when the haze is 1.0%or less, fine defects that may occur in the resist pattern tends to decrease.
  • ′′Haze′′ means cloudiness.
  • the haze in the present disclosure refers to a value measured by using a commercially available cloudiness meter (turbidimeter) in accordance with the method defined in JIS K 7105. Haze can be measured with a commercially available turbidimeter such as NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd. ) .
  • the thickness of the support may be 1 to 100 ⁇ m, 5 to 60 ⁇ m, 10 to 50 ⁇ m, 10 to 40 ⁇ m, 10 to 30 ⁇ m, or 10 to 25 ⁇ m.
  • the thickness of the support is 1 ⁇ m or more, and thereby the support tends to be prevented from being broken when the support is stripped.
  • the thickness of the support is 100 ⁇ m or less, which can suppress reduction of resolution in exposing through the support.
  • the photosensitive element may further comprise a protective layer as required.
  • a protective layer a film in which the adhesive force between the photosensitive layer and the protective layer is smaller than the adhesive force between the photosensitive layer and the support may be used, and a film with a low fish eye may be used. Specific examples thereof include one that can be used as the above support. From the viewpoint of stripping from the photosensitive layer, a polyethylene film may be used.
  • the thickness of the protective layer may be about 1 to 100 ⁇ m, depending on applications.
  • the photosensitive element can be manufactured as follows, for example.
  • a photosensitive resin composition solution (coating solution) is applied on a support to form a coating layer, and this is dried to form a photosensitive layer.
  • Covering the photosensitive layer surface opposite to the support with the protective layer provide a photosensitive element comprising the support, the photosensitive layer formed on the support, and the protective layer laminated on the photosensitive layer.
  • Application of the coating solution onto the support can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.
  • the drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer.
  • the drying may be performed at 70 to 150°C for about 5 to 30 minutes.
  • the amount of residual solvent in the photosensitive layer may be 2%by mass or less, from the viewpoint of preventing diffusion of the solvent in the subsequent step.
  • the thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on applications, and may be 1 to 100 ⁇ m, 1 to 50 ⁇ m, or 5 to 40 ⁇ m in thickness after drying. When the thickness is 1 ⁇ m or more, industrial coating becomes easy and productivity is improved. In addition, 100 ⁇ m or less in thickness improves adhesion and resolution.
  • the form of the photosensitive element is not particularly limited.
  • the form may be a sheet shape or a shape obtained by winding on a core in the roll shape. In winding in roll shape, winding may be performed so that the support film is an outer side.
  • the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, or ABS resin (acrylonitrile-butadiene-styrene copolymer) .
  • An end face separator may be provided on the end face of the roll-shaped photosensitive element from the viewpoint of end face protection, and a moisture-proof end face separator may be provided from the viewpoint of edge fusion resistance.
  • the photosensitive element may be wrapped in a black sheet with low moisture permeability.
  • the photosensitive element can be suitably used, for example, in a method of forming a resist pattern described below.
  • the photosensitive element is suitable for the application to the manufacturing method which forms a conductor pattern by plating treatment, from the viewpoint of resolution.
  • the method of forming a resist pattern comprises (i) a step of forming a photosensitive layer on a substrate using the above photosensitive resin composition or the above photosensitive element (photosensitive layer forming step) ; (ii) a step of irradiating at least a part (predetermined part) of the photosensitive layer with actinic light to form a photocured part (exposure step) ; and (iii) a step of removing at least a part other than the photocured part from the above substrate to form a resist pattern (developing step) , and may be composed of other steps as required.
  • the resist pattern can be referred to as a photocured product pattern of the photosensitive resin composition or a relief pattern.
  • the method for forming a resist pattern can be referred to as a method of manufacturing a substrate with a resist pattern.
  • the above photosensitive resin composition may be applied and dried, or after removing the protective layer from the photosensitive element, the photosensitive layer of the photosensitive element may be pressure-bonded to the above substrate while heating.
  • a photosensitive element provides a laminate consisting of a substrate, a photosensitive layer, and a support wherein these are sequentially laminated.
  • the above substrate is not particularly limited, and typically, a circuit forming substrate comprised with an insulating layer and a conductor layer formed on the insulating layer, or a die pad (alead frame substrate) such as an alloy base material is used.
  • the photosensitive layer forming step is preferable to be performed under reduced pressure, from the viewpoint of adhesion and followability.
  • the photosensitive layer and/or the substrate may be heated at a temperature of 70 to 130°C during the pressure bonding.
  • the pressure bonding may be performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm 2 ) , but these conditions are appropriately selected as required.
  • preheat treatment of the substrate in advance is not necessary, but preheat treatment of the substrate can be performed in order to further improve the adhesion and followability.
  • the photosensitive layer In the exposure step, at least a part of a photosensitive layer formed on a substrate is irradiated with actinic light, photocuring the part irradiated with the actinic light to form a latent image.
  • the photosensitive layer when the support is present on the photosensitive layer, the photosensitive layer can be irradiated with the actinic light through the support if the support is transparent to the actinic light, but the photosensitive layer is irradiated with the actinic light after the support is removed if the support is light-shielding.
  • Examples of the exposure method include a method of imagewise irradiating actinic light through a negative or positive mask pattern, referred to as an artwork (mask exposure method) .
  • the method of imagewise irradiating actinic light with a projection exposure method may be employed.
  • the method of imagewise irradiating actinic light by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.
  • LDI Laser Direct Imaging
  • DLP Digital Light Processing
  • a known light source can be used, and for example, carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid state lasers such as YAG lasers, ultraviolet rays such as semiconductor lasers, and those that effectively emit visible light are used.
  • the development step at least a part of the above photosensitive layer other than the photocured part is removed from the substrate, forming a resist pattern on the substrate.
  • the support When the support is present on the photosensitive layer, the support is removed, and then removal (development) of a region other than the above photocured part (also referred to as an unexposed part) is performed.
  • Development methods include wet development and dry development, and the wet development is widely used.
  • development is performed by a known development method using a developer corresponding to the photosensitive resin composition.
  • the development method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like, and from the viewpoint of improving resolution, a high-pressure spray method may be used. Development may be performed by combining these two or more methods.
  • the configuration of the developer is appropriately selected according to the configuration of the above photosensitive resin composition.
  • the developer include an alkaline aqueous solution and an organic solvent developer.
  • an alkaline aqueous solution may be used as the developer.
  • the base of the alkaline aqueous solution include alkali hydroxide such as hydroxide of lithium, sodium, or potassium; alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium, or ammonium; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1, 3-propanediol; 1, 3-diaminopropanol-2; and morpholine.
  • alkali hydroxide such as hydroxide of lithium, sodium, or potassium
  • alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium, or ammonium
  • alkali metal phosphates such as potassium
  • an alkaline aqueous solution used for development a dilute solution of sodium carbonate in 0.1 to 5%by mass, a dilute solution of potassium carbonate in 0.1 to 5%by mass, a dilute solution of sodium hydroxide in 0.1 to 5%by mass, a dilute solution of sodium tetraborate in 0.1 to 5%by mass, and the like can be used.
  • the pH of the alkaline aqueous solution may be in the range of 9 to 14, and the temperature can be adjusted according to the alkaline developability of the photosensitive layer.
  • a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
  • Examples of the organic solvent used in the alkaline aqueous solution include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.
  • organic solvent used in the organic solvent developer examples include 1, 1, 1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone.
  • these organic solvents may be added with water so as to be in the range of 1 to 20%by mass to obtain an organic solvent developer.
  • a step of further curing the resist pattern may be included by heating at about 60 to 250°C or exposure at about 0.2 to 10 J/cm 2 as required after removing the uncured part in the development step.
  • the method of forming a wiring pattern according to the present embodiment has a step of forming a conductor pattern by etching treatment or plating treatment of a substrate having the resist pattern formed thereon by the above method of forming a resist pattern.
  • the method of forming a wiring pattern may further comprise a step of removing the photocured part with an alkaline aqueous solution after the etching treatment or the plating treatment.
  • the plating treatment is performed on the conductor layer provided on the substrate by using the resist pattern formed on the substrate as a mask.
  • the resist may be removed by removing the resist pattern, which will be described below, and the conductor layer covered with the resist may be etched to form a conductor pattern.
  • the plating treatment method may be electro-plating treatment, electroless plating treatment, or electroless plating treatment.
  • the conductor layer provided on the substrate is removed by etching to form a conductor pattern.
  • the etching treatment method is appropriately selected according to the conductor layer to be removed.
  • the etching solution include a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.
  • the resist pattern on the substrate may be removed.
