Photosensitive resin composition

Abstract

The invention relates to a photosensitive resin composition. The present invention addresses the problem of providing: a photosensitive resin composition capable of providing a microlens having excellent chemical resistance by a heat flow method; a cured product of the photosensitive resin composition; a microlens formed from the cured product; and a method for producing an optical element using the photosensitive resin composition. [Solution] In a photosensitive resin composition containing a polyhydroxystyrene resin (A), a photoacid generator (B), and a cross-linking agent (C), the polyhydroxystyrene resin (A) in which some of the phenolic hydroxyl groups are protected by an acetal-type protecting group is used. The photosensitive resin composition is configured such that the photosensitive resin composition can provide a cured product that exhibits a refractive index of 1.50 or more at a wavelength of 550 nm.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product of the photosensitive resin composition, a microlens formed from the cured product, a method for manufacturing a cured product of the foregoing photosensitive resin composition, and a method for manufacturing an optical element using the cured product of the foregoing photosensitive resin composition. Background Art

[0002] Conventionally, solid-state imaging devices have been used in cameras, video cameras, etc. In such solid-state imaging devices, CCD (charge-coupled device) image sensors and CMOS (complementary metal-oxide semiconductor) image sensors have been used. In the image sensor, fine condenser lenses (hereinafter referred to as microlenses) are provided for the purpose of increasing the light collection rate.

[0003] As a method for forming the microlens, a method called the heat flow method has been widely adopted industrially.

[0004] In the heat flow method, first, a photoresist film is formed on the upper part of a CCD element or the like. The photoresist film is a film composed of a photosensitive resin composition or the like. Then, by exposing and developing the photoresist film, a dot pattern formed of resin is formed on the element. The dot pattern includes a plurality of dots located at the positions where microlenses are to be formed. Each dot constituting the dot pattern has a substantially cylindrical shape or a substantially frustoconical shape. By heating the dot pattern at a temperature above the glass transition temperature of the resin material constituting the dots, the resin material constituting the dots flows, and due to surface tension, the shape of each dot changes to a hemispherical lens shape. The microlens pattern is formed as described above (for example, see Patent Document 1).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2020-100793 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] The microlenses formed by the above heat flow method are sometimes frequently exposed to chemical liquids such as organic solvents during the process of manufacturing elements equipped with microlenses.

[0010] Therefore, for the photosensitive resin composition used in the heat flow method, it is required to provide microlenses with excellent chemical resistance.

[0011] The present invention has been made in view of such prior circumstances, and an object thereof is to provide a photosensitive resin composition capable of providing a micro-lens excellent in chemical resistance by a heat flow method, a cured product of the photosensitive resin composition, a micro-lens formed from the cured product, and a method for manufacturing an optical element using the above-mentioned photosensitive resin composition.

[0012] Means for Solving the Problem

[0013] The inventors of the present application have found that, in a photosensitive resin composition containing a polyhydroxystyrene resin (A), a photoacid generator (B) that generates an acid upon irradiation with actinic light or radiation, and a crosslinking agent (C), by using a polyhydroxystyrene resin (A) in which a part of the phenolic hydroxyl groups is protected with an acetal-type protecting group, and configuring the photosensitive resin composition such that the cured product exhibits a refractive index of 1.50 or more at a wavelength of 550 nm, the above-mentioned problem can be solved, and thus the present invention has been completed. Specifically, the present invention provides the following aspects.

[0014] A first aspect of the present invention is a photosensitive resin composition containing a polyhydroxystyrene resin (A), a photoacid generator (B) that generates an acid upon irradiation with actinic light or radiation, and a crosslinking agent (C),

[0015] in the polyhydroxystyrene resin (A), a part of the phenolic hydroxyl groups is protected with an acetal-type protecting group,

[0016] and the photosensitive resin composition can provide a cured product having a refractive index of 1.50 or more at a wavelength of 550 nm.

[0017] A second aspect of the present invention is a cured product of the photosensitive resin composition according to the first aspect.

[0018] A third aspect of the present invention is a micro-lens formed from the cured product according to the second aspect.

[0019] A fourth aspect of the present invention is a method for manufacturing a cured product, which includes a step of heating the photosensitive resin composition according to the first aspect.

[0020] A fifth aspect of the present invention is a method for manufacturing an optical element, the optical element having a plurality of micro-lenses on a substrate, the manufacturing method including the following steps:

[0021] a step of coating the substrate with the photosensitive resin composition according to the first aspect to form a coating film;

[0022] a step of selectively exposing the coating film at positions where a plurality of micro-lenses are to be formed on the substrate so as to form a plurality of dots;

[0023] A step of developing the exposed coating film to form a plurality of dots at positions where a plurality of microlenses are to be formed; and

[0024] A step of heating the plurality of dots, thereby deforming the plurality of dots by heat to form a plurality of microlenses,

[0025] In the manufacturing method, before heating the plurality of dots, the plurality of dots are exposed.

[0026] Advantages of the Invention

[0027] According to the present invention, there can be provided a photosensitive resin composition capable of providing microlenses with excellent chemical resistance by a heat flow method, a cured product of the photosensitive resin composition, microlenses formed from the cured product, and a method for manufacturing an optical element using the aforementioned photosensitive resin composition. Detailed Embodiments

[0028] <<Photosensitive Resin Composition>>

[0029] The photosensitive resin composition contains a polyhydroxystyrene resin (A), a photoacid generator (B) that generates an acid upon irradiation with active light or radiation, and a crosslinking agent (C).

[0030] In the polyhydroxystyrene resin (A), a part of the phenolic hydroxyl groups is protected with an acetal-type protecting group.

[0031] The photosensitive resin composition having the above configuration has excellent lithography characteristics. In addition, when using the photosensitive resin composition having the above configuration, microlenses with excellent chemical resistance can be formed by a heat flow method.

[0032] In addition, the photosensitive resin composition is configured such that the cured product can provide a refractive index of 1.50 or more at a wavelength of 550 nm. By using such a photosensitive resin composition, microlenses with high light condensing efficiency can be formed.

[0033] The refractive index of the cured product largely depends on the type of the crosslinking agent (C). Therefore, by using a crosslinking agent (C) having a structure that contributes to an increase in refractive index, the refractive index of the cured product can be increased.

[0034] In addition, within a range where the lithography characteristics, thermal fluidity, crosslinking reactivity, etc. of the photosensitive resin composition are not significantly impaired, various high refractive index materials can also be incorporated into the photosensitive resin composition to increase the refractive index of the cured product.

[0035] <Polyhydroxystyrene Resin (A)>

[0036] The photosensitive resin composition contains a polyhydroxystyrene resin (A). In the polyhydroxystyrene resin (A), a part of the phenolic hydroxyl groups is protected with an acetal-type protecting group.

[0037] Due to the action of the acid generated by the photoacid generator (B) upon exposure, such a polyhydroxystyrene resin (A) is deprotected well and becomes soluble in an alkaline developer. Therefore, if a photosensitive resin composition containing the above polyhydroxystyrene resin (A) is used and a patterned resin film is formed by a lithography method including alkali development, it is easy to obtain a resin film patterned into a desired shape.

[0038] As a preferred example of the polyhydroxystyrene resin (A), a resin having a structural unit represented by the following formula (a1) and a structural unit represented by the following formula (a2) can be cited. Hereinafter, the structural unit represented by the formula (a1) will also be referred to as "structural unit (a1)". The structural unit represented by the formula (a2) will also be referred to as "structural unit (a2)".

