Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• the present invention relates to a photosensitive resin composition, a cured product of the photosensitive resin composition, a microlens made of the cured product, a method for producing a cured product using the above-mentioned photosensitive resin composition, and the above-mentioned photosensitive resin composition.
• the present invention relates to a method of manufacturing an optical element using a material.
• a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor is used as the solid-state image sensor.
• the image sensor is provided with a fine condensing lens (hereinafter referred to as a microlens) for the purpose of improving the light condensing efficiency.
• a method called a thermal flow method is widely adopted industrially.
• a photoresist film is first formed on top of a CCD element or the like.
• a photoresist film is a film made of a photosensitive resin composition or the like.
• the photoresist film is exposed and developed to form a dot pattern made of resin on the element.
• the dot pattern consists of a plurality of dots located where microlenses are to be formed. Each dot constituting the dot pattern has a substantially cylindrical shape or a substantially truncated cone shape.
• an etch-back method is known as one of the methods for manufacturing a microlens for a CCD or CMOS image sensor (see Patent Document 2 and Patent Document 3).
• a microlens resin layer is formed on a color filter.
• a lens pattern is formed on the microlens resin layer using a photosensitive resin composition by a method similar to the thermal flow method described above.
• a microlens is produced by etching back the lower microlens resin layer using the lens pattern thus formed as an etching mask and transferring the lens pattern shape to the microlens resin layer.
• microlenses of different sizes may be formed in the optical element.
• many work steps are required to form a microlens pattern or a mask pattern having a microlens shape.
• dots, microlens patterns, mask patterns having microlens shapes, and the like are frequently exposed to chemical solutions such as organic solvents in the manufacturing process of optical elements.
• the photosensitive resin composition is required to have good photolithography properties.
• the photosensitive resin composition used for forming microlenses is required to have excellent photolithography properties and to be able to form a resin film with excellent chemical resistance.
• the present invention has been made in view of such conventional circumstances, and provides a photosensitive resin composition capable of forming a resin film having excellent photolithography properties and excellent chemical resistance, and a method for curing the photosensitive resin composition.
• the present invention aims to provide a microlens made of the cured product, a method for producing the cured product using the photosensitive resin composition described above, and a method for producing an optical element using the photosensitive resin composition. do.
• the present inventors have discovered that in a photosensitive resin composition containing a polyhydroxystyrene resin (A), a photoacid generator (B), and a methylol type crosslinking agent (C), some of the phenolic hydroxyl groups are in the acetal type.
• a polyhydroxystyrene resin (A) protected by a protecting group and a methylol-type crosslinking agent (C ) was found to be able to solve the above problems, leading to the present invention.
• the present invention provides the following.
• the first aspect of the present invention includes a polyhydroxystyrene resin (A), a photoacid generator (B), and a methylol-type crosslinking agent (C),
• a polyhydroxystyrene resin (A) a part of the phenolic hydroxyl group is protected by an acetal type protecting group,
• the second aspect of the present invention is a cured product of the photosensitive resin composition according to the first aspect.
• a third aspect of the present invention is a microlens made of the cured product according to the second aspect.
• a fourth aspect of the present invention is a method for producing a cured product, which includes heating the photosensitive resin composition according to the first aspect.
• the fifth aspect of the present invention is A method for manufacturing an optical element, comprising a plurality of microlenses including n types of microlenses of different sizes on a base material, the method comprising: n is an integer of 2 or more,
• the manufacturing method includes forming a resin film on a base material, forming a mask having a shape corresponding to the shape of the plurality of microlenses on the resin film; forming a plurality of microlenses to which the shape of the mask is transferred by etching the resin film together with the mask;
• the mask has the following (i) to (iii): (i) coating an mth photosensitive composition on the resin film to form an mth coating film; (ii) exposing and developing the m-th coating film to form an m-th dot on the base material at a position corresponding to the position where the m-th microlens is formed; (iii) heating the m-th dot to transform the m-th dot into a
• the sixth aspect of the present invention is A method for manufacturing an optical element comprising a plurality of microlenses on a base material, the method comprising: Applying the photosensitive resin composition according to the first aspect onto a substrate to form a coating film; position-selectively exposing the coating film so that a plurality of dots are formed at positions on the base material where a plurality of microlenses are formed; Developing the exposed coating film to form a plurality of dots at positions where a plurality of microlenses are to be formed; This manufacturing method includes heating the plurality of dots to thermally deform the plurality of dots to form the plurality of microlenses.
• a photosensitive resin composition capable of forming a resin film having excellent photolithography properties and excellent chemical resistance, a cured product of the photosensitive resin composition, a microlens made of the cured product, and the aforementioned It is possible to provide a method for producing a cured product using the photosensitive resin composition described above, and a method for producing an optical element using the photosensitive resin composition described above.
• the photosensitive resin composition includes a polyhydroxystyrene resin (A), a photoacid generator (B), and a methylol-type crosslinking agent (C).
• the polyhydroxystyrene resin (A) some of the phenolic hydroxyl groups are protected by an acetal type protecting group.
• the methylol type crosslinking agent (C) is a compound having two or more groups selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group in the molecule.
• a photosensitive resin composition having the above configuration has excellent photolithography properties. Furthermore, when using a photosensitive resin composition having the above configuration, a resin film having excellent chemical resistance is formed.
• the photosensitive resin composition contains polyhydroxystyrene resin (A).
• polyhydroxystyrene resin (A) some of the phenolic hydroxyl groups are protected by an acetal type protecting group.
• the polyhydroxystyrene resin (A) is effectively deprotected by the action of the acid generated by the photoacid generator (B) upon exposure, and becomes soluble in an alkaline developer. For this reason, when a patterned resin film is formed by a photolithography method including alkaline development using the photosensitive resin composition containing the above polyhydroxystyrene resin (A), the resin film is patterned into a desired shape. Easy to get.
• Suitable examples of the polyhydroxystyrene resin (A) include resins having a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2).
• the structural unit represented by formula (a1) will also be referred to as “structural unit (a1).”
• the structural unit represented by formula (a2) is also referred to as “constituent unit (a2).”
• R a1 is a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group.
• R a2 is a hydrogen atom or an alkyl group.
• p is an integer of 1 to 5.
• q is an integer between 0 and 4.
• R a3 is a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group.
• R a4 , R a5 , and R a6 are each independently a hydrogen atom or an alkyl group.
• .R a7 is an alkyl group or a cycloalkyl group.
• r is an integer of 1 to 5.
• s and t are each independently an integer of 0 to 4.
• R a1 and R a3 are a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group.
• the number of carbon atoms in the alkyl group as R a1 and R a3 is not particularly limited as long as the desired effect is not impaired.
• the number of carbon atoms in the alkyl group as R a1 and R a3 is preferably 1 or more and 5 or less.
• the alkyl groups as R a1 and R a3 may be linear or branched.
• alkyl groups as R a1 and R a3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group. , and neopentyl group.
• Methyl group is preferred industrially.
• halogen atoms as R a1 and R a3 or the halogen atom in the halogenated alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atoms are preferred.
• the halogenated alkyl group is preferably a group in which some or all of the hydrogen atoms in the above-mentioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms.
• the halogenated alkyl group may be linear or branched.
• Preferred specific examples of the halogenated alkyl group include fluorinated alkyl groups such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, and nonafluorobutyl.
• R a1 and R a3 a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.
• the number of carbon atoms in the alkyl group as R a2 and R a4 is preferably 1 or more and 5 or less.
• Preferable examples of the alkyl group as R a2 and R a4 are the same as the preferable examples of the alkyl group as R a1 and R a3 .
• q, s, and t are each independently an integer of 0 to 4. It is preferable that q, s, and t are each independently 0 or 1, and 0 is particularly preferable for industrial purposes.
• p is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1.
• s is an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, and more preferably 0 or 1.