  • the resist pattern can be removed by, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the above development step.
  • a strong alkaline aqueous solution for example, a 1 to 10%sodium hydroxide aqueous solution by mass and a 1 to 10%potassium hydroxide aqueous solution by mass are used.
  • the removal of the resist pattern may be performed at a temperature of 45 to 65°C by using a strong alkaline aqueous solution.
  • a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment to form a conductor pattern.
  • the etching treatment method in this case is appropriately selected according to the conductor layer to be removed. For example, the above etching solution can be applied.
  • the method of forming a wiring pattern according to the present embodiment can be applied not only to the manufacture of a single-layer printed wiring board but also to the manufacture of a multilayer printed wiring board, and also to the manufacture of a printed wiring board having a through-hole of small-diameter.
  • MA-TBDMS tert-Butyldimethylsilyl methacrylate
  • 96 g of propylene glycol monomethyl ether (MFG) and 64 g of toluene were supplied into 1000 mL of a three-necked flask comprising a stirrer, a nitrogen inlet tube, a reflux condenser, a dropping funnel, and a thermometer, and the temperature was raised to 80°C in a nitrogen atmosphere.
  • MFG propylene glycol monomethyl ether
  • the reaction solution was heated to 95°C and was stirred for 1.5 hours, and then was cooled to room temperature to obtain a polymer solution of an alkali-soluble resin (A1) .
  • the non-volatile content (solid content) of the polymer solution was 40%by mass.
  • a polymer solution of an alkali-soluble resin (A9) was obtained in the same manner as in Example 1, except that MA, STC, BzMA, and 2- (trimethylsilyloxy) ethyl methacrylate (HEMA-TMS) were used in the blending amounts shown in Table 1.
  • MA, STC, BzMA, and 2- (trimethylsilyloxy) ethyl methacrylate (HEMA-TMS) were used in the blending amounts shown in Table 1.
  • Polymer solution of alkali-soluble resins (A13) was obtained in the same manner as in Example 1, except that MA, STC, BzMA, and MA-TBDMS were used in the blending amounts shown in Table 1.
  • Polymer solution of alkali-soluble resins (A14) was obtained in the same manner as in Example 1, except that MA, STC, BzMA, and MA-TES were used in the blending amounts shown in Table 1.
  • a polymer solution of alkali-soluble resin (B1) was obtained in the same manner as in Example 1, except that MA, STC, and BzMA were used in the blending amounts shown in Table 1.
  • Mw was measured by gel permeation chromatography (GPC) and was derived by conversion using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • Hitachi L-6000 manufactured by Hitachi, Ltd.
  • Hitachi L-3300 RI manufactured by Hitachi, Ltd.
  • a photosensitive resin composition was prepared by mixing each component in the blending amounts (parts by mass) shown in Table 2 with respect to 140 parts by mass of the above polymer solution (alkali-soluble resin: 56 parts by mass) .
  • FA-321M (trade name) : 2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd. )
  • FA-MECH (trade name) : (2-hydroxy-3-chloro) propyl-2-methacryloyloxyethyl phthalate (manufactured by Hitachi Chemical Co., Ltd. )
  • BCIM (trade name) : 2, 2′-bis (2-chlorophenyl) -4, 4′, 5, 5′-tetraphenylbiimidazole (manufactured by Hampford Research Inc. )
  • SF-808H mixture of carboxybenzotriazole, 5-amino-1H-tetrazole, and methoxypropanol (Sanwa Kasei Co., Ltd. )
  • the photosensitive resin composition was applied onto a 16 ⁇ m thick polyethylene terephthalate (PET) film (trade name ′′G2J′′ , manufactured by Teijin Film Solution Co., Ltd. ) (support) , and was dried sequentially in a hot air convection dryer at 75°C and 125°C to form a photosensitive layer having a dried thickness of 25 ⁇ m.
  • PET polyethylene terephthalate
  • a polypropylene film product name ′′NF-13′′ , manufactured by Tamapoly Co., Ltd.
  • protecting layer was bonded onto this photosensitive layer to obtain each of the photosensitive element in which the support, the photosensitive layer, and the protective layer were laminated in this order.
  • the initial degree of hydrophilicity of the alkali-soluble resin, the degree of hydrophilicity after the polarity conversion, and the increasing rate of the degree of hydrophilicity were calculated from the degree of hydrophilicity of the above monomer and the copolymerization ratio of the monomer.
  • the degrees of hydrophilicity of the alkali-soluble resin in Examples were shown in Table 4, and the degrees of hydrophilicity of the alkali-soluble resin in Comparative Examples were shown in Table 5.
  • Copper clad laminate (trade name ′′MCL-E-67′′ , manufactured by Hitachi Chemical Co., Ltd. ) in which copper foil (thickness of 35 ⁇ m) was laminated on both sides of the glass fiber reinforced epoxy resin layer was washed with water, acid, and then water and was dried in an air stream.
  • the copper clad laminate was heated to 80°C and the photosensitive element was laminated on the copper surface of the copper clad laminate.
  • Lamination was performed at a pressing pressure of 0.4 MPa on the substrate and a roll speed of 1.0 m/min while removing the protective layer with a heat roll at 110°C.
  • the laminate in which the copper clad laminate, the photosensitive layer, and the support were laminated in this order was obtained.
  • a photosensitive layer having a film thickness of 25 ⁇ m was laminated on the substrate, and then the photosensitive layer was developed with a 1%sodium carbonate aqueous solution by mass at 30°C, and the development time when the remaining film disappeared was measured.
  • the case where the development time was 20 seconds or less was evaluated as ′′A′′
  • the case where the development time was less than 20 seconds was evaluated as ′′B′′ .
  • a glass chrome photo tool (resolution negative: line width/space width having x/x (x: 1 to 30, unit: ⁇ m) wiring pattern) was used as a negative for resolution evaluation, and exposure was performed with an energy amount such that the number of remaining step after development of the Hitachi 41 step tablet was 17.0. After the exposure, development treatment of the photosensitive layer was performed in the same manner as the photosensitivity evaluation.
  • the value of the smallest space width was used to evaluate resolution.
  • the case where the smallest space width was less than 15 ⁇ m was evaluated as ′′A′′
  • the case of 15 to 20 ⁇ m was as ′′B′′
  • the case of more than 20 ⁇ m was as ′′C′′ .
  • a laminate obtained by laminating a photosensitive layer having a film thickness of 25 ⁇ m on a substrate was irradiated with 30 mJ at 405 nm by using a direct drawing exposure apparatus, and using a 1%aqueous sodium carbonate solution by mass at 30°C, spray development was performed for a time twice as long as the minimum development time (the shortest time for removing the unexposed part) , and the unexposed part was removed (development treatment) . After the development treatment, a test piece having a 40 mm ⁇ 50 mm cured film formed on the substrate was obtained.
  • the test piece was immersed in a 3%sodium hydroxide aqueous solution by mass at 50°C, and the time until the cured film was stripped from the substrate was measured.
  • the case where the stripping time was less than 50 seconds was evaluated as ′′A′′
  • the case of 50 seconds or more but less than 60 seconds was as ′′B′′
  • the case of 60 seconds or more was as ′′C′′ .
  • the photosensitive resin composition containing the alkali-soluble resin including the structural unit which has a polarity converting group is compatible with developability, resolution, and stripping.

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Abstract

Alkali-soluble resin comprises a structural unit having a polarity converting group and a structural unit having a carboxy group, wherein the polarity converting group has a group being not eliminated under weak alkaline conditions but being eliminated under strong alkaline conditions.

Description

ALKALI-SOLUBLE RESIN, PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE ELEMENT, METHOD OF FORMING RESIST PATTERN, AND METHOD OF FORMING WIRING PATTERN Technical Field
The present invention relates to an alkali-soluble resin, a photosensitive resin composition, a photosensitive element, a method of forming a resist pattern, and a method of forming a wiring pattern.
Background Art
In the field of manufacturing of printed wiring boards, a photosensitive resin composition and a photosensitive element comprising a layer (hereinafter, also referred to as ″photosensitive layer″ ) formed by using a photosensitive resin composition on a support film are widely used as a resist material used for etching treatment or plating treatment.
The printed wiring board is manufactured by the following procedure, for example, by using the photosensitive element. That is, the photosensitive layer of the photosensitive element is laminated on a circuit forming substrate such as a copper clad laminate. The photosensitive layer is exposed through a mask film or the like to form a photocured part. At this time, the support film is stripped before or after exposure. Thereafter, regions other than the photocured part of the photosensitive layer are removed with a developer to form a resist pattern. Using the resist pattern as a resist, etching treatment or plating  treatment is performed to form a conductor pattern, and finally a photocured part (resist pattern) of the photosensitive layer is stripped (removed) .