[0039] [Chemical formula 1]

[0040]

[0041] (In the formula (a1), R a1 is a hydrogen atom, an alkyl group, a halogen atom, or a haloalkyl group. R a2 is a hydrogen atom or an alkyl group. p is an integer of 1 or more and 5 or less. q is an integer of 0 or more and 4 or less.)

[0042] [Chemical formula 2]

[0043]

[0044] (In the formula (a2), R a3 is a hydrogen atom, an alkyl group, a halogen atom, or a haloalkyl 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 or more and 5 or less. s and t are each independently an integer of 0 or more and 4 or less.)

[0045] In the formula (a1) and the formula (a2), R a1 and R a3 are a hydrogen atom, an alkyl group, a halogen atom, or a haloalkyl group.

[0046] As for the number of carbon atoms of the alkyl group of R a1 and R a3 , as long as the desired effect is not impaired, there is no particular limitation. As for R a1 and R a3The number of carbon atoms of the alkyl group is preferably 1 or more and 5 or less. As R a1 and R a3 The alkyl group may be linear or branched. Regarding the alkyl group as R a1 and R a3 Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl. Industrially, methyl is preferred.

[0047] Regarding the specific examples of the halogen atom in the halogen atom or haloalkyl group as R a1 and R a3 include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Among them, a fluorine atom is preferred. As the haloalkyl group, it is preferably a group obtained by substituting part or all of the hydrogen atoms in the above-mentioned alkyl group having 1 or more and 5 or less carbon atoms with halogen atoms. The haloalkyl group may be linear or branched. Specific preferred examples of the haloalkyl group include fluoroalkyl groups such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, and nonafluorobutyl.

[0048] As R a1 and R a3 , hydrogen atom and methyl are preferred, and hydrogen atom is more preferred.

[0049] The number of carbon atoms of the alkyl group as R a2 and R a4 is preferably 1 or more and 5 or less. The preferred examples of the alkyl group as R a2 and R a4 are the same as the preferred examples of the alkyl group as R a1 and R a3 .

[0050] q, s, and t are each independently an integer of 0 or more and 4 or less. Among them, q, s, and t are preferably 0 or 1, and particularly preferably 0 industrially.

[0051] In formula (a1), when q is 1, the substitution position of R a2 can be any position among ortho, meta, and para with respect to the carbon atom on the benzene ring in formula (a1) that is bonded to the carbon atom bonded to the same R a1 .

[0052] When q is an integer of 2 or more and 4 or less, R a2 can be bonded to any position on the benzene ring in formula (a1).

[0053] In formula (a2), when t is 1, the substitution position of R a4 can be any position among ortho, meta, and para with respect to the carbon atom on the benzene ring in formula (a2) that is bonded to the carbon atom bonded to the same R a3For the position of the carbon atom to which the bonded carbon atom is bonded, it can be any of ortho, meta, and para positions.

[0054] When t is an integer of 2 or more and 4 or less, R a4 can be bonded to any position on the benzene ring in formula (a2).

[0055] In formula (a1), 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.

[0056] In formula (a2), 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.

[0057] When p is 1 or s is 1, the substitution position of the hydroxyl group in formula (a1) and formula (a2) can be any of ortho, meta, and para positions with respect to the position of the carbon atom bonded to the carbon atom to which R a1 or R a3 is bonded on the benzene ring in formula (a1) or formula (a2). From the aspect of being able to easily obtain the monomer providing the structural unit represented by formula (a1) or formula (a2) and having a low price, the para position is preferred.

[0058] When p is an integer of 2 or more and 5 or less in formula (a1), or s is an integer of 2 or more and 4 or less in formula (a2), the hydroxyl group can be bonded to any position on the benzene ring in formula (a1) and formula (a2).

[0059] In formula (a2), 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.

[0060] When r is 1, the substitution position of the group represented by -C(R a5 )(R a6 )OR a7 can be any of ortho, meta, and para positions with respect to the position of the carbon atom bonded to the carbon atom to which the same R a3 is bonded on the benzene ring in formula (a2).

[0061] In formula (a2), when r is an integer of 2 or more and 5 or less, -C(R a5 )(R a6 )OR a7 the group represented by can be bonded to any position on the benzene ring in formula (a2).

[0062] In the acetal-type protecting group represented by -C(R a5 )(R a6 )OR a7 in formula (a2), R a5 and Ra6 Each independently represents a hydrogen atom or an alkyl group. R a7 represents an alkyl group or a cycloalkyl group. R a5 , R a6 and R a7 Among them, at least two can bond to each other to form a ring.

[0063] As R a5 or R a6 , the number of carbon atoms of the alkyl group is preferably 1 or more and 6 or less. As R a5 or R a6 , the alkyl group can be linear or branched.

[0064] As R a7 , the number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less. As R a7 , the alkyl group can be linear or branched.

[0065] As R a7 , the number of carbon atoms of the cycloalkyl group is preferably 3 or more and 10 or less, for example.

[0066] Regarding specific examples of the alkyl group as Ra 5 , R a6 or R a7 , examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl.

[0067] Regarding specific examples of the cycloalkyl group as R a7 , examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyl, and cyclooctyl.

[0068] As the specific examples of the acetal-type protecting group represented by -C(R a5 )(R a6 )OR a7 in the formula (a2), examples include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-methoxy-1-methyl-ethyl, and 1-ethoxy-1-methyl-ethyl.

[0069] The polyhydroxystyrene resin (A) may contain one or two or more structural units (a1). The polyhydroxystyrene resin (A) may contain one or two or more structural units (a2).

[0070] The total of the ratio of the structural unit (a1) and the ratio of the structural unit (a2) in the polyhydroxystyrene resin (A) is preferably 50 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, still 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%, relative to the total number of moles of all the structural units constituting the polyhydroxystyrene resin (A).

[0071] The proportion of the number of moles of the structural unit (a2) is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 40 mol% or less, relative to the total of the number of moles of the structural unit (a1) and the number of moles of the structural unit (a2). This ratio is the protection rate of the hydroxyl group derived from hydroxystyrene. When the protection rate is within the above range, a photosensitive resin composition with particularly good patterning properties can be easily obtained.

[0072] The proportion of the number of moles of the structural unit (a2) is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 40 mol% or less, relative to the total number of moles of all the structural units constituting the polyhydroxystyrene resin (A).

[0073] The polyhydroxystyrene resin (A) may contain other structural units (a3) in addition to the structural unit (a1) and the structural unit (a2).

[0074] Examples of the other monomers that provide the other structural units (a3) include (meth)acrylates, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and maleimides. These compounds can be used alone or in combination of two or more.

[0075] Examples of the (meth)acrylate include linear or branched (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, pentyl (meth)acrylate, and tert-octyl (meth)acrylate; 2-chloroethyl (meth)acrylate, 2,2-dimethyl-3-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, and furfuryl (meth)acrylate; glycidyl (meth)acrylate; and (meth)acrylates containing a group having an alicyclic skeleton.

[0076] In the (meth)acrylate containing a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be a monocyclic or polycyclic group. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. In addition, examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc.

[0077] Examples of the (meth)acrylamide include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide, etc.