• the substitution position of the hydroxyl group in formula (a1) and formula (a2) is R a1 on the benzene ring in formula (a1) or formula (a2).
• formula (a1) when p is an integer of 2 or more and 5 or less, or in formula (a2), when s is an integer of 2 or more and 4 or less, the hydroxyl group in formula (a1) and formula (a2) is can be bonded to any position on the benzene ring.
• r is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1.
• r is 1, the substitution position of the group represented by -C(R a5 )(R a6 )OR a7 in formula (a2) is bonded to R a3 on the benzene ring in formula (a2).
• the position of the carbon atom bonded to the carbon atom may be o-position, m-position, or p-position.
• R a5 and R a6 are each independently a hydrogen atom or an alkyl group.
• R a7 is an alkyl group or a cycloalkyl group. At least two of R a5 , R a6 , and R a7 may be bonded to each other to form a ring.
• the number of carbon atoms in the alkyl group as R a5 or R a6 is preferably 1 or more and 6 or less.
• the alkyl group as R a5 or R a6 may be linear or branched.
• the number of carbon atoms in the alkyl group as R a7 is preferably 1 or more and 10 or less.
• the alkyl group as R a7 may be linear or branched.
• the number of carbon atoms in the cycloalkyl group as R a7 is preferably 3 or more and 10 or less, for example.
• alkyl group as R a5 , R a6 , or R a7 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group. , isopentyl group, neopentyl group, and the like.
• Specific examples of the cycloalkyl group as R a7 include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, and cyclooctyl group.
• acetal protecting group represented by -C(R a5 )(R a6 )OR a7 in formula (a2) include 1-methoxyethyl group, 1-ethoxyethyl group, and 1-n-propoxyethyl group. group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group , 1-methoxy-1-methylethyl group, and 1-ethoxy-1-methylethyl group.
• the polyhydroxystyrene resin (A) may contain one or more types of structural units (a1).
• the polyhydroxystyrene resin (A) may contain one or more types of structural units (a2).
• the total of the ratio of the structural unit (a1) and the ratio of the structural unit (a2) in the polyhydroxystyrene resin (A) is 50 mol with respect to the number of moles of all the structural units constituting the polyhydroxystyrene resin (A). % or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, even more preferably 80 mol% or more and 100 mol% or less, particularly preferably 90 mol% or more and 100 mol% or less, and most preferably 100 mol%. preferable.
• the ratio of the number of moles of the structural unit (a2) to the total number of moles of the structural unit (a1) and the number of moles of the structural unit (a2) is preferably 10 mol% or more and 60 mol% or less, and 20 mol% or more. More preferably, it is 40 mol% or less.
• This ratio is the protection rate of hydroxyl groups derived from hydroxystyrene. When the protection rate is within the above range, it is easy to obtain a photosensitive resin composition with particularly good patterning properties.
• the ratio of the number of moles of the structural unit (a2) to the number of moles of all the structural units constituting the polyhydroxystyrene resin (A) is preferably 10 mol% or more and 60 mol% or less, and 20 mol% or more and 40 mol% or less. More preferred.
• the polyhydroxystyrene resin (A) may contain a structural unit (a1) and a structural unit (a3) other than the structural unit (a2).
• Examples of other monomers providing other structural units (a3) include (meth)acrylic esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and maleimides. . These compounds can be used alone or in combination of two or more.
• (meth)acrylic acid esters include linear or branched chains such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and tert-octyl (meth)acrylate.
• alkyl (meth)acrylate alkyl (meth)acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate,
• Examples include furfuryl (meth)acrylate; glycidyl (meth)acrylate; and (meth)acrylic acid ester having a group having an alicyclic skeleton.
• the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic.
• Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group.
• Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.
• (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, and N,N-aryl(meth)acrylamide. , N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, and the like.
• allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; etc.
• vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxy Aliphatic vinyl ethers such as ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4 -Vinyl aryl ethers such as dichlorophenyl ether, vinyl naphthyl ether
• vinyl esters examples include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Examples include vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl- ⁇ -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.
• styrenes examples include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene.
• ethoxymethylstyrene acetoxymethylstyrene
• alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene
• chlorostyrene dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo
• Halostyrenes such as styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and the like.
• maleimides include carbon atoms such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, etc.
• Maleimide N-substituted with an alkyl group having 1 to 10 atoms; N-substituted with an alicyclic group having 3 to 20 carbon atoms such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, etc.
• Maleimide N-arylmaleimide substituted with an aryl group having 6 to 20 carbon atoms such as N-phenylmaleimide, N- ⁇ -naphthylmaleimide, N- ⁇ -naphthylmaleimide; N-benzylmaleimide, N-phenethyl Examples include N-aralkylmaleimide substituted with an aralkyl group having 7 to 20 carbon atoms such as maleimide.
• the weight average molecular weight (Mw) of the polyhydroxystyrene resin (A) is preferably 5,000 or more and 30,000 or less.
• the weight average molecular weight is the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).
• the photosensitive resin composition contains a photoacid generator (B). Due to the action of the acid generated by the photoacid generator (B) upon exposure, the polyhydroxystyrene resin (A) is deprotected and becomes soluble in an alkaline developer. Therefore, the photosensitive resin composition can be suitably applied to patterning by photolithography.
• the photoacid generator (B) is not particularly limited, and any photoacid generator that has been conventionally blended into photosensitive resin compositions can be used without particular limitation.
• the photoacid generator (B) include onium salt type acid generators such as iodonium salts and sulfonium salts; oxime sulfonate type acid generators; diazomethane type acid generators; nitrobenzylsulfonate type acid generators; iminosulfonate type acid generators agents; disulfone type acid generators and the like.
• diazomethane type acid generators are preferred because they facilitate the production of photosensitive resin compositions with excellent photolithography properties.
• the diazomethane type acid generator is preferably used together with the onium salt type acid generator.
• the diazomethane type acid generator will also be referred to as diazomethane type acid generator (B1).
• the onium salt type acid generator is also referred to as an onium salt type acid generator (B2).
• the diazomethane type acid generator (B1) and the onium salt type acid generator (B2) will be explained below.
• the diazomethane type acid generator (B1) will be explained below.
• Examples of the diazomethane type acid generator (B1) include bissulfonyldiazomethane compounds such as bis(alkylsulfonyl)diazomethane, bis(cycloalkylsulfonyl)diazomethane, and bis(arylsulfonyl)diazomethane.
• bissulfonyldiazomethane compounds include bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, and bis(cyclohexyl).
• sulfonyl)diazomethane bis(2,4-dimethylphenylsulfonyl)diazomethane, and the like.
• Poly(bissulfonyl)diazomethane can also be used as the diazomethane type acid generator (B2).
• Examples of poly(bissulfonyl)diazomethane include 1,3-bis(phenylsulfonyldiazomethylsulfonyl)propane, 1,4-bis(phenylsulfonyldiazomethylsulfonyl)butane, and 1,6-bis(phenylsulfonyldiazomethylsulfonyl).
• hexane 1,10-bis(phenylsulfonyldiazomethylsulfonyl)decane, 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane, 1,3-bis(cyclohexylsulfonyldiazomethylsulfonyl)propane, 1,6-bis Examples include (cyclohexylsulfonyldiazomethylsulfonyl)hexane and 1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl)decane.
• Onium salt type acid generator (B2) Suitable examples of the onium salt type acid generator (B2) include a compound represented by the following formula (b-1) or a compound represented by the formula (b-2).
• the compound represented by formula (b-1) is also referred to as “component (b-1).”
• the compound represented by formula (b-2) is also referred to as “component (b-2).”
• R 101 and R 104 to R 105 each independently represent a cyclic group that may have a substituent, or a cyclic group that may have a substituent. It is a chain alkyl group or a chain alkenyl group which may have a substituent. R 104 and R 105 may be bonded to each other to form a ring. R 102 has 1 carbon atom 5 or less, or a fluorine atom.