From the viewpoint of influence on the environment, an aqueous stripping solution has been used instead of the conventionally used amine stripping solution for stripping the resist pattern (for example, refer to Patent Literature 1) .
Citation List
Patent Literature
Patent Literature 1: JP 2013-061556 A
Summary of Invention
Technical Problem
The photosensitive resin composition is not only required to form a resist pattern having a high developability in an unexposed part and having excellent resolution, but also required to have excellent stripping characteristics in the photocured part in order to strip and remove the resist pattern. On the other hand, when the aqueous stripping solution is used, the stripping time of the resist pattern is longer than that of the amine stripping solution, and the stripped pieces tend to be hard to be small. In order to improve the stripping characteristics, it is conceivable to increase the hydrophilicity of the binder resin contained in the photosensitive layer, but the exposed part of the photosensitive layer easily swells during development, resulting in a reduction in resolution. On the other hand, when the hydrophobicity of the binder resin is attempted to be increased, not only the developability of the unexposed part is reduced, but also the shorter  stripping time of the resist pattern and the smaller stripped pieces are unachievable.
An object of the present invention is to provide an alkali-soluble resin used in a photosensitive resin composition having excellent developability, resolution, and stripping characteristics; a photosensitive resin composition including the alkali-soluble resin; photosensitive element; the method of forming a resist pattern; and the method of forming a wiring pattern.
Solution to Problem
One aspect of the present invention relates to an alkali-soluble resin comprising a structural unit having a polarity converting group and a structural unit having a carboxy group, wherein the polar conversion group has a group being not eliminated under weak alkaline conditions but being eliminated under strong alkaline conditions.
In another aspect, the present invention relates to a photosensitive resin composition comprising a binder resin comprising the above alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.
In another aspect, the present invention relates to a photosensitive element comprising a support and a photosensitive layer formed on the support, wherein the photosensitive layer comprises the above photosensitive resin composition.
In another aspect, the present invention relates to a method for forming a resist pattern comprising: a step of forming a photosensitive layer on the substrate by using the photosensitive resin composition or the photosensitive element; a step of irradiating at least a part of the  photosensitive layer with actinic light to form a photocured part; and a step of removing at least a part other than the photocured part of the photosensitive layer from the substrate.
In another aspect, the present invention relates to a method of forming a wiring pattern comprising a step of forming a conductor pattern by etching treatment or plating treatment of a substrate having a resist pattern formed thereon by the method of forming a resist pattern.
Advantageous Effects of Invention
The present invention can provide an alkali-soluble resin used in a photosensitive resin composition having excellent developability, resolution, and stripping characteristics; a photosensitive resin composition including the alkali-soluble resin; photosensitive element; the method of forming a resist pattern; and the method of forming a wiring pattern.
Brief Description of Drawings
Figure 1 is a schematic cross-sectional view showing one embodiment of a photosensitive element.
Description of Embodiments
Hereinafter, embodiments of the present invention are described in detail. However, the present invention is not limited to the following embodiments.
In this description, the term ″step″ includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step is achieved. The numerical range shown using ″to″ shows the range which includes the numerical values described before and after ″to″ as the minimum  value and the maximum value, respectively. The term ″layer″ includes not only a structure of a shape formed on the entire surface but also a structure of a shape formed in part when it is observed as a plan view. ″(Meth) acrylic acid″ means at least one of ″acrylic acid″ and ″methacrylic acid″ corresponding thereto. The same applies to other similar expressions such as (meth) acryloyl.
In the present description, when a plurality of substances corresponding to each component are present, unless otherwise specified, the amount of each component in the photosensitive resin composition means the total amount of the plurality of the substances present in the photosensitive resin composition. In the numerical range described in the present description, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in Examples. Moreover, the aspect which arbitrarily combines the matters described in this description is also included in this invention. In the present description, ″solids″ refers to non-volatile components excluding volatiles such as water and solvents contained in the photosensitive resin composition. That is, ″solids″ refers to components other than the solvent which remains without volatilization in drying of the photosensitive resin composition described below, and also includes liquid, millet jelly-like, and wax components at room temperature (25℃) .
[Alkali-soluble resin]
The alkali-soluble resin according to the present embodiment comprises a structural unit having a polarity converting group and a structural unit having a carboxy group, wherein the polarity converting  group has a group being not eliminated under weak alkaline conditions but being eliminated under strong alkaline conditions.
An alkali-soluble resin is a resin that is soluble in an alkaline aqueous solution. Examples of the alkaline aqueous solution include a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, a metal carbonate aqueous solution, and an organic amine aqueous solution. Whether the resin is soluble in an alkaline aqueous solution can be confirmed, for example, as follows.
A varnish obtained by dissolving a resin in an arbitrary solvent is spin-coated on a substrate such as a silicon wafer to form a coating film having 5 μm thickness. This is immersed in a TMAH aqueous solution, a metal hydroxide aqueous solution, a metal carbonate aqueous solution, or an organic amine aqueous solution at 20 to 25℃. As a result, when the coating film can be dissolved uniformly, the resin can be regarded as soluble in an aqueous alkaline solution.
In the present embodiment, the ″polarity converting group″ means a functional group whose polarity is converted from hydrophobic to hydrophilic. The polarity converting group according to the present embodiment is stable and exhibits hydrophobicity under weak alkaline conditions, but can decompose under strong alkaline conditions to generate hydrophilic groups such as hydroxyl groups and carboxy groups. Examples of weak alkaline conditions include development with an alkaline aqueous solution of the photosensitive layer in the formation of a resist pattern described below. Examples of the strong alkali condition include stripping of the formed resist pattern with an alkaline aqueous solution. That is, the polarity conversion group  according to the present embodiment is a group that exhibits stable hydrophobicity against the weak alkaline aqueous solution used for developing the photosensitive layer, and can be decomposed by the strong alkaline aqueous solution used for stripping the resist pattern to change a hydrophilic group.
The alkali-soluble resin according to the present embodiment can be used as a binder resin of a photosensitive resin composition, and can improve the developability, resolution, and stripping characteristics of a photosensitive layer formed from the photosensitive resin composition. In addition, using the alkali-soluble resin according to the present embodiment for a photosensitive resin composition for thick film applications can improve the stripping characteristics while maintaining the resolution.
The alkali-soluble resin comprises the structural unit which has a polarity conversion group from the viewpoint of stripping characteristics. From the viewpoint of further improving the stripping characteristics, the polar conversion group may be a group represented by the following formula (1) .
Figure PCTCN2019126633-appb-000001
In the formula (1) , R 2 represents a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, or a trityl group. The group represented by the formula (1) can be converted to ″-OH″ by elimination of R 2 under strong alkaline conditions.
From the viewpoint of excellent balance between resolution and  stripping characteristics, the structural unit having the above polarity converting group may be a structural unit based on a compound represented by the following formula (2) .
Figure PCTCN2019126633-appb-000002
In the formula (2) , R 1 represents a hydrogen atom or a methyl group, L 1 represents an alkylene group having 1 to 6 carbon atoms, and R 2 represents a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, or a trityl group. From the viewpoint of improving the alkali solubility, L 1 is preferable to be an alkylene group having 1 to 4 carbon atoms, more preferable to be an alkylene group having 1 to 3 carbon atoms, and still more preferable to be an alkylene group having 2 or 3 carbon atoms.
Examples of the compound represented by the formula (2) include 2- (trimethylsilyloxy) ethyl (meth) acrylate, trimethylsilyl (meth) acrylate, and trityl (meth) acrylate.
The alkali-soluble resin according to the present embodiment can be manufactured, for example, by radical polymerization of a monomer having a polarity converting group and a monomer having a carboxy group.
From the viewpoint of further improving the stripping characteristics, the content of the monomer having a polarity converting group may be 1%by mass or more, 2%by mass or more, 3%by mass  or more, or 4%by mass or more, based on the total amount of the monomer constituting the alkali-soluble resin. From the viewpoint of further improving developability, the content of the monomer having a polarity converting group may be 35%by mass or less, 30%by mass or less, or 25%by mass or less.
The alkali-soluble resin comprises a structural unit having a carboxy group from the viewpoint of alkaline developability. Examples of the monomer having a carboxy group include (meth) acrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, maleic acid monoesters such as monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. From the viewpoint of further improving alkaline developability, the monomer having a carboxy group may be (meth) acrylic acid or methacrylic acid.