[0078] Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.; allyloxyethanol; and so on.

[0079] Examples of the vinyl ether include aliphatic vinyl ethers such as 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-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether, etc.; and so on.

[0080] Examples of the vinyl ester include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.

[0081] Examples of styrenes include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and so on.

[0082] Examples of maleimides include maleimides obtained by N-substitution with an alkyl group having 1 to 10 carbon atoms such as N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-n-pentylmaleimide, and N-n-hexylmaleimide; maleimides obtained by N-substitution with an alicyclic group having 3 to 20 carbon atoms such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, and N-cycloheptylmaleimide; N-arylmaleimides obtained by N-substitution with an aryl group having 6 to 20 carbon atoms such as N-phenylmaleimide, N-α-naphthylmaleimide, and N-β-naphthylmaleimide; and N-arylalkylmaleimides obtained by N-substitution with an arylalkyl group having 7 to 20 carbon atoms such as N-benzylmaleimide and N-phenethylmaleimide.

[0083] The weight average molecular weight (Mw) of the polyhydroxystyrene resin (A) is preferably 5000 or more and 30000 or less. It should be noted that in this specification, the weight average molecular weight is the weight average molecular weight in terms of polystyrene based on gel permeation chromatography (GPC).

[0084] <Photoacid generator (B)>

[0085] The photosensitive resin composition contains a photoacid generator (B) that generates an acid upon irradiation with actinic light or radiation. Due to the action of the acid generated by the photoacid generator (B) upon exposure, the polyhydroxystyrene resin (A) undergoes deprotection and becomes soluble in an alkaline developer, and thus, it can be suitably applied to patterning the photosensitive resin composition by lithography.

[0086] In addition, after forming a plurality of points by a heat flow method including a lithography process and before modifying the plurality of points with heat to form microlenses, the plurality of points are exposed, whereby microlenses having excellent chemical resistance can be formed.

[0087] The reason is that acid is generated at the dots by exposure. By deforming the dots containing the acid using heat, the crosslinking of the polyhydroxystyrene resin (A) based on the crosslinking agent (C) proceeds well, and a microlens can be formed.

[0088] As the photoacid generator (B), there is no particular limitation, and the photoacid generators previously incorporated in the photosensitive resin composition can be used without particular limitation.

[0089] Examples of the photoacid generator (B) include onium salt type photoacid generators such as iodonium salts and sulfonium salts; sulfonate type photoacid generators such as oxime sulfonate type photoacid generators and imide sulfonate type photoacid generators; diazomethane type photoacid generators; disulfone type photoacid generators, etc.

[0090] Among them, from the viewpoint of easily obtaining a photosensitive resin composition having excellent lithography characteristics, sulfonate type photoacid generators and onium salt type photoacid generators are preferred.

[0091] That is, the photoacid generator (B) preferably contains a sulfonate type photoacid generator (B1) and / or an onium salt type photoacid generator (B2).

[0092] Hereinafter, the sulfonate type photoacid generator (B1) and the onium salt type photoacid generator (B2) will be described.

[0093] 〔Sulfonate type photoacid generator (B1)〕

[0094] The sulfonate type photoacid generator (B1) may be any compound having a sulfonate structure represented by -O-SO 2 -, and there is no particular limitation.

[0095] As the sulfonate type photoacid generator (B1), for example, a compound represented by the following formula (b0-1) is preferably used.

[0096] [Chemical formula 3]

[0097]

[0098] In formula (b0-1), Rb 1 is an organic group. Rb 2 is a group represented by the following formula (b0-r-1) or the following formula (b0-r-2).

[0099] [Chemical formula 4]

[0100]

[0101] In formula (b0-r-1), Rb 201 and Rb 202 are each independently an organic group. * represents a bonding site.

[0102] In formula (b0-r-2), Xb is a group that, together with -(O=)C-N-C(=O)-, forms a cyclic group having a cyclic imide structure. * represents a linking bond.]

[0103] As a preferred example of the compound represented by formula (b0-1), compounds represented by any of the following formulas (b0-1-1) to (b0-1-6) can be cited, etc.

[0104] As the sulfonate-type photoacid generator (B1), an oxime sulfonate-type photoacid generator (B1-1) and an imide sulfonate-type photoacid generator (B1-2) are preferred.

[0105] The compound represented by any of the following formulas (b0-1-1) to (b0-1-6) is an oxime sulfonate compound having a structure represented by >C=N-O-SO 2 -, or an imide sulfonate compound having a structure represented by >N-O-SO 2 -. The nitrogen atom in the structure represented by >N-O-SO 2 - forms a dicarboximide ring.

[0106] [Chemical formula 5]

[0107]

[0108] In formula (b0-1-1), Rb 11 and Rb 21 are each independently an aliphatic group.

[0109] [Chemical formula 6]

[0110]

[0111] In formula (b0-1-2), Rb 12 is an alkyl or haloalkyl group. Rb 22 is an aromatic group.

[0112] [Chemical formula 7]

[0113]

[0114] In formula (b0-1-3), Rb 13 is a hydrocarbon group that may have a substituent, or a heterocyclic group that may have a substituent. nb3 is 2 or 3. Ab is a divalent or trivalent organic group.

[0115] [Chemical formula 8]

[0116]

[0117] In formula (b0-1-4), Rb14 is a polycyclic aromatic hydrocarbon group which may have substituents, or a polycyclic aliphatic hydrocarbon group which may have substituents and may have unsaturated bonds. Rb 24 is an inactive organic group.

[0118] [Chemical Formula 9]

[0119]

[0120] In formula (b0-1-5), Rb 15 is a monovalent aliphatic hydrocarbon group which may have substituents and may have unsaturated bonds, or an aromatic group which may have substituents. Xb 5 is a group which, together with -(O=)C-N-C(=O)-, forms a cyclic group having a cyclic imide structure.

[0121] [Chemical Formula 10]

[0122]

[0123] In formula (b0-1-6), Rb 16 is an alkyl group which may have substituents, a cycloalkyl group which may have substituents, or an aromatic hydrocarbon group which may have substituents. Rb 261 ~Rb 263 are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. nb6 is an integer of 0 or more and 5 or less.

[0124] In formula (b0-1-1), regarding the aliphatic groups as Rb 11 and Rb 21 , examples thereof include an alkyl group, a haloalkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a cycloalkoxy group, and an adamantyl group.

[0125] Regarding the alkyl groups as Rb 11 and Rb 21 , a linear or branched alkyl group having 1 to 12 carbon atoms is preferred. Specific examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-octyl group, and a n-dodecyl group.

[0126] Regarding the number of halogen atoms in the haloalkyl group as Rb 11 and Rb 21 , there is no particular limitation. The number of halogen atoms may be 1, or may be 2 or more.

[0127] As the halogen atom, any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom may be used.

[0128] As the haloalkyl group, a haloalkyl group having 1 or more and 4 or less carbon atoms is preferred. Specific examples of the haloalkyl group having 1 or more and 4 or less carbon atoms include chloromethyl, trichloromethyl, trifluoromethyl, 2-bromopropyl, and the like.

[0129] Regarding Rb as 11 and Rb 21 the alkenyl group, a linear or branched alkenyl group having 2 or more and 6 or less carbon atoms is preferred. As the alkenyl group having 2 or more and 6 or less carbon atoms, vinyl, 1-propenyl, isopropenyl, 2-butenyl, and the like are preferred.