• Y 101 is a divalent linking group containing an oxygen atom, or a single bond.
• V 101 to V 103 are each independently a single bond, an alkylene group or a fluorinated alkylene group.
• L 101 to L 102 are each independently a single bond or an oxygen atom.
• m is an integer of 1 or more.
• M' m+ is an m-valent onium cation
• R 101 is a cyclic group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
• R 101 is a cyclic group that may have a substituent
• the cyclic group is preferably a cyclic hydrocarbon group.
• the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an alicyclic hydrocarbon group.
• the alicyclic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
• the number of carbon atoms in the aromatic hydrocarbon group as R 101 is preferably 6 or more and 30 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 15 or less, particularly preferably 6 or more and 10 or less.
• the above number of carbon atoms does not include the number of carbon atoms of the substituent.
• aromatic hydrocarbon ring contained in the aromatic hydrocarbon group as R 101 include a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring.
• the cyclic group as R 101 may include an aromatic heterocycle in which some of the carbon atoms constituting the above-mentioned aromatic hydrocarbon ring are substituted with hetero atoms.
• the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
• aromatic hydrocarbon group as R 101 examples include phenyl group, naphthalen-1-yl group, naphthalen-2-yl group, 4-phenylphenyl group, 3-phenylphenyl group, and 2-phenylphenyl group. etc.
• Examples of the alicyclic hydrocarbon group as R 101 include aliphatic hydrocarbon groups containing a ring in the structure.
• the aliphatic hydrocarbon group containing a ring in its structure includes an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an alicyclic hydrocarbon ring), an alicyclic hydrocarbon group in which the alicyclic hydrocarbon group is linear or Examples include a group bonded to the end of a branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group.
• the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less.
• the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
• a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable.
• the number of carbon atoms in the monocycloalkane is preferably 3 or more and 6 or less. Specific examples of monocycloalkanes include cyclopentane and cyclohexane.
• a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferable.
• the number of carbon atoms in the polycycloalkane is preferably 7 or more and 30 or less.
• polycycloalkane examples include polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; condensed cyclic groups having a steroid skeleton; Examples include polycycloalkanes having a polycyclic skeleton.
• the alicyclic hydrocarbon group as R 101 is preferably a monocycloalkane or polycycloalkane with one or more hydrogen atoms removed, more preferably a polycycloalkane with one hydrogen atom removed, An adamantyl group and a norbornyl group are particularly preferred, and an adamantyl group is most preferred.
• the number of carbon atoms in the linear aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and even more preferably 1 or more and 4 or less. , most preferably 1 or more and 3 or less.
• a linear alkylene group is preferable. Preferred specific examples of linear alkylene groups include methylene group, ethane-1,2-diyl group (ethylene group), propane-1,3-diyl group (trimethylene group), and butane-1,4-diyl group. (tetramethylene group), and pentane-1,5-diyl group (pentamethylene group).
• the number of carbon atoms of the branched aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group is preferably 2 or more and 10 or less, more preferably 3 or more and 6 or less, and even more preferably 3 or 4. 3 is most preferred.
• a branched alkylene group is preferable, and specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 Alkylethylene groups such as CH 3 ) 2 -CH 2 -; -CH(CH 3 )CH 2 CH 2 -, alkyltrimethylene groups such as -CH 2 CH(CH 3 )CH 2 -; -CH(CH 3 ) Examples include alkylal
• the cyclic group as R 101 is a lactone-containing cyclic group, a -SO 2 --containing cyclic group represented by formulas (br2-1) to (br2-4) described below, and other heterocycles. Examples include formula groups.
• the "--SO 2 --containing cyclic group” is a cyclic group containing a ring containing an --SO 2 -- bond in its ring skeleton.
• the -SO 2 --containing cyclic group may be a monocyclic group or a polycyclic group.
• the -SO 2 --containing cyclic group consists only of -SO 2 --containing rings, the -SO 2 --containing cyclic group is a monocyclic group.
• the -SO 2 --containing cyclic group When the -SO 2 --containing cyclic group consists of two or more -SO 2 - rings, or has a ring of another structure in the -SO 2 - ring structure together with the -SO 2 - ring, the -SO 2 - -The containing cyclic group is a polycyclic group.
• a cyclic group containing an -O-SO 2 - bond in its ring skeleton is particularly preferred.
• Such cyclic groups contain sultone rings. More specific examples of the -SO 2 --containing cyclic group include groups represented by the following formulas (br2-1) to (br2-4).
• R'' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or an -SO 2 -containing cyclic group
• B'' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom, an alkylene group having 1 to 5 carbon atoms which may contain a sulfur atom, an oxygen atom, or sulfur. atoms; n' is 0, 1, or 2)
• the alkyl group as R b21 is preferably an alkyl group having 1 to 6 carbon atoms.
• the alkyl group may be linear or branched.
• Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group. and n-hexyl group.
• methyl group and ethyl group are preferred, and methyl group is particularly preferred.
• the alkoxy group as R b21 is preferably an alkoxy group having 1 or more and 6 or less carbon atoms.
• the alkoxy group may be linear or branched.
• Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, Examples include isopentyloxy group, neopentyloxy group, and n-hexyloxy group. Among these, methoxy group and ethoxy group are preferred, and methoxy group is particularly preferred.
• halogen atom as R b21 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atoms are preferred.
• halogenated alkyl group as R b21 examples include groups in which some or all of the hydrogen atoms of the alkyl group as R b21 are substituted with the halogen atoms.
• the halogenated alkyl group is preferably a fluorinated alkyl group, particularly a perfluoroalkyl group.
• R'' is a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO 2 --containing cyclic group.
• the alicyclic hydrocarbon group as R'' may be substituted with a fluorine atom or a fluorinated alkyl group.
• the alkylene group having 1 to 5 carbon atoms as B'' may be linear or branched.
• Specific examples of the alkylene group include a methylene group, ethylene group, n-propylene group, isopropylene group, etc.
• specific examples include the alkylene group. Examples include groups in which -O- or -S- is present at the end of the group or between carbon atoms. More specifically, for example, O-CH 2 -, -CH 2 -O-CH 2 -, -S- Examples include CH 2 -, -CH 2 -S-CH 2 -, etc.
• B'' is preferably an alkylene group having 1 to 5 carbon atoms, or -O-, and alkylene having 1 to 5 carbon atoms. groups are more preferred, and methylene groups are most preferred. Specific examples of groups represented by formulas (br2-1) to (br2-4) are listed below. "Ac” in the formula represents an acetyl group.
• examples of the substituent that the cyclic group as R 101 may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. Examples include groups.
• the alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, and tert-butyl group.
• the alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, isopropyloxy group, n-butyloxy group, or tert-butyloxy group. Most preferred are methoxy and ethoxy groups.
• halogen atom as a substituent, a fluorine atom is preferable.
• the halogenated alkyl group as a substituent is preferably a halogenated alkyl group having 1 to 5 carbon atoms, such as a halogenated methyl group, a halogenated ethyl group, a halogenated propyl group, a halogenated n-butyl group, and a halogenated alkyl group.
• a tert-butyl group is more preferred.
• the halogenated alkyl group may be a group in which some of the hydrogen atoms in the alkyl group are substituted with halogen atoms, or may be a group in which all hydrogen atoms in the alkyl group are substituted with halogen atoms.
• a carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) constituting a ring contained in a cyclic group.
• the chain alkyl group as R 101 may be linear or branched.
• the number of carbon atoms in the linear alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and most preferably 1 or more and 10 or less.
• linear alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, Examples include n-nonadecyl group and n-icosyl group.
• the number of carbon atoms in the branched alkyl group is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and most preferably 3 or more and 10 or less.
• Preferred specific examples of the branched alkyl group include 1-methylethyl group (isopropyl group), 1-methylpropyl group (sec-butyl group), 2-methylpropyl group (isobutyl group), and 1-methylbutyl group.