From the point of improving the balance between alkaline developability and alkali resistance, the content of the structural unit derived from the monomer having a carboxy group may be 10 to 45%by mass, 15 to 40%by mass, or 20 to 35%by mass, based on the total amount of the monomer constituting the alkali-soluble resin. When the content is 10%by mass or more, alkaline developability tends to be improved, and when the content is 45%by mass or less, alkali resistance tends to be excellent.
The alkali-soluble resin may have a structural unit based on styrene or a styrene derivative from the viewpoints of adhesion and  stripping characteristics. Styrene derivatives are a polymerizable compound such as vinyl toluene and α-methylstyrene in which α-position of styrene or a hydrogen atom in an aromatic ring has been replaced. The content of the structural unit based on styrene or styrene derivatives in the alkali-soluble resin may be 10 to 60%by mass, 15 to 55%by mass, or 25 to 50%by mass. When this content is 10%by mass or more, the adhesion tends to be improved, and when this content is 60%by mass or less, an increase in the size of the stripped pieces during development can be suppressed and the longer time required for stripping tends to be suppressed.
The alkali-soluble resin may have a structural unit based on (meth) acrylic acid benzyl ester from the viewpoint of resolution and aspect ratio. The content of the structural unit derived from the (meth) acrylic acid benzyl ester in the alkali-soluble resin may be 5 to 50%by mass, 15 to 45%by mass, or 10 to 40%by mass from the viewpoint of improving resolution.
The alkali-soluble resin may have a structural unit based on (meth) acrylic acid alkyl ester from the viewpoint of improving plasticity. Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester.
From the viewpoint of improving the resolution, the weight average molecular weight (Mw) of the alkali-soluble resin may be 1000 or more, 2000 or more, 3000 or more, or 5000 or more. From the viewpoint of suitable development, Mw of the alkali-soluble resin may be 30000 or less, 28000 or less, 26000 or less, or 24000 or less. Mw can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
The degree of hydrophilicity of the alkali-soluble resin can be calculated by the following formula from the degree of hydrophilicity of the monomer constituting the alkali-soluble resin and the copolymerization ratio of the monomer. The degree of hydrophilicity of the monomer is the amount of water (%by mass) included in the monomer as measured by the Karl Fischer method after adding ion-exchanged water to the monomer and leaving at 23℃ for 12 hours. Degree of hydrophilicity of alkali-soluble resin = monomer copolymerization ratio (%by mass) × degree of hydrophilicity of monomer
The hydrophilicity of the alkali-soluble resin before the polarity converting group is decomposed may be 80 to 120, 82 to 115, or 84 to 110 from the viewpoint of alkali resistance during development of the exposed part. The degree of the hydrophilicity of the alkali-soluble resin after the polarity conversing group has been decomposed may be 95 to 120, 98 to 115, or 100 to 110 from the viewpoint of the stripping characteristics. From the viewpoint of further improving the balance of developability, resolution, and stripping characteristics, the rate of increase in the degree of hydrophilicity after polarity conversion may be  3 to 45%, 5 to 40%, or 10 to 35%.
[Photosensitive resin composition]
The photosensitive resin composition according to the present embodiment contains (A) binder resin (hereinafter sometimes referred to as ″component (A) ″) ; (B) a photopolymerizable compound (hereinafter sometimes referred to as ″component (B) ″ ) ; and (C) photopolymerization initiator (hereinafter sometimes referred to as ″component (C) ″ ) . Hereinafter, each component which the photosensitive resin composition may contain is explained in detail.
＜ (A) Binder resin＞
 The binder resin as the component (A) includes an alkali-soluble resin according to the present embodiment (hereinafter sometimes referred to as ″component (A1) ″ ) . Containing the component (A1) improves the alkali resistance during development of the exposed part, allowing a resist pattern having excellent resolution to be formed. The resist pattern can be stripped with a strong alkaline aqueous solution. The component (A1) may be composed of only one resin, or may be composed of two or more resins.
The component (A) may further include an alkali-soluble resin other than the component (A1) . The alkali-soluble resin may be a resin having a phenolic hydroxyl group. Examples of the resin having a phenolic hydroxyl group include polyhydroxystyrene, hydroxystyrene-based resins such as copolymers including hydroxystyrene as a monomer unit, phenolic resins, polybenzoxazole precursors such as poly (hydroxyamide) , poly (hydroxyphenylene) ether, and polynaphthol.
The content of the component (A) may be 30 to 90 parts by mass, 40 to 85 parts by mass, or 50 to 80 parts by mass with respect to 100 parts by mass of total amounts of the component (A) and the component (B) . When the content of the component (A) is within this range, the strength of the photocured part of the photosensitive layer becomes better.
＜ (B) Photopolymerizable compound ＞
The component (B) is a compound having a functional group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenyl ethynyl group, a maleimide group, a nadimide group, and a (meth) acryloyl group as a functional group which exhibits photopolymerization. The component (B) is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups. As a functional group which exhibits photopolymerization, a (meth) acryloyl group is preferable. The component (B) may be used singly or in combination of two or more.
Examples of the photopolymerizable compound having one ethylenically unsaturated group include (meth) acrylic acids, alkyl (meth) acrylates, and phthalic acid-based (meth) acrylate compounds.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and hydroxylethyl (meth) acrylate.
From the viewpoint of suitably improving resolution, adhesion, and resist shape, the component (B) may include a phthalic acid-based compound. Examples of the phthalic acid-based compound include  γ-chloro-β-hydroxypropyl-β′- (meth) acryloyloxyethyl-o-phthalate (aka: 3-chloro-2-hydroxypropyl-2- (meth) acryloyloxyethylphthalate) , β-hydroxyethyl-β′- (meth) acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β′- (meth) acryloyloxyethyl-o-phthalate.
Examples of the photopolymerizable compound having two ethylenically unsaturated groups include polyethylene glycol di(meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2, 2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane, bisphenol A diglycidyl ether di (meth) acrylate, and alkylene oxide-modified bisphenol A di (meth) acrylate.
From the viewpoint of improving alkali developability and resolution, the component (B) may include an alkylene oxide-modified bisphenol A di (meth) acrylate. Examples of the alkylene oxide modified bisphenol A di (meth) acrylate include 2, 2-bis (4- ( (meth) acryloxypolyethoxy) phenyl) propane (for example: 2, 2-bis (4- ( (meth) acryloxypentaethoxy) phenyl) propane) , 2, 2-bis (4- ( (meth) acryloxypolypropoxy) phenyl) propane, 2, 2-bis (4- ( (meth) acryloxypolybutoxy) phenyl) propane, and 2, 2-bis (4- ( (meth) acryloxypolyethoxypolypropoxy) phenyl) propane.
Examples of the photopolymerizable compound having 3 or more ethylenically unsaturated groups include (meth) acrylate having a skeleton derived from trimethylolpropane such as trimethylolpropane tri (meth) acrylate; (meth) acrylate having a skeleton derived from tetramethylolmethane such as tetramethylolmethane tri (meth) acrylate and tetramethylolmethane tetra (meth) acrylate; (meth) acrylate having a  skeleton derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate; (meth) acrylate having a skeleton derived from dipentaerythritol such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; (meth) acrylate having a skeleton derived from ditrimethylolpropane such as ditrimethylolpropane tetra (meth) acrylate; and (meth) acrylate having a skeleton derived from diglycerin. Among them, from the viewpoint of enhancing the chemical resistance after curing (exposure) and increasing the difference in developer resistance between the exposed area and the unexposed area, (meth) acrylate compounds having a skeleton derived from dipentaerythritol are preferable and dipentaerythritol penta (meth) acrylate is more preferable.
From the viewpoint of improving the alkaline developability of the unexposed part of the photosensitive resin composition and improving the adhesive strength of the exposed part, the component (B) may include a photopolymerizable compound having an ethylenically unsaturated group and an acid-modified group. Examples of the acidic group to be modified include a carboxy group, a sulfo group, and a phenolic hydroxyl group, and among them, the carboxy group is preferable.
Examples of the photopolymerizable compound having an ethylenically unsaturated group and an acidic group include styrene-maleic acid-based resin and acid-modified epoxy derivative containing a vinyl group.
The styrene-maleic acid-based resin is a hydroxyethyl (meth) acrylate modified product of a styrene-maleic anhydride  copolymer. The acid-modified epoxy derivative containing a vinyl group is a compound obtained by reacting a compound having epoxy resin modified with vinyl group-containing organic acid with saturated or unsaturated group-containing polybasic acid anhydride.
The epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups. Examples of the epoxy resin include a glycidyl ether type epoxy resin, a glycidylamine type epoxy resin, and a glycidyl ester type epoxy resin. Among them, from the viewpoint of reliability in mounting semiconductor chips, a bisphenol novolac type epoxy resin is preferable and a bisphenol F novolac type epoxy resin is more preferable.
The vinyl group-containing organic acid is not particularly limited, and may be a vinyl group-containing monocarboxylic acid. Examples of the vinyl group-containing monocarboxylic acid include acrylic acid derivatives such as acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid; a half ester compound which is a reaction product of a hydroxyl group-containing acrylate and a dibasic acid anhydride; and a half ester compound which is a reaction product of a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride.
The ethylenically unsaturated bond is not particularly limited as long as photopolymerization is possible. Examples of the ethylenically unsaturated bond include an α, β-unsaturated carbonyl group such as a (meth) acryloyl group. Examples of the photopolymerizable compound having an α, β-unsaturated carbonyl group include α, β-unsaturated  carboxylic acid ester of polyhydric alcohol, bisphenol type (meth) acrylate, α, β-unsaturated carboxylic acid adduct of a glycidyl group-containing compound, (meth) acrylate having a urethane bond, nonylphenoxypolyethyleneoxyacrylate, and (meth) acrylic acid alkyl ester.
Examples of the α, β-unsaturated carboxylic acid ester of a polyhydric alcohol include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, polyethylene/polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, and a (meth) acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol. ″EO-modified″ means having the block structure of ethylene oxide (EO) groups, and ″PO-modified″ means having the block structure of propylene oxide (PO) groups.
The component (B) may include polyalkylene glycol di (meth) acrylate from the viewpoint of improving the flexibility of the resist pattern. The polyalkylene glycol di (meth) acrylate may have at least one of an EO group and a PO group, or may have both an EO group and a PO group. In the polyalkylene glycol di (meth) acrylate having both the EO group and the PO group, each of the EO group and the PO group may be continuously present in block or may be present  randomly. The PO group may be either an oxy-n-propylene group or an oxyisopropylene group. In the (poly) oxyisopropylene group, the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.
Examples of commercially available products of polyalkylene glycol di (meth) acrylate include FA-023M (manufactured by Hitachi Chemical Co., Ltd. ) , FA-024M (manufactured by Hitachi Chemical Co., Ltd. ) , and NK ester HEMA-9P (manufactured by Shin-Nakamura Chemical Co., Ltd. ) .
The component (B) may include (meth) acrylate having urethane bond from the viewpoint of improving the flexibility of the resist pattern. Examples of the (meth) acrylate having urethane bond include an addition reaction product of (meth) acrylic monomer having OH group at β-position and diisocyanate (such as isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, and 1, 6-hexamethylene diisocyanate) , tris ( (meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO-and PO-modified urethane di (meth) acrylate.
Examples of commercially available EO-modified urethane di (meth) acrylates include ″UA-11″ and ″UA-21EB″ (manufactured by Shin-Nakamura Chemical Co., Ltd. ) . Examples of commercially available EO-and PO-modified urethane di (meth) acrylates include ″UA-13″ (manufactured by Shin-Nakamura Chemical Co., Ltd. ) .
The component (B) may include a (meth) acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol, from the viewpoint of easily forming a thick resist pattern and improving the  resolution and adhesion in a balanced manner. The (meth) acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol is preferable to have four or more (meth) acryloyl groups, and may be dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate.
From the viewpoint of further improving the resolution and the stripping characteristics after curing, the component (B) may include bisphenol (meth) acrylate, and may include bisphenol A (meth) acrylate among bisphenol (meth) acrylates. Examples of the bisphenol A (meth) acrylate include 2, 2-bis (4- ( (meth) acryloxypolyethoxy) phenyl) propane, 2, 2-bis (4- ( (meth) acryloxypolypropoxy) phenyl) propane, 2, 2-bis (4- ( (meth) acryloxypolybutoxy) phenyl) propane, and 2, 2-bis (4- ( (meth) acryloxypolyethoxypolypropoxy) phenyl) propane. Among these, 2, 2-bis (4- ( (meth) acryloxypolyethoxy) phenyl) propane is preferable from the viewpoint of further improving the resolution and the patterning ability.
As commercially available products, examples of 2, 2-bis (4- ( (meth) acryloxydipropoxy) phenyl) propane include BPE-200 (Shin-Nakamura Chemical Co., Ltd. ) , and examples of 2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane include BPE-500 (Shin-Nakamura Chemical Co., Ltd. ) and FA-321M (Hitachi Chemical Co., Ltd. ) .
Examples of nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate,  nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.
＜ (C) Photopolymerization initiator＞
The component (C) is not particularly limited as long as it is a component capable of polymerizing the component (B) , and can be appropriately selected from commonly used photopolymerization initiators. The component (C) can be used singly or in combination of two or more.
Examples of the component (C) include photopolymerization initiators such as acylphosphine oxide, oxime ester, aromatic ketone, quinone, alkylphenone, imidazole, acridine, phenylglycine, and coumarin.
The component (C) may include an acridine photopolymerization initiator, a phenylglycine photopolymerization initiator, or an imidazole photopolymerization initiator, from the viewpoint of improving sensitivity and resolution in a balanced manner.
Examples of the acridine photopolymerization initiator include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine, 9-pentylaminoacridine, bis (9-acridinyl) alkanes such as 1, 2-bis (9-acridinyl) ethane, 1, 4-bis (9-acridinyl) butane,  1, 6-bis (9-acridinyl) hexane, 1, 8-bis (9-acridinyl) octane, 1, 10-bis (9-acridinyl) decane, 1, 12-bis (9-acridinyl) dodecane, 1, 14-bis (9-acridinyl) tetradecane, 1, 16-bis (9-acridinyl) hexadecane, 1, 18-bis (9-acridinyl) octadecane, and 1, 20-bis (9-acridinyl) eicosane, 1, 3-bis (9-acridinyl) -2-oxapropane, 1, 3-bis (9-acridinyl) -2-thiapropane, and 1, 5-bis (9-acridinyl) -3-thiapentane.
Examples of the phenylglycine photopolymerization initiator include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
Examples of the imidazole photopolymerization initiator include 2- (o-chlorophenyl) -4, 5-diphenylbiimidazole, 2, 2′, 5-tris- (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4′, 5′-diphenylbiim idazole, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylbiimidazole , 2, 4, 5-tris- (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -biimidazole, 2, 2′-bis- (2-fluorophenyl) -4, 4′, 5, 5′-tetrakis- (3-methoxyphenyl) -biimidazo le, 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) -biimi dazole, and 2, 2′-bis- (2, 5-difluorophenyl) -4, 4′, 5, 5′-tetrakis- (3-methoxyphenyl) -biimi dazole.
The content of the component (C) may be 0.1 to 10 parts by mass, 0.2 to 5 parts by mass, or 0.5 to 4 parts by mass with respect to  100 parts by mass of total amounts of the component (A) and the component (B) . When the content of the component (C) is 0.1 parts by mass or more, the photosensitivity, resolution, and adhesion tend to be improved, and when the content is 10 parts by mass or less, the resist patterning ability tends to be excellent.
＜Component (D) : photosensitizer＞
The photosensitive resin composition according to the present embodiment may further include a photosensitizer as the component (D) . Containing the component (D) allows the absorption wavelength of actinic light used for exposure to be effectively used. The component (D) may be used singly or in combination of two or more.
Examples of the component (D) include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. The component (D) may include a pyrazoline compound or an anthracene compound from the viewpoint of further improving the resolution.
Examples of the pyrazoline compound include 1- (4-methoxyphenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1, 5-bis- (4-methoxyphenyl) -3- (4-methoxystyryl) -pyrazoline, 1- (4-isopropylphenyl) -3-styryl-5-phenyl-pyrazoline,  1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1, 5-bis- (4-isopropylphenyl) -3- (4-isopropylstyryl) -pyrazoline, 1- (4-methoxyphenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyr azoline, 1- (4-tert-butyl-phenyl) -3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyraz oline, 1- (4-isopropyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -py razoline, 1- (4-tert-butyl-phenyl) -3- (4-isopropyl-styryl) -5- (4-isopropyl-phenyl) -py razoline, 1- (4-methoxyphenyl) -3- (4-isopropylstyryl) -5- (4-isopropyllbphenyl) -pyr azoline, 1- (4-isopropyl-phenyl) -3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyra zoline, 1-phenyl-3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline,  1- (4-methoxyphenyl) -3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxypheny l) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxypheny l) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxypheny l) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxypheny l) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxypheny l) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxypheny l) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxypheny l) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxypheny l) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxypheny l) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxypheny l) -pyrazoline,  1- (4-isopropyl-phenyl) -3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxypheny l) -pyrazoline, and 1- (4-isopropyl-phenyl) -3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxypheny l) -pyrazoline.