[0130] Regarding Rb as 11 and Rb 21 the cycloalkyl group, a cycloalkyl group having 5 or more and 12 or less carbon atoms is preferred. As the cycloalkyl group having 5 or more and 12 or less carbon atoms, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, and the like are preferred.

[0131] Regarding Rb as 11 and Rb 21 the cycloalkenyl group, a cycloalkenyl group having 4 or more and 8 or less carbon atoms is preferred. As the cycloalkenyl group having 4 or more and 8 or less carbon atoms, 1-cyclobutenyl, 1-cyclopentenyl, 1-cyclohexenyl, 1-cycloheptenyl, 1-cyclooctenyl, and the like are preferred.

[0132] Regarding Rb as 11 and Rb 21 the alkoxy group, an alkoxy group having 1 or more and 8 or less carbon atoms is preferred. As the alkoxy group having 1 or more and 8 or less carbon atoms, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, and the like are preferred.

[0133] Regarding Rb as 11 and Rb 21 the cycloalkoxy group, a cycloalkoxy group having 5 or more and 8 or less carbon atoms is preferred. As the cycloalkoxy group having 5 or more and 8 or less carbon atoms, cyclopentyloxy, cyclohexyloxy, and the like are preferred.

[0134] As Rb in the formula (b0-1-1) 11 , an alkyl group, a haloalkyl group, and a cycloalkyl group are preferred, and an alkyl group is more preferred.

[0135] As Rb 21 , an alkyl group, a cycloalkyl group, and a cycloalkenyl group are preferred, and a cycloalkenyl group is more preferred.

[0136] In the formula (b0-1-1), particularly preferably, Rb 11 is an alkyl group having 1 or more and 4 or less carbon atoms, and Rb 21 is cyclopentenyl.

[0137] As specific examples of the compound represented by the formula (b0-1-1), α-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclooctenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-cyclohexylacetonitrile, α-(ethylsulfonyloxyimino)-ethylacetonitrile, α-(propylsulfonyloxyimino)-propylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, and α-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile, etc. can be mentioned.

[0138] Regarding Rb in the formula (b0-1-2) 12 as the alkyl group, a linear or branched alkyl group having 1 to 4 carbon atoms can be mentioned. As specific examples of the alkyl group having 1 to 4 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, etc. can be mentioned.

[0139] Regarding Rb 12 as the haloalkyl group, a haloalkyl group having 1 to 4 carbon atoms can be mentioned. As specific examples of the haloalkyl group having 1 to 4 carbon atoms, chloromethyl, trichloromethyl, trifluoromethyl, and 2-bromopropyl, etc. can be mentioned.

[0140] In the formula (b0-1-2), as Rb 22 the aromatic group is a group that exhibits the physical and chemical properties peculiar to aromatic compounds. As specific examples of the aromatic group, phenyl, naphthyl, furyl, and thienyl, etc. can be mentioned.

[0141] As Rb 22 the aromatic group may have one or more substituents. As the substituents, a halogen atom, an alkyl group, an alkoxy group, and a nitro group, etc. can be mentioned.

[0142] As specific examples of the compound represented by the formula (b0-1-2), α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(methylsulfonyloxyimino)-4-methylphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-4-methylphenylacetonitrile, and α-(methylsulfonyloxyimino)-4-bromophenylacetonitrile, etc. can be cited.

[0143] In the formula (b0-1-3), regarding the hydrocarbon group which may have a substituent as Rb 13 an aromatic hydrocarbon group which may have a substituent and an aliphatic hydrocarbon group which may have a substituent can be cited.

[0144] As the aromatic group, a hydrocarbon group having 6 to 14 carbon atoms is preferred.

[0145] As specific examples of the aromatic hydrocarbon group which may have a substituent, phenyl, tolyl, methoxyphenyl, xylyl, biphenyl, naphthyl, anthryl, etc. can be cited.

[0146] Regarding Rb 13 the aliphatic hydrocarbon group may be a chain aliphatic hydrocarbon group or an alicyclic hydrocarbon group. As the aliphatic hydrocarbon group, for example, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, etc. can be cited.

[0147] The alkyl group and the alkenyl group may be linear or branched. The number of carbon atoms of the alkyl group and the alkenyl group is preferably 1 to 12.

[0148] The number of carbon atoms of the cycloalkyl group and the cycloalkenyl group is preferably 4 to 12.

[0149] As specific examples of the alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-octyl, n-dodecyl, etc. can be cited.

[0150] As specific examples of the alkenyl group, vinyl, propenyl, butenyl, hexenyl, etc. can be cited.

[0151] Respectively, as examples of the cycloalkyl group, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl can be cited, and as examples of the cycloalkenyl group, 1-cyclobutenyl, 1-cyclopentenyl, 1-cyclohexenyl, 1-cycloheptenyl, 1-cyclooctenyl, etc. can be cited.

[0152] Regarding Rb 13The heterocyclic group can be an aromatic heterocyclic group or an aliphatic heterocyclic group. As the heterocyclic group, an aromatic heterocyclic group is preferred. Specific examples of the aromatic heterocyclic group include a furyl group, a pyridyl group, a quinolinyl group, and the like.

[0153] As Rb in formula (b0-1-3) 13 The hydrocarbon group and the heterocyclic group may have substituents. Examples of the substituents include a halogen atom, a hydroxyl group, an alkoxy group, an acyl group, and the like.

[0154] Regarding the divalent or trivalent organic group as Ab in formula (b0-1-3), examples include a divalent or trivalent aliphatic hydrocarbon group and a divalent or trivalent aromatic hydrocarbon group.

[0155] Specific examples of the compound represented by formula (b0-1-3) are shown below.

[0156] [Chemical formula 11]

[0157]

[0158] [Chemical formula 12]

[0159]

[0160] Regarding Rb in formula (b0-1-4) 14 Examples of the polycyclic aromatic hydrocarbon group include fused polycyclic aromatic hydrocarbon groups such as 2-indanyl, 1-naphthyl, 2-naphthyl, and 2-anthryl; non-fused polycyclic aromatic hydrocarbon groups such as biphenyl and terphenyl.

[0161] The polycyclic aromatic hydrocarbon group may have substituents such as halogen atoms such as a chlorine atom, a bromine atom, and an iodine atom, a nitro group, an amino group, a hydroxyl group, an alkyl group, and an alkoxy group.

[0162] Specific examples of the polycyclic aromatic hydrocarbon group having a substituent include 5-hydroxynaphthalen-1-yl and 4-aminonaphthalen-1-yl.

[0163] Regarding Rb in formula (b0-1-4) 14 Examples of the polycyclic aliphatic hydrocarbon group having an unsaturated bond include a polycyclic terpene residue and an adamantyl group. As the polycyclic aliphatic hydrocarbon group, a polycyclic terpene residue is preferred.

[0164] The polycyclic aliphatic hydrocarbon group may have substituents such as halogen atoms such as a chlorine atom, a bromine atom, and an iodine atom, a nitro group, an amino group, a hydroxyl group, an alkyl group, and an alkoxy group.

[0165] As Rb 14In the polycyclic aliphatic hydrocarbon group, one or more methylene groups constituting the polycyclic aliphatic hydrocarbon group may be replaced with a carbonyl group (>C=O). However, in the polycyclic aliphatic hydrocarbon group, not all methylene groups will be replaced with carbonyl groups.