• the chain alkenyl group as R 101 may be linear or branched.
• the number of carbon atoms in the chain alkenyl group is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, even more preferably 2 or more and 4 or less, and particularly preferably 3.
• Preferred specific examples of the linear alkenyl group include, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), and a butenyl group.
• Preferred specific examples of the branched alkenyl group include, for example, 1-methylvinyl group, 1-methylpropenyl group, and 2-methylpropenyl group.
• linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
• Examples of substituents that the chain alkyl group or chain alkenyl group as R 101 may have include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and an amino group. , and the cyclic group as R 101 above.
• R 101 is preferably a cyclic group that may have a substituent, more preferably a cyclic hydrocarbon group that may have a substituent. More specifically, phenyl groups, naphthyl groups, groups obtained by removing one or more hydrogen atoms from polycycloalkanes, lactone-containing cyclic groups, and formulas (br2-1) to (br2-4) A -SO 2 --containing cyclic group represented by the following is preferred.
• Y 101 is a single bond or a divalent linking group containing an oxygen atom.
• the Y 101 may contain atoms other than the oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.
• a sulfonyl group (-SO 2 -) may be further linked to this combination.
• Examples of such a divalent linking group containing an oxygen atom include linking groups represented by the following formulas (by-1) to (by-7).
• V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms
• V' 102 is a (It is a divalent saturated hydrocarbon group of 30 or less.)
• the divalent saturated hydrocarbon group as V' 102 may be a chain saturated hydrocarbon group or a cyclic saturated hydrocarbon group, or a combination of a chain saturated hydrocarbon group and a cyclic saturated hydrocarbon group. It may be.
• the divalent saturated hydrocarbon group as V' 102 is preferably an alkylene group.
• the number of carbon atoms in the alkylene group is preferably 1 or more and 30 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less.
• alkylene groups as V' 101 and V' 102 may be linear or branched, and are preferably linear.
• Specific examples of alkylene groups as V' 101 and V' 102 include methylene group; -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C( Alkylmethylene groups such as CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, and -C(CH 2 CH 3 ) 2 -; ethylene group (-CH 2 CH 2 -); -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, and -CH(CH 2 CH 3 )CH 2 Alkylethylene groups such as -; trimethylene groups (-CH 2 CH 2 CH 2 -); alkyltrimethylene groups such as -CH (CH 3 ) CH
• some methylene groups may be substituted with a divalent aliphatic cyclic group having 5 or more and 10 or less carbon atoms.
• the aliphatic cyclic group may be a monocyclic group or a polycyclic group.
• the aliphatic hydrocarbon group which is a monocyclic group a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable.
• the number of carbon atoms in the monocycloalkane is preferably 3 or more and 6 or less.
• groups obtained by removing two hydrogen atoms from a monocycloalkane include a cyclopentylene group and a cyclohexylene group.
• cyclohexylene group is more preferred.
• aliphatic hydrocarbon group which is a polycyclic group a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable.
• the number of carbon atoms in the polycycloalkane is preferably 7 or more and 12 or less.
• Groups obtained by removing two hydrogen atoms from polycycloalkane include adamantanediyl group, norbornanediyl group, isobornanediyl group, tricyclodecanediyl group, and tetracyclododecanediyl group.
• adamantane-1,5-diyl group and adamantane-2,6-diyl group are more preferred.
• the aliphatic cyclic group may have a substituent.
• substituents include -R P1 , -R P2 -O-R P1 , -R P2 -CO-R P1 , -R P2 -CO- OR P1 , -R P2 -O-CO-R P1 , Examples include -R P2 -OH, -R P2 -CN, and -R P2 -COOH.
• R P1 is an alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.
• R P2 is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or 6 or more carbon atoms. It is a divalent aromatic hydrocarbon group of 30 or less.
• R P1 and R P2 are groups in which some or all of the hydrogen atoms of the above-mentioned chain saturated hydrocarbon group, cyclic saturated hydrocarbon group, and aromatic hydrocarbon group are substituted with fluorine atoms; Good too.
• the above cyclic hydrocarbon group may have one or more of the above substituents, or may have one or more of each of the above substituents.
• Examples of the monovalent alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and decyl group.
• Examples of the monovalent cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and cyclododecyl group.
• cycloalkyl group cycloalkyl group; bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.0 2,6 ]decanyl group, tricyclo[3.3.1.1 3,7 ]decanyl group, tetracyclo[ 6.2.1.1 3,6 . 0 2,7 ], polycyclic saturated hydrocarbon groups such as dodecanyl group and adamantyl group.
• monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include phenyl group, biphenylyl group, fluorenyl group, naphthyl group, anthryl group, and phenanthryl group.
• Y 101 is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, each represented by the above formulas (by-1) to (by-5). A linking group is more preferred.
• V 101 is a single bond, an alkylene group, or a fluorinated alkylene group.
• the number of carbon atoms in the alkylene group and fluorinated alkylene group as V 101 is preferably 1 or more and 4 or less.
• Examples of the fluorinated alkylene group as V 101 include groups in which some or all of the hydrogen atoms of the alkylene group as V 101 are substituted with fluorine atoms.
• V 101 is preferably a single bond or a fluorinated alkylene group having 1 or more and 4 or less carbon atoms.
• R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
• R 102 a fluorine atom and a perfluoroalkyl group having 1 or more and 5 or less carbon atoms are preferable, and a fluorine atom is more preferable.
• anion moiety represented by formula (b-1) include fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anions and perfluorobutanesulfonate anions.
• Y 101 is a divalent linking group containing an oxygen atom
• specific examples of the anion moiety represented by the formula (b-1) include those represented by the following formulas (ba-1) to (ba-3). Examples include anions such as
• R" 101 is an aliphatic cyclic group that may have a substituent, a monovalent heterocyclic group, or an aliphatic cyclic group that may have a substituent, or is a good alkyl group .
• R''103 is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or an -SO 2 -containing cyclic group.
• V" 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms.
• R102 is fluorine an atom or a fluorinated alkyl group having 1 or more and 5 or less carbon atoms.
• v" is each independently an integer of 0 or more and 3 or less
• q" is each independently an integer of 0 or more and 20 or less
• n is 0 or 1.
• the aliphatic cyclic group which may have a substituent as R" 101 , R" 102 and R" 103 is exemplified as the alicyclic hydrocarbon group as R 101 in formula (b-1).
• substituent include the same groups as those that may substitute the alicyclic hydrocarbon group as R 101 in formula (b-1).
• the aromatic cyclic group which may have a substituent as R'' 103 is a group exemplified as an aromatic hydrocarbon group as a cyclic hydrocarbon group for R 101 in formula (b-1).
• substituents include the same substituents that may substitute the aromatic hydrocarbon group as R 101 in formula (b-1).
• the chain alkyl group which may have a substituent as R'' 101 is preferably the group exemplified as the chain alkyl group as R 101 in formula (b-1).
• the chain alkenyl group which may have a substituent as R'' 103 is preferably the group exemplified as the chain alkenyl group as R 101 in formula (b-1).
• R 104 and R 105 each independently represent a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group that may be present. Examples of these groups include the same groups as R 101 in formula (b-1). R 104 and R 105 may be bonded to each other to form a ring. R 104 and R 105 are preferably an alkyl group that may have a substituent, more preferably an alkyl group or a fluorinated alkyl group. The alkyl group and fluorinated alkyl group may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 7 or less, and even more preferably 1 or more and 3 or less.
• the number of carbon atoms in the alkyl group as R 104 and R 105 is preferably as small as possible because the onium salt type acid generator (B2) is easily dissolved in a solvent.
• the fluorinated alkyl groups as R 104 and R 105 are substituted with fluorine atoms because of their strong acid strength and high transparency to high-energy light and electron beams with a wavelength of 250 nm or less. The larger the number of hydrogen atoms, the more preferable.