Examples of the anthracene compound include 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-dipropoxyanthracene, 9, 10-dibutoxyanthracene, and 9, 10-dipentoxyanthracene.
From the viewpoint of improving photosensitivity and resolution, the content of the component (D) may be 0.01 to 5 parts by mass, 0.01 to 1 part by mass, or 0.01 to 0.2 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) .
(Other components)
As required, the photosensitive resin composition according to the present embodiment may further contain additives such as dyes, photochromic agents, thermochromic inhibitors, plasticizers, pigments, fillers, antifoaming agents, flame retardants, adhesion promoters, leveling agents, stripping accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and polymerization inhibitors. These additives can be used singly or in combination of two or more.
Examples of the dye include malachite green, victoria pure blue, brilliant green, and methyl violet. Examples of the photochromic agent include tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline. Examples of the plasticizer include  p-toluenesulfonamide.
As required, the photosensitive resin composition is dissolved in a solvent, such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, and propylene glycol monomethyl ether, or a mixed solvent thereof, allowing a solution having a solid content of about 30 to 60%by mass to be prepared.
[Photosensitive element]
The photosensitive element of the present embodiment comprises a support and a photosensitive layer formed on the support, and the photosensitive layer comprises the above photosensitive resin composition. When the photosensitive element of the present embodiment is used, the photosensitive layer is laminated on the substrate and then may be exposed without stripping the support (support film) . As shown in the schematic cross-sectional view of the example in Figure 1, the photosensitive element 1 according to the present embodiment is formed by comprising a support 2 and a photosensitive layer 3 derived from the above photosensitive resin composition formed on the support 2, and comprising other layers such as a protective layer 4 provided as required.
(Support)
Examples of the support include polyester films such as polyethylene terephthalate (PET) , polybutylene terephthalate (PBT) , and polyethylene-2, 6-naphthalate (PEN) , and polyolefin films such as polypropylene and polyethylene. Among these, a PET film may be used from the viewpoint of being easily available and excellent in  handling in the manufacturing process (particularly, heat resistance, thermal shrinkage, and breaking strength) .
The haze of the support may be 0.01 to 1.0%or 0.01 to 0.5%. When the haze is 0.01%or more, the support itself tends to be easily manufactured, and when the haze is 1.0%or less, fine defects that may occur in the resist pattern tends to decrease. ″Haze″ means cloudiness. The haze in the present disclosure refers to a value measured by using a commercially available cloudiness meter (turbidimeter) in accordance with the method defined in JIS K 7105. Haze can be measured with a commercially available turbidimeter such as NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd. ) .
The thickness of the support may be 1 to 100 μm, 5 to 60 μm, 10 to 50 μm, 10 to 40 μm, 10 to 30 μm, or 10 to 25 μm. The thickness of the support is 1 μm or more, and thereby the support tends to be prevented from being broken when the support is stripped. In addition, the thickness of the support is 100 μm or less, which can suppress reduction of resolution in exposing through the support.
(Protective layer)
The photosensitive element may further comprise a protective layer as required. As the protective layer, a film in which the adhesive force between the photosensitive layer and the protective layer is smaller than the adhesive force between the photosensitive layer and the support may be used, and a film with a low fish eye may be used. Specific examples thereof include one that can be used as the above support. From the viewpoint of stripping from the photosensitive layer, a polyethylene film may be used. The thickness of the  protective layer may be about 1 to 100 μm, depending on applications.
The photosensitive element can be manufactured as follows, for example. A photosensitive resin composition solution (coating solution) is applied on a support to form a coating layer, and this is dried to form a photosensitive layer. Covering the photosensitive layer surface opposite to the support with the protective layer provide a photosensitive element comprising the support, the photosensitive layer formed on the support, and the protective layer laminated on the photosensitive layer.
Application of the coating solution onto the support can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.
The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, the drying may be performed at 70 to 150℃ for about 5 to 30 minutes. After drying, the amount of residual solvent in the photosensitive layer may be 2%by mass or less, from the viewpoint of preventing diffusion of the solvent in the subsequent step.
The thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on applications, and may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm in thickness after drying. When the thickness is 1 μm or more, industrial coating becomes easy and productivity is improved. In addition, 100 μm or less in thickness improves adhesion and resolution.
The form of the photosensitive element is not particularly limited. For example, the form may be a sheet shape or a shape  obtained by winding on a core in the roll shape. In winding in roll shape, winding may be performed so that the support film is an outer side. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, or ABS resin (acrylonitrile-butadiene-styrene copolymer) .
An end face separator may be provided on the end face of the roll-shaped photosensitive element from the viewpoint of end face protection, and a moisture-proof end face separator may be provided from the viewpoint of edge fusion resistance. The photosensitive element may be wrapped in a black sheet with low moisture permeability.
The photosensitive element can be suitably used, for example, in a method of forming a resist pattern described below. Particularly, the photosensitive element is suitable for the application to the manufacturing method which forms a conductor pattern by plating treatment, from the viewpoint of resolution.
[Method of forming resist pattern]
The method of forming a resist pattern according to the present embodiment comprises (i) a step of forming a photosensitive layer on a substrate using the above photosensitive resin composition or the above photosensitive element (photosensitive layer forming step) ; (ii) a step of irradiating at least a part (predetermined part) of the photosensitive layer with actinic light to form a photocured part (exposure step) ; and (iii) a step of removing at least a part other than the photocured part from the above substrate to form a resist pattern (developing step) , and may be composed of other steps as required. The resist pattern can be referred  to as a photocured product pattern of the photosensitive resin composition or a relief pattern. The method for forming a resist pattern can be referred to as a method of manufacturing a substrate with a resist pattern.
( (i) Photosensitive layer forming step)
As a method of forming a photosensitive layer on a substrate, for example, the above photosensitive resin composition may be applied and dried, or after removing the protective layer from the photosensitive element, the photosensitive layer of the photosensitive element may be pressure-bonded to the above substrate while heating. Using a photosensitive element provides a laminate consisting of a substrate, a photosensitive layer, and a support wherein these are sequentially laminated. The above substrate is not particularly limited, and typically, a circuit forming substrate comprised with an insulating layer and a conductor layer formed on the insulating layer, or a die pad (alead frame substrate) such as an alloy base material is used.
When the photosensitive element is used, the photosensitive layer forming step is preferable to be performed under reduced pressure, from the viewpoint of adhesion and followability. The photosensitive layer and/or the substrate may be heated at a temperature of 70 to 130℃ during the pressure bonding. The pressure bonding may be performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm 2) , but these conditions are appropriately selected as required. When the photosensitive layer is heated to 70 to 130℃, preheat treatment of the substrate in advance is not necessary, but preheat treatment of the substrate can be performed in order to further improve the adhesion and  followability.
( (ii) Exposure step)
In the exposure step, at least a part of a photosensitive layer formed on a substrate is irradiated with actinic light, photocuring the part irradiated with the actinic light to form a latent image. In this case, when the support is present on the photosensitive layer, the photosensitive layer can be irradiated with the actinic light through the support if the support is transparent to the actinic light, but the photosensitive layer is irradiated with the actinic light after the support is removed if the support is light-shielding.
Examples of the exposure method include a method of imagewise irradiating actinic light through a negative or positive mask pattern, referred to as an artwork (mask exposure method) . The method of imagewise irradiating actinic light with a projection exposure method may be employed. The method of imagewise irradiating actinic light by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.
As a light source of the actinic light, a known light source can be used, and for example, carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid state lasers such as YAG lasers, ultraviolet rays such as semiconductor lasers, and those that effectively emit visible light are used.
( (iii) Development step)
In the development step, at least a part of the above  photosensitive layer other than the photocured part is removed from the substrate, forming a resist pattern on the substrate.
When the support is present on the photosensitive layer, the support is removed, and then removal (development) of a region other than the above photocured part (also referred to as an unexposed part) is performed. Development methods include wet development and dry development, and the wet development is widely used.
In the case of the wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the development method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like, and from the viewpoint of improving resolution, a high-pressure spray method may be used. Development may be performed by combining these two or more methods.
The configuration of the developer is appropriately selected according to the configuration of the above photosensitive resin composition. Examples of the developer include an alkaline aqueous solution and an organic solvent developer.