[0166] Regarding Rb 14 Preferred examples of the polycyclic aliphatic hydrocarbon group include camphor-3-yl, camphor-8-yl, camphor-10-yl, 3-bromocamphor-10-yl, and the like.

[0167] Among the groups described above, as Rb 14 , naphthyl and camphor-10-yl are preferred, and 1-naphthyl is particularly preferred in terms of the excellent resolution of the photosensitive resin composition.

[0168] In formula (b0-1-4), the inactive organic group as Rb 24 may be any organic group that is inactive with respect to coexisting components under the use conditions and is not particularly limited.

[0169] As the inactive organic group, an aromatic group is preferred in terms of sensitivity to excimer laser, electron beam, and X-ray. Examples of the aromatic group include phenyl, naphthyl, furyl, and thienyl.

[0170] The aromatic group may have halogen atoms such as chlorine atom, bromine atom, and iodine atom, and inactive substituents such as alkyl group, alkoxy group, and nitro group.

[0171] Specific examples of the compound represented by formula (b0-1-4) include α-(1-naphthylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(2-naphthylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(1-naphthylsulfonyloxyimino)benzyl cyanide, α-(2-naphthylsulfonyloxyimino)benzyl cyanide, α-(10-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(10-camphorsulfonyloxyimino)benzyl cyanide, α-(3-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide, and α-(3-bromo-10-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide.

[0172] As Rb in formula (b0-1-5) 15 The monovalent aliphatic hydrocarbon group which may have a substituent and may have an unsaturated bond preferably has 1 to 8 carbon atoms. It should be noted that the carbon atoms in the number of carbon atoms do not include the carbon atoms of the substituent.

[0173] The structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures.

[0174] Examples of the substituent include a halogen atom, nitro group, acetylamino group, alkoxy group, phenyl group, etc. Among these substituents, a halogen atom and an alkoxy group are preferred.

[0175] Regarding the aromatic group which may have a substituent as Rb 15 Examples include a monocyclic aromatic group and a bicyclic aromatic group. As the aromatic group, a phenyl group substituted with one or more groups selected from a vinyl group, alkyl group, alkoxy group, halogen atom, etc. is preferred.

[0176] In formula (b0-1-5), as Xb 5 Examples of the ring having a cyclic imide structure formed with -(O=)C-N-C(=O)- include a succinimide ring, maleimide ring, glutarimide ring, phthalimide ring, naphthalimide ring, etc.

[0177] Xb 5 The ring having a cyclic imide structure formed with -(O=)C-N-C(=O)- may have a substituent. Examples of the substituent include a halogen atom, nitro group, acetylamino group, alkoxy group, phenyl group, etc.

[0178] Specific examples of the compound represented by formula (b0-1-5) include N-methylsulfonyloxysuccinimide, N-isopropylsulfonyloxysuccinimide, N-chloroethylsulfonyloxysuccinimide, N-(p-methoxyphenyl)sulfonyloxysuccinimide, N-(p-vinylphenyl)sulfonyloxysuccinimide, N-naphthylsulfonyloxysuccinimide, N-phenylsulfonyloxysuccinimide, N-(2,4,6-trimethylphenyl)sulfonyloxysuccinimide, N-methylsulfonyloxymaleimide, N-isopropylsulfonyloxymaleimide, N-chloroethylsulfonyloxymaleimide, N-(p-methoxyphenyl)sulfonyloxymaleimide, N-(p-vinylphenyl)sulfonyloxymaleimide, N-naphthylsulfonyloxymaleimide, N-phenylsulfonyloxymaleimide, N-(2,4,6-trimethylphenyl)sulfonyloxymaleimide, N-methylsulfonyloxyphthalimide, N-isopropylsulfonyloxyphthalimide, N-chloroethylsulfonyloxyphthalimide, N-(p-methoxyphenyl)sulfonyloxyphthalimide, N-(p-vinylphenyl)sulfonyloxyphthalimide, N-naphthylsulfonyloxyphthalimide, N-phenylsulfonyloxyphthalimide, N-(2,4,6-trimethylphenyl)sulfonyloxyphthalimide, and the compounds described in paragraphs

[0089] -

[0091] of Japanese Patent Laid-Open No. 10-097075, etc.

[0179] In formula (b0-1-6), regarding the Rb16 The alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and still more preferably a linear or branched alkyl group having 1 to 5 carbon atoms.

[0180] Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl.

[0181] In formula (b0-1-6), regarding Rb 16 The cycloalkyl group is preferably a cycloalkyl group having 3 to 18 carbon atoms.

[0182] Regarding Rb 16 The cycloalkyl group includes cyclopentyl, cyclohexyl, cyclooctyl, and cyclododecyl.

[0183] As Rb 16 The alkyl group and the cycloalkyl group may have substituents. Examples of the substituents include halogen atoms, haloalkyl groups, cyano groups, nitro groups, phenyl groups, alkoxy groups, carboxyl groups, sulfonyl groups, and amino groups.

[0184] As Rb 16 In the alkyl group or cycloalkyl group of Rb, one or more methylene groups constituting the alkyl group or cycloalkyl group may be replaced by a carbonyl group (>C=O). However, in the alkyl group or cycloalkyl group, not all methylene groups will be replaced by a carbonyl group.

[0185] In formula (b0-1-6), regarding Rb 16 The aromatic group includes phenyl, naphthyl, phenanthryl, anthryl, and heteroaryl groups.

[0186] As Rb 16 The aromatic group may have substituents. Examples of the substituents include halogen atoms, haloalkyl groups, cyano groups, nitro groups, phenyl groups, alkoxy groups, carboxyl groups, sulfonyl groups, and amino groups.

[0187] Specific examples of the compound represented by formula (b0-1-6) include the compound represented by the following formula (b0-1-61), the compounds of Examples 25 to 40 and 53 of Japanese Patent Application Laid-Open No. 2002-508774, and the like.

[0188] [Chemical formula 13]

[0189]

[0190] As other specific examples of the sulfonate-type photoacid generator (B1) other than the sulfonate-type photoacid generator (B1) described above, compounds described in paragraphs

[0056] ,

[0058] ,

[0060] and

[0063] of Japanese Patent No. 4110392, compounds described in paragraphs

[0053] ,

[0054] ,

[0056] ,

[0058] and

[0060] -

[0062] of Japanese Patent No. 4000469, etc. can be cited.

[0191] Among the sulfonate-type photoacid generators (B1) described above, at least one selected from the group consisting of the compound represented by formula (b0-1-2), the compound represented by formula (b0-1-3), the compound represented by formula (b0-1-5) and the compound represented by formula (b0-1-6) is preferred, and at least one selected from the group consisting of the compound represented by formula (b0-1-2), the compound represented by formula (b0-1-3) and the compound represented by formula (b0-1-6) is more preferred.

[0192] As the sulfonate-type photoacid generator (B1), the compounds represented by the following formulas (B0-1) to (B0-3) are particularly preferred.

[0193] [Chemical formula 14]

[0194]

[0195] [Onium salt-type photoacid generator (B2)]

[0196] As the onium salt-type photoacid generator (B2), conventionally known onium salt-type photoacid generators such as iodonium salts and sulfonium salts can be used without particular limitation.