• the proportion of fluorine atoms in the fluorinated alkyl group is preferably 70 to 100%, more preferably 90 to 100%. Most preferred is a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms.
• V 102 and V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and each is the same bond as V 101 in formula (b-1), or a group.
• L 101 and L 102 are each independently a single bond or an oxygen atom.
• M' m+ represents an m-valent onium cation.
• the onium cation a sulfonium cation is preferred.
• m is an integer of 1 or more.
• the organic cation represented by M' m+ is not particularly limited, and any organic cation known as a cation moiety constituting a conventionally known onium salt type acid generator can be used as appropriate.
• a sulfonium cation is preferable.
• Specific examples include sulfonium cations represented by the following formula (bc-1) or (bc-2).
• R bc1 to R bc8 each independently represent an aryl group, an alkyl group, a cycloalkyl group, or an alkenyl group that may have a substituent.
• R bc1 to R bc5 may combine with each other to form a ring with the sulfur atom in the formula.
• R bc6 to R bc7 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• R bc8 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an SO 2 which may have a substituent. --containing cyclic group.
• examples of the aryl group as R bc1 to R bc5 include unsubstituted aryl groups having 6 to 20 carbon atoms.
• the unsubstituted aryl group phenyl group and naphthyl group are preferable.
• the number of carbon atoms in the alkyl group as R bc1 to R bc5 is preferably 1 or more and 30 or less.
• the number of carbon atoms in the cycloalkyl group as R bc1 to R bc5 is preferably 3 or more and 30 or less.
• the number of carbon atoms in the alkenyl group as R bc1 to R bc5 is preferably 2 or more and 10 or less.
• substituents that R bc1 to R bc5 and R bc8 may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and the following formula (bc- Examples include groups represented by r-1) to (bc-r-7), respectively.
• R' b11 each independently represents a hydrogen atom, a cyclic group that may have a substituent, or a cyclic group that may have a substituent. (It is a good alkyl group or an alkenyl group that may have a substituent.)
• the cyclic group as R' b11 is preferably a cyclic hydrocarbon group.
• the cyclic hydrocarbon group may be an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. good.
• the alicyclic hydrocarbon group may be saturated or unsaturated.
• the alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group.
• the number of carbon atoms in the aromatic hydrocarbon group as R' b11 is preferably 3 or more and 30 or less, more preferably 5 or more and 30 or less, even more preferably 5 or more and 20 or less, particularly preferably 6 or more and 15 or less, and 6 or more and 10 or less. is most preferred. However, the number of carbon atoms does not include the number of carbon atoms of substituents.
• aromatic hydrocarbon ring contained in the aromatic hydrocarbon group as R' b11 include a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring.
• the cyclic group as R' b11 may include an aromatic heterocycle in which some of the carbon atoms constituting the above-mentioned aromatic hydrocarbon ring are substituted with hetero atoms.
• the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
• aromatic hydrocarbon group as R' b11 examples include phenyl group, naphthalen-1-yl group, naphthalen-2-yl group, 4-phenylphenyl group, 3-phenylphenyl group, and 2-phenylphenyl group. Examples include groups.
• the number of carbon atoms in the alicyclic hydrocarbon group as R' b11 is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less.
• the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
• the monocyclic alicyclic hydrocarbon group is a cycloalkyl group.
• the number of carbon atoms in the cycloalkyl group is preferably 3 or more and 6 or less.
• Preferred specific examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
• As the polycyclic alicyclic hydrocarbon group a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferable.
• the number of carbon atoms in the polycycloalkane is preferably 7 or more and 30 or less.
• Preferred specific examples of polycycloalkanes include polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; cyclic groups having a steroid skeleton; Examples include polycycloalkanes having a polycyclic skeleton of a fused ring system.
• an adamantyl group and a norbornyl group are preferable, and an adamantyl group is more preferable.
• the cyclic hydrocarbon group as R' b11 may be a heterocycle containing a heteroatom.
• Specific examples include lactone-containing cyclic groups, -SO 2 --containing cyclic groups represented by formulas (br2-1) to (br2-4), and other heterocyclic groups.
• Examples of the substituent in the cyclic group as R' b11 in formulas (bc-r-1) to (bc-r-7) include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, Examples include carbonyl group and nitro group.
• the alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, and tert-butyl group.
• alkoxy group an alkoxy group having 1 to 5 carbon atoms is preferable, and methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group are more preferable.
• methoxy group and an ethoxy group are more preferable.
• halogen atom a fluorine atom is preferable.
• halogenated alkyl group as a substituent examples include an alkyl group having 1 to 5 carbon atoms, such as a part of a hydrogen atom such as a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group; Examples include groups entirely substituted with halogen atoms.
• the carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) constituting a cyclic hydrocarbon group.
• the alkyl group as R' b11 may be either linear or branched.
• the number of carbon atoms in the linear alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and even more preferably 1 or more and 10 or less.
• the number of carbon atoms in the branched alkyl is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and even more preferably 3 or more and 10 or less.
• branched alkyl examples include isopropyl group, sec-butyl group, isobutyl group, sec-pentyl group, 2-methylbutyl group, isopentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group. , 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.
• the alkenyl group as R' b11 may be either linear or branched.
• the number of carbon atoms in the linear alkenyl group is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, even more preferably 2 or more and 4 or less, and particularly preferably 3.
• Specific examples of the linear alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group (allyl group), and butenyl group.
• Specific examples of the branched alkenyl group include 1-methylvinyl group, 1-methylpropenyl group, and 2-methylpropenyl group.
• a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.
• Examples of the substituent that the alkyl group and alkenyl group as R' b11 may have include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above R' Examples of b11 include a cyclic group.
• R' b11 is preferably a cyclic group that may have a substituent, and more preferably a cyclic hydrocarbon group that may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, a lactone-containing cyclic group, formulas (br2-1) to (br2-4 ) -SO 2 -containing cyclic groups represented by ) are preferred.
• one ring containing a sulfur atom in its ring skeleton in the formula is preferably a 3- to 10-membered ring, and particularly preferably a 5- to 7-membered ring.
• the ring include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiine ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring. etc.
• R bc6 to R bc7 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• R bc6 to R bc7 are preferably a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms.
• R bc6 and R bc7 may be bonded to each other to form a ring.
• R bc8 is an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an SO 2 -containing group that may have a substituent It is a cyclic group.
• the aryl group is preferably an unsubstituted aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a naphthalen-1-yl group, and a naphthalen-2-yl group. preferable.
• R bc8 is an alkyl group
• the alkyl group may be a chain or cyclic alkyl group.
• the number of carbon atoms in the alkyl group is preferably 1 or more and 30 or less.
• R bc8 is an alkenyl group
• the number of carbon atoms in the alkenyl group is preferably 2 or more and 10 or less.
• the SO 2 -containing cyclic group which may have a substituent as R bc8 is preferably a "-SO 2 -containing polycyclic group".
• g1, g2, and g3 indicate the number of repetitions of the groups in parentheses, g1 is an integer of 1 to 5, and g2 is 0 to 5. It is an integer of 20 or less, and g3 is an integer of 0 or more and 20 or less.
• R" b11 is a hydrogen atom or a substituent, and the substituent is the same as the substituent that R bc1 to R bc5 and R bc8 may have.
• cation represented by the formula (bc-2) include cations represented by the following formulas (bc-2-1) to (bc-2-6).
• cations represented by formulas (bc-1) and (bc-2) are preferable.
• cations represented by formulas (bc-1-1) to (bc-1-6) and (bc-1-52) to (bc-1-60) are preferred.
• R b1 to R b3 each independently represent an aryl group which may have a substituent. Any two of R b1 to R b3 bond to each other to form the formula may form a ring together with the sulfur atom in R101.
• R101 is a cyclic group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. group.
• R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom.