From the viewpoint of safety, stability, and good operability, an alkaline aqueous solution may be used as the developer. Examples of the base of the alkaline aqueous solution include alkali hydroxide such as hydroxide of lithium, sodium, or potassium; alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium, or ammonium; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium  pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1, 3-propanediol; 1, 3-diaminopropanol-2; and morpholine.
As an alkaline aqueous solution used for development, a dilute solution of sodium carbonate in 0.1 to 5%by mass, a dilute solution of potassium carbonate in 0.1 to 5%by mass, a dilute solution of sodium hydroxide in 0.1 to 5%by mass, a dilute solution of sodium tetraborate in 0.1 to 5%by mass, and the like can be used. The pH of the alkaline aqueous solution may be in the range of 9 to 14, and the temperature can be adjusted according to the alkaline developability of the photosensitive layer. In the alkaline aqueous solution, for example, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
Examples of the organic solvent used in the alkaline aqueous solution include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.
Examples of the organic solvent used in the organic solvent developer include 1, 1, 1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. In order to prevent ignition, these organic solvents may be added with water so as to be in the range of 1 to 20%by mass to obtain an organic solvent developer.
In the method of forming a resist pattern according to the present embodiment, a step of further curing the resist pattern may be included by heating at about 60 to 250℃ or exposure at about 0.2 to 10 J/cm 2 as required after removing the uncured part in the development step.
[Method of forming wiring pattern]
The method of forming a wiring pattern according to the present embodiment has a step of forming a conductor pattern by etching treatment or plating treatment of a substrate having the resist pattern formed thereon by the above method of forming a resist pattern. The method of forming a wiring pattern may further comprise a step of removing the photocured part with an alkaline aqueous solution after the etching treatment or the plating treatment.
In the plating treatment, the plating treatment is performed on the conductor layer provided on the substrate by using the resist pattern formed on the substrate as a mask. After the plating treatment, the resist may be removed by removing the resist pattern, which will be described below, and the conductor layer covered with the resist may be etched to form a conductor pattern. The plating treatment method may be electro-plating treatment, electroless plating treatment, or electroless plating treatment.
On the other hand, in the etching treatment, using the resist pattern formed on the substrate as a mask, the conductor layer provided on the substrate is removed by etching to form a conductor pattern. The etching treatment method is appropriately selected according to the conductor layer to be removed. Examples of the etching solution  include a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.
After the etching treatment or the plating treatment, the resist pattern on the substrate may be removed. The resist pattern can be removed by, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the above development step. As the strong alkaline aqueous solution, for example, a 1 to 10%sodium hydroxide aqueous solution by mass and a 1 to 10%potassium hydroxide aqueous solution by mass are used. The removal of the resist pattern may be performed at a temperature of 45 to 65℃ by using a strong alkaline aqueous solution.
When the resist pattern is removed after performing the plating treatment, a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment to form a conductor pattern. The etching treatment method in this case is appropriately selected according to the conductor layer to be removed. For example, the above etching solution can be applied.
The method of forming a wiring pattern according to the present embodiment can be applied not only to the manufacture of a single-layer printed wiring board but also to the manufacture of a multilayer printed wiring board, and also to the manufacture of a printed wiring board having a through-hole of small-diameter.
Examples
Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these  Examples.
(1) Trityl methacrylate (MA-Tr)
150 mL of petroleum ether, 0.10 mol of triphenylmethyl, 0.11mol of methacrylic acid, and 0.10 mol of triethylamine were supplied into 1000mL of a three-necked flask comprising a stirrer, nitrogen inlet tube, and reflux condenser, and were reacted at room temperature for 6 hours. After removing triethylamine hydrochloride produced as a product from the reaction solution, 100 mL of a 3%aqueous sodium carbonate solution by mass was added to the reaction solution and was washed three times. The washed reaction solution was dried with magnesium sulfate, and then the solvent was removed by vacuum drying to obtain MA-Tr. The yield was 90%.
(2) tert-Butyldimethylsilyl methacrylate (MA-TBDMS)
150 mL of dichloromethane, 0.20mol of methacrylic acid, and 0.22 mol of triethylamine were supplied into 500mL of a three-necked flask comprising a stirrer, nitrogen inlet tube, and reflux condenser, and were stirred for 10 minutes. Then, 0.21mmol of tert-butyldimethylsilyl Chloride was dropped into the flask and reacted at room temperature for 24hours. The reaction solution was washed twice using a 3%hydrochloric acid and then washed three times using pure water. The washed reaction solution was dried with magnesium sulfate, and then the solvent was removed by vacuum drying to obtain MA-TBDMS. The yield was 98%.
(3) Triethylsilyl methacrylate (MA-TES)
150 mL of dichloromethane, 0.20mol of methacrylic acid, and 0.22 mol of triethylamine were supplied into 500mL of a three-necked  flask comprising a stirrer, nitrogen inlet tube, and reflux condenser, and were stirred for 10 minutes. Then, 0.21mmol of triethylsilyl chloride was dropped into the flask and reacted at room temperature for 24hours. The reaction solution was washed twice using a 3%hydrochloric acid and then washed three times using pure water. The washed reaction solution was dried with magnesium sulfate, and then the solvent was removed by vacuum drying to obtain MA-TES. The yield was 90%.
(4) Alkali-soluble resin
(Example 1)
96 g of propylene glycol monomethyl ether (MFG) and 64 g of toluene were supplied into 1000 mL of a three-necked flask comprising a stirrer, a nitrogen inlet tube, a reflux condenser, a dropping funnel, and a thermometer, and the temperature was raised to 80℃ in a nitrogen atmosphere. In a flask, a mixture of 20 g of methacrylic acid (MA) , 30 g of styrene (STC) , 40 g of benzyl methacrylate (BzMA) , 10 g of trimethylsilyl methacrylate (MA-TMS) , and 1 g of azobisisobutyronitrile (AIBN) was dropped for 3 hours, and then a mixture of 6 g of MFG, 4 g of toluene, and 0.20 g of AIBN was dropped for 2 hours, and 6 g of MFG and 4 g of toluene were further dropped to perform reaction. The reaction solution was heated to 95℃ and was stirred for 1.5 hours, and then was cooled to room temperature to obtain a polymer solution of an alkali-soluble resin (A1) . The non-volatile content (solid content) of the polymer solution was 40%by mass.
(Examples 2 to 4)
Polymer solutions of alkali-soluble resins (A2) to (A4) were obtained in the same manner as in Example 1, except that MA, STC,  BzMA, and MA-TMS were used in the blending amounts shown in Table 1.
(Examples 5 to 8)
Polymer solutions of alkali-soluble resins (A5) to (A8) were obtained in the same manner as in Example 1, except that MA, STC, BzMA, and MA-Tr were used in the blending amounts shown in Table 1.
(Example 9)
A polymer solution of an alkali-soluble resin (A9) was obtained in the same manner as in Example 1, except that MA, STC, BzMA, and 2- (trimethylsilyloxy) ethyl methacrylate (HEMA-TMS) were used in the blending amounts shown in Table 1.
(Examples 10 to 12)
Polymer solutions of alkali-soluble resins (A10) to (A12) were obtained in the same manner as in Example 1, except that MA, methyl methacrylate (MMA) , STC, BzMA, and HEMA-TMS were used in the blending amounts shown in Table 1.
(Example 13)
Polymer solution of alkali-soluble resins (A13) was obtained in the same manner as in Example 1, except that MA, STC, BzMA, and MA-TBDMS were used in the blending amounts shown in Table 1.
(Example 14)
Polymer solution of alkali-soluble resins (A14) was obtained in the same manner as in Example 1, except that MA, STC, BzMA, and MA-TES were used in the blending amounts shown in Table 1.
(Comparative Example 1)
A polymer solution of alkali-soluble resin (B1) was obtained in the same manner as in Example 1, except that MA, STC, and BzMA were used in the blending amounts shown in Table 1.
(Comparative Examples 2 to 3)
Polymer solutions of alkali-soluble resins (B2) to (B3) were obtained in the same manner as in Example 1, except that MA, MMA, STC, and BzMA were used in the blending amounts shown in Table 1.
(Weight average molecular weight)
120 mg of the polymer solution was collected and was dissolved in 5 mL of THF to prepare a sample for Mw measurement. Mw was measured by gel permeation chromatography (GPC) and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
(GPC conditions)
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd. )
Column: Gelpack GL-R420, Gelpack GL-R430, and Gelpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd., column specification: 10.7 mmφ × 300 mm)
Eluent: Tetrahydrofuran (THF)
Measurement temperature: 40℃
Injection volume: 200 μL
Pressure: 49 Kgf/cm 2 (4.8MPa)
Flow rate: 2.05 mL/min
Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd. )
[Table 1]
Figure PCTCN2019126633-appb-000003
(5) Photosensitive resin composition
A photosensitive resin composition was prepared by mixing each component in the blending amounts (parts by mass) shown in Table 2 with respect to 140 parts by mass of the above polymer solution (alkali-soluble resin: 56 parts by mass) .