[0197] As the onium salt-type photoacid generator (B2), onium salts having a naphthalene ring in the cationic part can be cited. The "having a naphthalene ring" means having a structure derived from naphthalene, indicating a structure of at least two rings and maintaining their aromaticity. The naphthalene ring may have substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (with one free valence), or a divalent group (with two or more free valences) or more, but a monovalent group is desired (wherein, in this case, the part bonded to the above substituents is excluded when counting the free valences). The number of naphthalene rings is preferably 1 to 3.

[0198] As the cationic part of such an onium salt having a naphthalene ring in the cationic part, the structure represented by the following formula (b1) is preferred.

[0199] [Chemical formula 15]

[0200]

[0201] In the above formula (b1), at least one of R 1b , R 2b , R 3b represents a group represented by the following formula (b2), and the rest represent a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group which may have a substituent, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R 1b , R 2b , R 3b is a group represented by the following formula (b2), and the remaining two are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and their ends may be bonded to form a ring.

[0202] Regarding specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms as R 1b , R 2b , R 3b , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl can be cited.

[0203] Regarding specific examples of the linear or branched alkoxy group having 1 to 6 carbon atoms as R 1b , R 2b , R 3b , methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, and n-hexyloxy can be cited.

[0204] When R 1b , R 2b , R 3b is a phenyl group which may have a substituent, preferred substituents include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

[0205] [Chemical formula 16]

[0206]

[0207] In the above formula (b2), R 4b , R 5b each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R 6brepresents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have substituents. l and m each independently represent an integer of 0 or more and 2 or less, and l + m is 3 or less. Among them, R 4b When there are a plurality of them, they may be the same as or different from each other. Further, R 5b When there are a plurality of them, they may be the same as or different from each other.

[0208] Regarding the linear or branched alkoxy group having 1 to 6 carbon atoms as R 4b and R 5b Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, and n-hexyloxy.

[0209] Regarding the linear or branched alkyl group having 1 to 6 carbon atoms as R 4b and R 5b Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0210] Regarding the linear or branched alkylene group having 1 to 6 carbon atoms as R 6b Specific examples include methylene, ethane-1,2-diyl (ethylene), ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, propane-2,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0211] From the viewpoint of the stability of the compound, the number of the groups represented by the above formula (b2) in the above R 1b 、R 2b 、R 3b is preferably 1, and the rest are linear or branched alkylene groups having 1 to 6 carbon atoms, and their ends may be bonded to form a ring. In this case, the above two alkylene groups contain a sulfur atom to form a 3- to 9-membered ring. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

[0212] In addition, examples of the substituent that the above alkylene group may have include an oxygen atom (in this case, forming a carbonyl group together with the carbon atom constituting the alkylene group), a hydroxyl group, and the like.

[0213] In addition, examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

[0214] Regarding the preferred structures for these cationic moieties, structures represented by the following formulas (b3), (b4-1), and (b4-2) can be mentioned, etc., and structures represented by the following formulas (b4-1) and (b4-2) are particularly preferred.

[0215] [Chemical formula 17]

[0216]

[0217] As such a cationic moiety, it can be an iodonium salt or a sulfonium salt, but considering aspects such as acid generation efficiency, a sulfonium salt is desired.

[0218] Therefore, regarding the anions preferred as the anionic moiety of the sulfonium salt having a naphthalene ring in the cationic moiety, anions capable of forming a sulfonium salt are desired.

[0219] As the anionic moiety of such an acid generator, it is a fluoroalkylsulfonate ion or an arylsulfonate ion in which some or all of the hydrogen atoms are fluorinated.

[0220] The alkyl group in the fluoroalkylsulfonate ion can be linear, branched, or cyclic with 1 to 20 carbon atoms. Considering the large volume of the generated acid and its diffusion distance, it is preferably 1 to 10 carbon atoms. In particular, when it is a branched or cyclic alkyl group, the diffusion distance is short, so it is preferred. In addition, considering the aspect of being able to be synthesized inexpensively, preferred examples include methyl, ethyl, propyl, butyl, octyl, etc.

[0221] The aryl group in the arylsulfonate ion is an aryl group with 6 to 20 carbon atoms, and examples include phenyl and naphthyl that can be substituted or unsubstituted by an alkyl group or a halogen atom. In particular, considering the aspect of being able to be synthesized inexpensively, it is preferably an aryl group with 6 to 10 carbon atoms. Specific examples of the preferred aryl group include phenyl, toluenesulfonyl, ethylphenyl, naphthyl, methylnaphthyl, etc.

[0222] In the above fluoroalkylsulfonate ion or arylsulfonate ion, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100% or less. In particular, the product obtained by substituting all hydrogen atoms with fluorine atoms has a stronger acid strength, so it is preferred. As such substances, specifically, trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, etc. can be mentioned.

[0223] Among them, as the preferred anionic moiety, the anionic moiety represented by the following formula (b5) can be mentioned.

[0224] [Chemical formula 18]

[0225] R7b SO 3 (b5)

[0226] In the above formula (b5), R 7b represents a group represented by the following formulas (a10), (a11) and (a12).

[0227] [Chemical formula 19]

[0228]

[0229] In the above formula (b6), x represents an integer of 1 or more and 4 or less. Further, in the above formula (b7), R 8b represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 or more and 6 or less carbon atoms, or a linear or branched alkoxy group having 1 or more and 6 or less carbon atoms, and y represents an integer of 1 or more and 3 or less. Among them, from the viewpoint of safety, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred.

[0230] Further, as the anionic part, a nitrogen-containing anionic part represented by the following formulas (b9) and (b10) can also be used.

[0231] [Chemical formula 20]

[0232]

[0233] In the above formulas (b9) and (b10), X b represents a linear or branched alkylene group in which at least one hydrogen atom is substituted by a fluorine atom, the alkylene group having 2 or more and 6 or less carbon atoms, preferably 3 or more and 5 or less carbon atoms, and most preferably 3 carbon atoms. Further, Y b , Z b each independently represents a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, the alkyl group having 1 or more and 10 or less carbon atoms, preferably 1 or more and 7 or less carbon atoms, and more preferably 1 or more and 3 or less carbon atoms.

[0234] X b The smaller the number of carbon atoms of the alkylene group or Y a , Z a the alkyl group, the better the solubility in the organic solvent, and thus it is preferred.

[0235] Further, the alkylene group of X b or Y b , Z bIn the alkyl group, the more hydrogen atoms are substituted by fluorine atoms, the stronger the acid strength, so it is preferred. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate, is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably a perfluoroalkylene group or perfluoroalkyl group obtained by substituting all hydrogen atoms with fluorine atoms.

[0236] Regarding the compounds preferably used as such onium salts having a naphthalene ring in the cationic part, the compounds represented by the following formulas (b11-1), (b11-2), and (b12) can be mentioned.

[0237] [Chemical formula 21]

[0238]

[0239] In the photosensitive resin composition, the photoacid generator (B) can be used alone as one kind, or two or more kinds can be used in combination.

[0240] Based on 100 parts by mass of the polyhydroxystyrene resin (A), 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 or less, and more preferably 2 parts by mass or more and 10 parts by mass or less.

[0241] When the content of the photoacid generator (B) is within the above range, it is easy to obtain a photosensitive resin composition with particularly good lithography characteristics.