• Y 101 is a divalent linking group containing an oxygen atom, or a single bond. V 101 is , a single bond, or an oxygen atom)
• R 101 , Y 101 , V 101 , and R 102 are the same as R 101 , Y 101 , V 101 , and R 102 in formula (b-1).
• R b1 to R b3 are each independently an aryl group which may have a substituent. Any two of R b1 to R b3 may be bonded to each other to form a ring with the sulfur atom in the formula.
• the aryl groups in R b1 to R b3 are the same as the aryl groups in R bc1 to R bc3 in the above formula (bc-1).
• the substituents that the aryl group may have are the same as the substituents that the aryl group in R bc1 to R bc3 of the above formula (bc-1) may have.
• R bc1 to R bc3 in the above formula (bc-1) bond to each other to form a sulfur atom in the formula. Examples include rings similar to those formed with atoms.
• one type of photoacid generator (B) may be used alone, or two or more types may be used in combination.
• the content of the photoacid generator (B) in the photosensitive resin composition is 0.5 parts by mass or more and 30 parts by mass or less, preferably 1 part by mass or more and 15 parts by mass, based on 100 parts by mass of the polyhydroxystyrene resin (A). It is not more than 2 parts by mass and more preferably not less than 2 parts by mass and not more than 10 parts by mass.
• the content of the photoacid generator (B) is within the above range, it is easy to obtain a photosensitive resin composition with particularly good photolithography properties.
• the photoacid generator (B) includes a diazomethane type acid generator (B1) and an onium salt type acid generator (B2)
• the onium salt type acid generator relative to the mass of the photoacid generator (B)
• the total ratio of the mass of (B1) to the mass of the diazomethane type acid generator (B2) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and 90% by mass. The above is particularly preferable, and 100% by mass is most preferable.
• the ratio of the mass of the diazomethane type acid generator (B1) to the total mass of the diazomethane type acid generator (B1) and the mass of the onium salt type acid generator (B2) is 50% by mass or more and 100% by mass or less is preferable, and more preferably 60% by mass or more and 90% by mass or less.
• the photosensitive resin composition contains a methylol type crosslinking agent (C).
• the methylol type crosslinking agent (C) is a compound having two or more groups selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group in the molecule.
• the alkoxy group in the alkoxymethyl group and the acyl group in the acyloxymethyl group may be substituted with a halogen atom.
• the methylol type crosslinking agent (C) is preferably a compound having two or more groups selected from methylol groups and alkoxymethyl groups.
• the photosensitive resin composition contains the methylol-type crosslinking agent (C)
• the polyhydroxystyrene resin (A) is crosslinked by the methylol-type crosslinking agent (C) by heating the photosensitive resin composition.
• a cured product with excellent chemical resistance is formed.
• the polyhydroxystyrene resin (A) is crosslinked with the methylol type crosslinking agent by heating the patterned coating film.
• a patterned resin film (cured film) with excellent chemical resistance is formed.
• the number of groups selected from methylol groups and alkoxymethyl groups in one molecule in the methylol type crosslinking agent (C) is as follows: The number is preferably 2 or more and 10 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 4 or less.
• the number of carbon atoms in the alkoxy group in the alkoxymethyl group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, particularly preferably 1 or 2, and most preferably 1. That is, the most preferred alkoxymethyl group is a methoxymethyl group.
• An alkoxy group in the alkoxymethyl group may be linear or branched, preferably linear.
• the acyloxy group in the acyloxymethyl group is not particularly limited as long as it is a group represented by R-CO-O-.
• R is an organic group. R is bonded to the carbonyl group through a C—C bond.
• As the organic group for R an alkyl group and an aryl group are preferable, and an alkyl group is more preferable.
• the number of carbon source atoms in the organic group as R is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 6 or less.
• Suitable examples of the methylol-type crosslinking agent (C) include methylolmelamine compounds, methylolguanamine compounds, methylolurea compounds, resol resins, and aromatic compounds having a methylol group or alkoxymethyl group on an aromatic ring.
• methylolmelamine compounds, methylolguanamine compounds, methylolurea compounds, and aromatic compounds having a methylol group or an alkoxymethyl group on an aromatic ring are preferred.
• aromatic compounds having a methylol group or an alkoxymethyl group on an aromatic ring include compounds described in paragraphs [0136] to [0139] of JP-A-2013-064829, and paragraphs of JP-A-10-0120940. Examples include compounds described in [0029] to [0036].
• methylol type crosslinking agent (C) compounds having a methylol group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom are particularly preferred.
• the methylol-type crosslinking agent (C) having a methylol group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom is preferably a methylolmelamine compound, a methylolguanamine compound, or a methylolurea compound; Urea compounds are more preferred, and methylolmelamine compounds are even more preferred.
• methylolmelamine compound a compound represented by the following formula (C1) is preferable.
• R c11 to R c16 are each independently a hydrogen atom or a group represented by -CH 2 -O-R c .
• R c is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms. However, at least two of R c11 to R c16 are groups represented by -CH 2 -O-R c .
• the alkyl group as R c may be linear or branched, and is preferably linear.
• the number of carbon atoms in the alkyl group as R c is 1 or more and 6 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, even more preferably 1 or 2, and particularly preferably 1.
• the number of groups represented by -CH 2 -O-R c among R c11 to R c16 is preferably 4 or more and 6, more preferably 5 or 6, and even more preferably 6.
• methylolguanamine compound a compound represented by the following formula (C2) is preferable.
• R c21 is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
• R c22 to R c25 are each independently a hydrogen atom or a group represented by -CH 2 -O-R c . At least two of R c22 to R c25 are groups represented by -CH 2 -O-R c .
• the alkyl group as R c21 may be linear or branched, and is preferably linear.
• the number of carbon atoms in the alkyl group as R c21 is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, even more preferably 1 or 2, and particularly preferably 1.
• the number of carbon atoms in the cycloalkyl group as R c21 is preferably 3 or more and 10 or less, more preferably 3 or more and 8 or less, even more preferably 4 or more and 7 or less, and particularly preferably 5 or 6.
• the number of carbon atoms in the aryl group as R c21 is preferably 6 or more and 14 or less, more preferably 6 or more and 10 or less.
• R c21 is preferably a hydrogen atom, a methyl group, or a phenyl group, more preferably a hydrogen atom or a phenyl group, and even more preferably a phenyl group.
• the number of groups represented by -CH 2 -O-R c from R c22 to R c25 is preferably 2 or more and 4 or less, more preferably 3 or 4, and even more preferably 4. .
• methylol urea compound a compound represented by the following formula (C3) is preferable.
• R c31 and R c33 are each independently a hydrogen atom, an alkyl group, or a cycloalkyl group.
• R c32 and R c34 are groups represented by -CH 2 -O-R c .
• R c31 and R c33 may be combined with each other to form a ring. Another ring may be fused to the ring formed by combining R c31 and R c33 .
• Compounds represented by formula (C3) and containing a ring formed by bonding R c31 and R c33 may be condensed.
• the alkyl group as R c31 or R c33 may be linear or branched, and preferably linear.
• the number of carbon atoms in the alkyl group as R c31 or R c33 is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less, and even more preferably 1 or more and 4 or less.
• the number of carbon atoms in the cycloalkyl group as R c31 or R c33 is preferably 3 or more and 10 or less, more preferably 3 or more and 8 or less, even more preferably 4 or more and 7 or less, and particularly preferably 5 or 6.
• R c31 and R c33 are preferably both hydrogen atoms or bond to each other to form a ring.
• the compound represented by the formula (C3) is preferably a compound represented by the following formula (C4) or the following formula (C5).
• the compound represented by the following formula (C5) is also referred to as a methylol glycoluril compound.
• R c41 and R c42 are groups represented by -CH 2 -O-R c .
• R c43 and R c44 are hydrogen atoms or monovalent organic groups.