Details of each component shown in Table 2 are as follows.
(Photopolymerizable compound)
FA-321M (trade name) : 2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd. )
FA-023M (trade name) : polyalkylene glycol di (meth) acrylate (manufactured by Hitachi Chemical Co., Ltd. )
FA-MECH (trade name) :  (2-hydroxy-3-chloro) propyl-2-methacryloyloxyethyl phthalate (manufactured by Hitachi Chemical Co., Ltd. )
(Photopolymerization initiator)
BCIM (trade name) : 2, 2′-bis (2-chlorophenyl) -4, 4′, 5, 5′-tetraphenylbiimidazole (manufactured by Hampford Research Inc. )
(Sensitizer)
DBA (trade name) : 9, 10-dibutoxyanthracene (Kawasaki Chemical Industry Co., Ltd. )
(Photochromic agent)
LCV: Leuco Crystal Violet (Yamada Chemical Co., Ltd. )
(Adhesion imparting agent)
SF-808H: mixture of carboxybenzotriazole, 5-amino-1H-tetrazole, and methoxypropanol (Sanwa Kasei Co., Ltd. )
(Dye)
MKG: Malachite Green (Osaka Organic Chemical Industry Co., Ltd. )
[Table 2]
Figure PCTCN2019126633-appb-000004
(6) Photosensitive element
The photosensitive resin composition was applied onto a 16 μm thick polyethylene terephthalate (PET) film (trade name ″G2J″ , manufactured by Teijin Film Solution Co., Ltd. ) (support) , and was dried sequentially in a hot air convection dryer at 75℃ and 125℃ to form a photosensitive layer having a dried thickness of 25 μm. A polypropylene film (product name ″NF-13″ , manufactured by Tamapoly Co., Ltd. ) (protective layer) was bonded onto this photosensitive layer to obtain each of the photosensitive element in which the support, the photosensitive layer, and the protective layer were laminated in this order.
[Evaluation]
(Degree of hydrophilicity)
7 g of a monomer put into 20 mL of a glass bottle, and ion exchanged water was added and left at 23℃ for 12 hours, and then only the monomer was recovered with a syringe and the moisture amount included in the monomer was determined by the Karl Fischer method. The moisture content (%by mass) included in a monomer was regarded as the degree of hydrophilicity of the monomer. The degree of hydrophilicity of each monomer is shown in Table 3.
[Table 3]
Monomer Degree of hydrophilicity
MA 3.2 (literature value)
MMA 1.2
STC 0.1
BzMA 0.4
MA-TMS 0.5
MA-Tr 0.2
MA-TBDMA 0.1
MA-TES 0.1
The initial degree of hydrophilicity of the alkali-soluble resin, the degree of hydrophilicity after the polarity conversion, and the increasing rate of the degree of hydrophilicity were calculated from the degree of hydrophilicity of the above monomer and the copolymerization ratio of the monomer. The degrees of hydrophilicity of the alkali-soluble resin in Examples were shown in Table 4, and the degrees of hydrophilicity of the alkali-soluble resin in Comparative Examples were shown in Table 5.
(Laminate)
Copper clad laminate (trade name ″MCL-E-67″ , manufactured by Hitachi Chemical Co., Ltd. ) in which copper foil (thickness of 35 μm) was laminated on both sides of the glass fiber reinforced epoxy resin layer was washed with water, acid, and then water and was dried in an air stream. The copper clad laminate was heated to 80℃ and the photosensitive element was laminated on the copper surface of the copper clad laminate. Lamination was performed at a pressing pressure of 0.4 MPa on the substrate and a roll speed of 1.0 m/min while  removing the protective layer with a heat roll at 110℃. Thus, the laminate in which the copper clad laminate, the photosensitive layer, and the support were laminated in this order was obtained.
(Developability)
A photosensitive layer having a film thickness of 25 μm was laminated on the substrate, and then the photosensitive layer was developed with a 1%sodium carbonate aqueous solution by mass at 30℃, and the development time when the remaining film disappeared was measured. The case where the development time was 20 seconds or less was evaluated as ″A″ , and the case where the development time was less than 20 seconds was evaluated as ″B″ .
(Resolution)
On the support of the laminate, a glass chrome photo tool (resolution negative: line width/space width having x/x (x: 1 to 30, unit: μm) wiring pattern) was used as a negative for resolution evaluation, and exposure was performed with an energy amount such that the number of remaining step after development of the Hitachi 41 step tablet was 17.0. After the exposure, development treatment of the photosensitive layer was performed in the same manner as the photosensitivity evaluation.
Of resist patterns obtained by clearly removing the space part (unexposed part) after the development treatment and by forming the line part (exposed part) with no meandering or chipping, the value of the smallest space width was used to evaluate resolution. The case where the smallest space width was less than 15 μm was evaluated as ″A″ , the case of 15 to 20 μm was as ″B″ , and the case of more than 20  μm was as ″C″ .
(Stripping characteristics)
A laminate obtained by laminating a photosensitive layer having a film thickness of 25 μm on a substrate was irradiated with 30 mJ at 405 nm by using a direct drawing exposure apparatus, and using a 1%aqueous sodium carbonate solution by mass at 30℃, spray development was performed for a time twice as long as the minimum development time (the shortest time for removing the unexposed part) , and the unexposed part was removed (development treatment) . After the development treatment, a test piece having a 40 mm × 50 mm cured film formed on the substrate was obtained. The test piece was immersed in a 3%sodium hydroxide aqueous solution by mass at 50℃, and the time until the cured film was stripped from the substrate was measured. The case where the stripping time was less than 50 seconds was evaluated as ″A″ , the case of 50 seconds or more but less than 60 seconds was as ″B″ , and the case of 60 seconds or more was as ″C″ .
[Table 4]
Figure PCTCN2019126633-appb-000005
[Table 5]
Figure PCTCN2019126633-appb-000006
From the above result, it can be confirmed that the photosensitive resin composition containing the alkali-soluble resin including the structural unit which has a polarity converting group is compatible with developability, resolution, and stripping.
Reference Signs List
1: Photosensitive element, 2: Support, 3: Photosensitive layer, 4: Protective layer.

Claims (8)

  1. An alkali-soluble resin comprising a structural unit having a polarity converting group and a structural unit having a carboxy group, wherein the polarity converting group has a group being not eliminated under weak alkaline conditions but being eliminated under strong alkaline conditions.
  2. The alkali-soluble resin according to claim 1, wherein the polarity converting group is a group represented by the following formula (1) :
    Figure PCTCN2019126633-appb-100001
    wherein R 2 represents a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, or a trityl group.
  3. The alkali-soluble resin according to claim 2, wherein the structural unit having a polarity converting group is a structural unit based on a compound represented by the following formula (2) :
    Figure PCTCN2019126633-appb-100002
    wherein R 1 represents a hydrogen atom or a methyl group, L 1 represents an alkylene group having 1 to 6 carbon atoms, and R 2 represents a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl  group, or a trityl group.
  4. A photosensitive resin composition comprising:
    a binder resin comprising the alkali-soluble resin according to any one of claims 1 to 3;
    a photopolymerizable compound; and
    a photopolymerization initiator.
  5. A photosensitive element comprising:
    a support; and
    a photosensitive layer formed on the support, wherein
    the photosensitive layer comprises the photosensitive resin composition according to claim 4.
  6. A method of forming a resist pattern, comprising:
    a step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to claim 4 or the photosensitive element according to claim 5;
    a step of irradiating at least a part of the photosensitive layer with actinic light to form a photocured part; and
    a step of removing at least a part other than the photocured part of the photosensitive layer from the substrate to form a resist pattern.
  7. A method of forming a wiring pattern, comprising a step of forming a conductor pattern by etching treatment or plating treatment of a substrate having a resist pattern formed thereon by the method of  forming a resist pattern according to claim 6.
  8. The method of forming a wiring pattern according to claim 7, further comprising a step of removing the photocured part with an alkaline aqueous solution after the etching treatment or the plating treatment.
PCT/CN2019/126633 2019-12-19 2019-12-19 Alkali-soluble resin, photosensitive resin composition, photosensitive element, method of forming resist pattern, and method of forming wiring pattern WO2021120106A1 (en)

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