[0242] <Crosslinking agent (C)>

[0243] The photosensitive resin composition contains a crosslinking agent (C). The crosslinking agent (C) may be any compound that can crosslink the molecular chains of the polyhydroxystyrene resin (A) by reacting with the polyhydroxystyrene resin (A), and is not particularly limited.

[0244] Typically, the crosslinking agent (C) is a compound having two or more crosslinkable groups. As the crosslinkable groups, hydroxymethyl, alkoxymethyl, acyloxymethyl, epoxy group, and oxetanyl are preferred.

[0245] From the aspect of the high refractive index of the cured product formed using the photosensitive resin composition, the crosslinking agent (C) preferably contains a heterocyclic compound having a crosslinkable group. As the heteroatoms contained in the heterocycle of the heterocyclic compound, oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, etc. can be mentioned. Among these heteroatoms, from the aspect of the high refractive index of the cured product, nitrogen atom is preferred.

[0246] That is, the heterocyclic compound as the crosslinking agent (C) is preferably a nitrogen-containing heterocyclic compound.

[0247] From the viewpoint of the refractive index of the cured product, the nitrogen-containing heterocyclic compound as the crosslinking agent (C) preferably has a 1,3,5-triazine-2,4,6-triyl or 1,3,5-triazine-2,4,6-trione-1,3,5-triyl, and more preferably has a 1,3,5-triazine-2,4,6-trione-1,3,5-triyl.

[0248] From the viewpoints of crosslinking reactivity and ease of obtaining, preferred crosslinking agents (C) include hydroxymethyl type crosslinking agents (C1) and polyfunctional epoxy compounds (C2).

[0249] Hereinafter, the hydroxymethyl type crosslinking agent (C1) and the polyfunctional epoxy compound (C2) will be described.

[0250] 〔Hydroxymethyl type crosslinking agent (C1)〕

[0251] The hydroxymethyl type crosslinking agent (C1) is a compound having two or more groups selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl in the molecule.

[0252] The alkoxy group in alkoxymethyl and the acyl group in acyloxymethyl may be substituted by a halogen atom. The hydroxymethyl type crosslinking agent (C1) is preferably a compound having two or more groups selected from hydroxymethyl and alkoxymethyl.

[0253] When the photosensitive resin composition contains the hydroxymethyl type crosslinking agent (C1), by heating the photosensitive resin composition, the polyhydroxystyrene resin (A) is crosslinked with the hydroxymethyl type crosslinking agent (C1). As a result, a cured product excellent in chemical resistance can be formed.

[0254] In addition, after patterning the coating film formed from the photosensitive resin composition by exposure and development, the patterned coating film is heated. Thus, the polyhydroxystyrene resin (A) is crosslinked with the hydroxymethyl type crosslinking agent. As a result, a microlens excellent in chemical resistance can be formed.

[0255] From the viewpoint of the chemical resistance of the cured product obtained by heating the photosensitive resin composition, the number of groups selected from hydroxymethyl and alkoxymethyl in one molecule of the hydroxymethyl type crosslinking agent (C) is preferably 2 or more and 10 or less, more preferably 2 or more and 8 or less, and further preferably 2 or more and 4 or less.

[0256] The number of carbon atoms of the alkoxy group in alkoxymethyl is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, further preferably 1 or more and 3 or less, particularly preferably 1 or 2, and most preferably 1. That is, as alkoxymethyl, methoxymethyl is most preferred.

[0257] The alkoxy group in alkoxymethyl can be linear or branched, preferably linear.

[0258] The acyloxy group in acyloxymethyl 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. Regarding the organic group as R, an alkyl group and an aryl group are preferred, and an alkyl group is more preferred. The number of carbon atoms of the organic group as R is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and further preferably 1 or more and 6 or less.

[0259] Preferred examples of the hydroxymethyl type crosslinking agent (C1) include hydroxymethyl melamine compounds, hydroxymethyl guanamine compounds, hydroxymethyl urea compounds, Resol resins, and aromatic compounds having a hydroxymethyl group or an alkoxymethyl group on an aromatic ring.

[0260] Among them, hydroxymethyl melamine compounds, hydroxymethyl guanamine compounds, hydroxymethyl urea compounds, and aromatic compounds having a hydroxymethyl group or an alkoxymethyl group on an aromatic ring are preferred.

[0261] Examples of the aromatic compound having a hydroxymethyl group or an alkoxymethyl group on an aromatic ring include the compounds described in paragraphs

[0136] to

[0139] of Japanese Patent Application Laid-Open No. 2013-064829 and the compounds described in paragraphs

[0029] to

[0036] of Japanese Patent Application Laid-Open No. 10-0120940.

[0262] As the hydroxymethyl type crosslinking agent (C1), a compound having a hydroxymethyl group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom is particularly preferred.

[0263] As the hydroxymethyl type crosslinking agent (C1) having a hydroxymethyl group bonded to a nitrogen atom or an alkoxymethyl group bonded to a nitrogen atom, a hydroxymethyl melamine compound, a hydroxymethyl guanamine compound, and a hydroxymethyl urea compound are preferred, a hydroxymethyl melamine compound and a hydroxymethyl urea compound are more preferred, and a hydroxymethyl melamine compound is further preferred.

[0264] As the hydroxymethyl melamine compound, a compound represented by the following formula (C1) is preferred.

[0265] [Chemical formula 22]

[0266]

[0267] In formula (C1), R c11 ~R c16 are each independently a hydrogen atom or a group represented by -CH 2 -O-R c R cis a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, R c11 ~R c16 at least two of which are groups represented by -CH 2 -O-R c .

[0268] As R c , the alkyl group can be linear or branched, preferably linear. The number of carbon atoms of the alkyl group as R c is 1 to 6, preferably 1 to 4, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

[0269] In formula (C1), the number of groups represented by -CH c11 ~R c16 in R 2 -O-R c is preferably 4 to 6, more preferably 5 or 6, and still more preferably 6.

[0270] As the hydroxymethylguanamine compound, a compound represented by the following formula (C2) is preferred.

[0271] [Chemical formula 23]

[0272]

[0273] In formula (C2), R c21 is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R c22 ~R c25 are each independently a hydrogen atom or a group represented by -CH 2 -O-R c . At least two of R c22 ~R c25 are groups represented by -CH 2 -O-R c .

[0274] As R c21 , the alkyl group can be linear or branched, preferably linear. The number of carbon atoms of the alkyl group as R c21 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

[0275] As R c21 , the number of carbon atoms of the cycloalkyl group is preferably 3 to 10, more preferably 3 to 8, still more preferably 4 to 7, and particularly preferably 5 or 6.

[0276] As R c21The number of carbon atoms of the aryl group is preferably 6 or more and 14 or less, more preferably 6 or more and 10 or less. As the aryl group, phenyl is preferred.

[0277] As R c21 , it is preferably a hydrogen atom, a methyl group or a phenyl group, more preferably a hydrogen atom and a phenyl group, and further preferably a phenyl group.

[0278] In formula (C2), the number of groups represented by R c22 ~R c25 -CH 2 -O-R c is preferably 2 or more and 4 or less, more preferably 3 or 4, and further preferably 4.

[0279] As the hydroxymethylurea compound, a compound represented by the following formula (C3) is preferred.