• L is a single bond or a divalent linking group.
• both R c41 and R c42 are preferably methoxymethyl groups.
• R c43 and R c44 are preferably monovalent organic groups.
• the monovalent organic group is not particularly limited.
• an alkyl group and an alkoxy group are preferable, and an alkoxy group is more preferable.
• the number of carbon atoms in the alkyl group and the alkoxy group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, even more preferably 1 or more and 3 or less, particularly preferably 1 or 2, and most preferably 1.
• L is preferably a single bond.
• the divalent linking group as L is preferably an alkylene group.
• the alkylene group may be interrupted by an oxygen atom, a carbonyl group, or a carboxylic acid ester bond.
• R c51 to R c54 are hydrogen atoms or groups represented by -CH 2 -O-R c . At least two of R c51 to R c54 are groups represented by -CH 2 -O-R c . The number of groups represented by -CH 2 -O-R c as R c51 to R c54 is preferably 3 or 4, and more preferably 4.
• Preferred specific examples of the methylol-type crosslinking agent (C) described above include the following compounds.
• methylol type crosslinking agent (C) commercially available products can also be used. Specific examples of commercial products include Nikalak MX-270, Nikalak MW-100LM, Nikalak MX-280, and Nikalak MX-290 (all manufactured by Sanwa Chemical Co., Ltd.).
• the methylol type crosslinking agent (C) may be used alone or in combination of two or more.
• the content of the methylol type crosslinking agent (C) in the photosensitive resin composition is not particularly limited as long as the desired effect is not impaired.
• the content of the methylol type crosslinking agent (C) in the photosensitive resin composition is preferably 1.0 parts by mass or more and 5.0 parts by mass or less, based on 100 parts by mass of the polyhydroxystyrene resin (A). More preferably 0 parts by mass or more and 3.0 parts by mass or less, particularly preferably 1.0 parts by mass or more and 2.0 parts by mass or less.
• the methylol type crosslinking agent (C) can also be used in an amount exceeding 5.0 parts by mass with respect to 100 parts by mass of the polyhydroxystyrene resin (A).
• the mass of the photoacid generator (B) is preferably 0.8 times or more and no more than 2 times the mass of the methylol type crosslinking agent (C), and preferably 1 time or more and no more than 1.5 times. More preferred.
• the photosensitive resin composition may contain a quencher (D).
• a quencher (D) a low molecular compound (non-polymer) is usually used.
• the quencher (D) include amines such as aliphatic amines and aromatic amines.
• aliphatic amines are preferred, and secondary aliphatic amines and tertiary aliphatic amines are particularly preferred.
• an aliphatic amine is an amine having one or more aliphatic groups. The number of carbon atoms in the aliphatic group that the aliphatic amine has is preferably 1 or more and 20 or less.
• aliphatic amines examples include ammonia (NH 3 ) in which at least one hydrogen atom is substituted with an alkyl group having 20 or less carbon atoms, and ammonia (NH 3 ) in which at least one hydrogen atom is substituted with a hydroxyalkyl group. Included are group-substituted alkanolamines and cyclic amines.
• alkylamines and alkanolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; diethylamine, di-n-propylamine, di- Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropyl
• Examples of the cyclic amine include nitrogen-containing heterocyclic compounds.
• the nitrogen-containing heterocyclic compound may be a monocyclic aliphatic amine or a polycyclic aliphatic amine.
• aliphatic monocyclic amine examples include piperidine and piperazine.
• the number of carbon atoms in the aliphatic polycyclic amine is preferably 6 or more and 10 or less.
• Examples of aliphatic polycyclic amines include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, and hexamethylenetetramine. , and 1,4-diazabicyclo[2.2.2]octane.
• aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris ⁇ 2-(2-methoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(2-methoxyethoxymethoxy)ethyl ⁇ Amine, Tris ⁇ 2-(1-methoxyethoxy)ethyl ⁇ amine, Tris ⁇ 2-(1-ethoxyethoxy)ethyl ⁇ amine, Tris ⁇ 2-(1-ethoxypropoxy)ethyl ⁇ amine, Tris[2- ⁇ 2 -(2-hydroxyethoxy)ethoxy ⁇ ethylamine and the like.
• aromatic amines include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, Examples include 2,2'-dipyridyl and 4,4'-dipyridyl.
• Quenchers (D) may be used alone or in combination of two or more.
• the amount of quencher (D) contained in the photosensitive resin composition is preferably 0.01 parts by mass or more and 5.0 parts by mass or less based on 100 parts by mass of polyhydroxystyrene resin (A).
• the photosensitive resin composition may contain an organic solvent (S). Containing the organic solvent (S) in the photosensitive resin composition improves the coating properties of the photosensitive resin composition and the thickness of the positive photosensitive resin composition layer formed using the photosensitive resin composition. Easy to adjust.
• the organic solvent (S) can be used alone or in combination of two or more.
• organic solvent (S) examples include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, and propylene glycol monoacetate.
• dipropylene glycol, and dipropylene glycol monoacetate and polyhydric alcohols such as their monomethyl ethers (e.g., propylene glycol monomethyl ether acetate), monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether, and their Derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxy acetate, methoxypropion Methyl acid, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate,
• the content of the organic solvent (S) is preferably 50 parts by mass or more and 3000 parts by mass or less, and 100 parts by mass or more and 2000 parts by mass or less, based on 100 parts by mass of the polyhydroxystyrene resin (A). More preferably, it is less than parts by mass.
• the content is within the above range, the coating properties of the photosensitive resin composition are likely to improve, and the thickness of the coating film formed using the photosensitive resin composition. It is easy to adjust.
• the photosensitive resin composition may contain various additives in addition to the above-mentioned components as long as the desired effects are not impaired.
• the additive may be appropriately selected from various additives conventionally blended into photosensitive resin compositions. Specific examples of other components include polyvinyl resin, surfactant, and acid or acid anhydride.
• the photosensitive resin composition may contain a polyvinyl resin in order to improve the plasticity of the formed film.
• polyvinyl resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinylethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. can be mentioned.
• the photosensitive resin composition may contain an adhesion aid to improve adhesion to the support.
• the photosensitive resin composition may contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties, etc.
• a surfactant include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by DIC), and Florado FC.
• the photosensitive resin composition may contain an acid or an acid anhydride in order to finely adjust the solubility in a developer.
• acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxy monocarboxylic acids such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, etc.
• monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid
• lactic acid, 2-hydroxybutyric acid Hydroxy monocarboxylic acids such as 3-hydroxybutyric acid,
• Acids oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid acids, polyhydric carboxylic acids such as butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, anhydride Succinic acid, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, himic anhydr
• the photosensitive resin composition can be prepared by mixing and stirring the above components in a conventional manner. If necessary, dispersion and mixing may be performed using a dispersing machine such as a dissolver, homogenizer, or three-roll mill. Furthermore, after mixing, the mixture may be further filtered using a mesh, membrane filter, or the like.
• a dispersing machine such as a dissolver, homogenizer, or three-roll mill.
• the mixture may be further filtered using a mesh, membrane filter, or the like.
• the photosensitive resin composition provides a cured product with excellent chemical resistance when heated. Therefore, the above-described photosensitive resin composition is suitably used in a method for manufacturing an optical element, which includes a plurality of microlenses including n types of microlenses of different sizes on a base material. In such a manufacturing method, the cured product of the photosensitive resin composition frequently comes into contact with a chemical solution such as an organic solvent.
• n is an integer of 2 or more.
• n is preferably an integer of 2 or more and 4 or less, more preferably 2 or 3, and particularly preferably 2.
• an optical element including two types of microlenses of different sizes is preferably manufactured.
• the above manufacturing method includes forming a resin film on a base material, forming a mask having a shape corresponding to the shape of the plurality of microlenses on the resin film; This includes forming a plurality of microlenses onto which the shape of the mask is transferred by etching the resin film together with the mask.
• the resin film is formed as described above as a lens material layer.
• an image element including a photodiode (organic photodiode, inorganic photodiode, etc.), a silicon wafer provided with a color filter layer, etc., a substrate such as a silicon wafer further formed with an antireflection film if necessary, etc. can be mentioned.
• a mask having a shape corresponding to the shape of the plurality of microlenses is formed on the resin film.
• the mask is formed by repeating the operations (i) to (iii) below n times.
• the above m is an integer greater than or equal to 1 and less than or equal to n.
• the first to nth photosensitive compositions used in forming the mask may be the same or different. At least one of the first to nth photosensitive compositions is the photosensitive resin composition described above.
• a method for forming a microlens-shaped mask on a resin film for forming the first microlens will be described.
• a first photosensitive composition is applied onto a resin film to form a first coating film.
• any photosensitive composition used for forming a microlens-shaped mask in the above-mentioned etchback method can be used without particular limitation.
• the first photosensitive composition is preferably the photosensitive resin composition described above.
• the method of applying the first photosensitive composition is not particularly limited.
• the first photosensitive composition can be coated using a contact transfer coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact coating device such as a spinner (rotary coating device) or curtain flow coater.
• the first coating film can be formed by coating the material to a desired thickness.
• the first coating film made of the photosensitive composition may be appropriately subjected to heat treatment (pre-bake (post-apply bake (PAB) treatment) to remove the solvent in the first coating film.
• pre-bake post-apply bake (PAB) treatment
• PAB post-apply bake
• the conditions for the heat treatment described above vary depending on the type of each component of the photosensitive composition, the blending ratio, the coating film thickness, etc.
• the heating temperature is, for example, preferably 60°C or more and 150°C or less, more preferably 70°C or more and 140°C or less.
• the heating time is, for example, preferably 0.5 minutes or more and 60 minutes or less, more preferably 1 minute or more and 50 minutes or less.
• the thickness of the first coating film is preferably in the range of 100 nm or more and 4.0 ⁇ m or less, more preferably 400 nm or more and 2.0 ⁇ m or less.
• the first coating film is exposed and developed to form a first dot on the base material at a position corresponding to the position where the first microlens is to be formed.
• Exposure is performed positionally selectively so that the first dot is formed at a predetermined position.
• Position-selective exposure can be performed, for example, via a desired mask pattern.
• the wavelength of the light beam used for exposure is not particularly limited. Exposure can be performed using radiation such as KrF excimer laser, ArF excimer laser, F2 excimer laser, EUV (extreme ultraviolet light), VUV (vacuum ultraviolet light), EB (electron beam), X-rays, soft X-rays, and the like.
• PEB post-exposure bake
• PEB heat treatment post-exposure heat treatment
• the conditions for the PEB treatment vary depending on the type of each component in the first coating film, the blending ratio, the coating film thickness, etc.
• the heating temperature is preferably 60°C or higher and 150°C or lower, more preferably 70°C or higher and 140°C or lower.
• the heating time is, for example, preferably 0.5 minutes or more and 60 minutes or less, more preferably 1 minute or more and 50 minutes or less.
• the exposed first coating film is developed. This dissolves and removes unnecessary parts.
• Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.
• An aqueous solution of an alkali such as 0]-5-nonane can be used.
• an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above-mentioned alkali can also be used as the developer.
• a tetramethylammonium hydroxide aqueous solution having a concentration of 0.1% by mass or more and 10% by mass or less is preferred.
• the development time varies depending on the composition of the first photosensitive composition, the thickness of the first coating film, etc., but is usually 1 minute or more and 30 minutes or less.
• the developing method may be any of the piling method, dipping method, paddle method, spray developing method, and the like.
• the developed first coating film is washed with running water or the like, if necessary, and then dried. In this way, a dot pattern consisting of the first dot is formed.
• the heating conditions vary depending on the type of each component in the first photosensitive composition, the blending ratio, the coating film thickness, etc.
• the heating temperature is preferably 130°C or higher and 170°C or lower, more preferably 140°C or higher and 160°C or lower.
• the heating time is, for example, preferably 1 minute or more and 30 minutes or less, more preferably 3 minutes or more and 10 minutes or less.
• a mask having a shape corresponding to the shape of the first microlens is formed on the resin film.
• a second photosensitive composition is used on the resin film whose surface is provided with a mask having a shape corresponding to the shape of the first microlens, to form a mask having a shape corresponding to the shape of the second microlens. form a mask.
• the method of forming a mask having a shape corresponding to the shape of the second microlens is the same as the method of forming a mask having a shape corresponding to the shape of the first microlens.
• the second photosensitive composition the above-mentioned photosensitive resin composition is preferable.
• n types of masks corresponding to the shapes of n types of microlenses are formed on the resin film.
• etching a resin film with n types of masks so that the resin film is etched together with the mask, a plurality of microlenses with the shapes of the n types of masks transferred are formed on the base material. be done.
• an optical element including a plurality of microlenses can be manufactured on a base material also by the following method. Specifically, this method: Coating the aforementioned photosensitive resin composition onto a substrate to form a coating film; position-selectively exposing the coating film so that a plurality of dots are formed at positions on the base material where a plurality of microlenses are formed; Developing the exposed coating film to form a plurality of dots at positions where a plurality of microlenses are to be formed; The method includes heating the plurality of dots to thermally deform the plurality of dots to form the plurality of microlenses.
• the photosensitive resin composition described above is applied directly onto the substrate rather than onto the resin film formed on the substrate.
• This method is carried out in the same manner as the method for manufacturing a mask in the method for manufacturing an optical element, which includes a plurality of microlenses.
• Example 1 to Example 8 Comparative Example 1, and Comparative Example 2
• A-1 and A-2 consisting of the following units were used as the polyhydroxystyrene resin (A).
• the number attached to each repeating unit is the ratio (mol %) of each unit to the total units contained in the resin (A).
• the weight average molecular weight (Mw) of Resin A-1 measured by gel permeation chromatography in terms of polystyrene is 20,000.
• the weight average molecular weight (Mw) of Resin A-2 measured by gel permeation chromatography in terms of polystyrene is 10,000.
• B1 diazomethane type acid generator
• B1 Bis(cyclohexylsulfonyl)diazomethane was used.
• B2-1 to B2-3 were used as the onium salt type acid generator (B2).
• the photosensitive compositions of each Example and each Comparative Example were applied onto a silicon substrate using a spin coater.
• the photosensitive composition coated on the silicon substrate was baked at 100° C. for 60 seconds to obtain a coating film with a thickness of about 300 nm.
• the obtained coating film was baked at 200° C. for 5 minutes to obtain a cured film.
• a positive photosensitive composition that becomes soluble in an alkaline developer upon exposure to light was applied onto the obtained cured film.
• the applied positive photosensitive composition was baked at 100° C. for 60 seconds to obtain a coating film with a thickness of about 700 nm.
• the exposed coating film of the positive photosensitive composition was removed by contacting with an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass for 60 seconds at room temperature.
• the remaining film rate was calculated based on the following formula from the thickness T1 of the cured film before the removal of the positive photosensitive composition and the thickness T2 of the cured film after the removal of the positive photosensitive composition.
• Remaining film rate (%) T2/T1 x 100 Based on the calculated residual film rate, chemical resistance was evaluated according to the following criteria. A: The residual film rate was 98% or more. B: The residual film rate was 80% or more and less than 98%. C: The residual film rate was less than 80%.
• the optimum exposure amount (EOP) was 50 mJ/cm 2 or less.
• the optimum exposure amount (EOP) was more than 50 mJ/cm 2 and less than 60 mJ/cm 2 .
• C The optimum exposure amount (EOP) was more than 60 mJ/cm 2 .

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• 2023
  • 2023-09-01 JP JP2024545637A patent/JPWO2024053579A1/ja active Pending
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