[0280] [Chemical formula 24]

[0281]

[0282] In formula (C3), 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 bonded to each other to form a ring. On the ring formed by the bonding of R c31 and R c33 , other rings may also be fused. Compounds represented by formula (C3) and containing a ring formed by the bonding of R c31 and R c33 may also be fused with each other.

[0283] As the alkyl group of R c31 or R c33 , it may be linear or branched, and a linear one is preferred. The number of carbon atoms of the alkyl group of R c31 or R c33 is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less, and further preferably 1 or more and 4 or less.

[0284] As the cycloalkyl group of R c31 or R c33 , the number of carbon atoms is preferably 3 or more and 10 or less, more preferably 3 or more and 8 or less, further preferably 4 or more and 7 or less, and particularly preferably 5 or 6.

[0285] In formula (C3), preferably, R c31 and Rc33 are all hydrogen atoms or are bonded to each other to form a ring. In R c31 and R c33 When forming a ring, the compound represented by 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 called a hydroxymethyl glycoluril compound.

[0286] [Chemical formula 25]

[0287]

[0288] In formula (C4), 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.

[0289] In formula (C4), preferably R c41 and R c42 are both methoxymethyl.

[0290] In formula (C4), R c43 and R c44 are preferably monovalent organic groups. There is no particular limitation on the monovalent organic group. As the monovalent organic group, an alkyl group and an alkoxy group are preferred, and an alkoxy group is more preferred. The number of carbon atoms of 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, further preferably 1 or more and 3 or less, particularly preferably 1 or 2, and most preferably 1.

[0291] In formula (C4), L is preferably a single bond. Regarding the divalent linking group as L, an alkylene group is preferred. This alkylene group may be interrupted by an oxygen atom, a carbonyl group or a carboxylic acid ester bond.

[0292] In formula (C5), 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 As the -CH c51 to R c54 of -O-R 2 -O-R c The number of the represented groups is preferably 3 or 4, and more preferably 4.

[0293] As a preferred specific example of the hydroxymethyl type crosslinking agent (C1) described above, the following compounds can be cited.

[0294] [Chemical formula 26]

[0295]

[0296] [Chemical formula 27]

[0297]

[0298] [Chemical formula 28]

[0299]

[0300] As the hydroxymethyl type crosslinking agent (C1), commercially available products can also be used. As specific examples of commercially available products, for example, NIKALAC MX-270, NIKALAC MW-100LM, NIKALAC MX-280, and NIKALAC MX-290 (all manufactured by Sanwa Chemical Co., Ltd.) can be cited.

[0301] The hydroxymethyl type crosslinking agent (C1) can be used alone as one kind, or two or more kinds can be used in combination.

[0302] [Polyfunctional epoxy compound (C2)]

[0303] As the polyfunctional epoxy compound (C2), for example, bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl - p - aminophenol, tetraglycidyl m - xylylenediamine, and tetraglycidyl bis(aminomethyl)cyclohexane; heterocyclic epoxy resins such as isocyanuric acid triglycidyl ester; phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2 - [4 - (2,3 - epoxypropoxy)phenyl] - 2 - [4 - [1,1 - bis[4 - (2,3 - epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3 - bis[4 - [1 - [4 - (2,3 - epoxypropoxy)phenyl] - 1 - [4 - [1 - [4 - (2,3 - epoxypropoxy)phenyl] - 1 - methylethyl]phenyl]ethyl]phenoxy] - 2

[0304] Trifunctional epoxy resins such as -propanol; Tetrafunctional epoxy resins such as pentaerythritol tetraglycidyl ether, tetrahydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, resorcinol diglycidyl ether, and tetra (glycidyloxy) biphenyl.

[0305] Among the above polyfunctional epoxy compounds, the compound represented by the following formula (c1-I) is preferred.

[0306] [Chemical formula 29]

[0307]

[0308] In formula (c1-I), X c1 , X c2 and X c3 are each independently a hydrogen atom or an organic group that may contain an epoxy group, and the total number of epoxy groups in X c1 , X c2 and X c3 is 2 or more. )

[0309] As the compound represented by the above formula (c1-I), the compound represented by the following formula (a1-II) is preferred.

[0310] [Chemical formula 30]

[0311]

[0312] In formula (c1-II), R c1 to R c3 are linear, branched or cyclic alkylene groups, arylene groups, -O-, -C(=O)-, -NH-, and groups formed by combinations thereof, and they may be the same or different from each other. E 1 to E 3 are epoxy groups or hydrogen atoms. Among them, at least two of E 1 to E 3 are epoxy groups.

[0313] In formula (c1-II), regarding the groups represented by R c1 and E 1 , R c2 and E 2 , and R c3 and E 3 , for example, it is preferred that at least two of them are each a group represented by the following formula (c1-IIa), and more preferably each of them is a group represented by the following formula (c1-IIa). The multiple groups represented by formula (c1-IIa) bonded in one compound are preferably the same group.

[0314] -L-C c (c1-IIa)

[0315] In formula (c1-IIa), L is a linear, branched or cyclic alkylene group, arylene group, -O-, -C(=O)-, -NH-, or a group formed by a combination thereof, and C a is an epoxy group. In formula (c1-IIa), L and C a can be bonded to form a cyclic structure.)

[0316] In formula (c1-IIa), regarding the linear, branched or cyclic alkylene group as L, it is preferably an alkylene group having 1 to 10 carbon atoms, and regarding the arylene group as L, it is preferably an arylene group having 5 to 10 carbon atoms. In formula (a1-IIa), L is preferably a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C(=O)-, -NH-, or a group formed by a combination thereof, preferably at least one of a linear alkylene group having 1 to 3 carbon atoms such as a methylene group and a phenylene group, or a group formed by a combination of at least one of them with -O-, -C(=O)- and NH-.

[0317] In formula (c1-IIa), in the case where L and C a are bonded to form a cyclic structure, for example, in the case where a branched alkylene group and an epoxy group are bonded to form a cyclic structure (a structure of an epoxy group having an alicyclic structure), the organic groups represented by the following formulas (c1-IIb) to (c1-IId) can be cited.

[0318] [Chemical formula 31]

[0319]

[0320] In formula (c1-IIb), R c4 is a hydrogen atom or a methyl group.

[0321] Hereinafter, as examples of the compound represented by formula (c1-II), examples of an epoxy compound having an oxiranyl group or an alicyclic epoxy group are shown, but are not limited thereto.

[0322] [Chemical formula 32]

[0323]

[0324] [Chemical formula 33]

[0325]

[0326] The content of the crosslinking agent (C) in the photosensitive resin composition is not particularly limited as long as the desired effects are not impaired. With respect to 100 parts by mass of the polyhydroxystyrene resin (A), the content of the crosslinking agent (C) in the photosensitive resin composition is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 25 parts by mass or less, and particularly preferably 5 parts by mass or more and 20 parts by mass or less.

[0327] <Quencher (D)>

[0328] The photosensitive resin composition may contain a quencher (D). As the quencher (D), low molecular weight compounds (non-polymers) are usually used. As the quencher (D), for example, amines such as aliphatic amines and aromatic amines can be cited. As the quencher (D), aliphatic amines are preferred, and aliphatic secondary amines and aliphatic tertiary amines are particularly preferred. Here, the so-called aliphatic amine is an amine having one or more aliphatic groups. The number of carbon atoms of the aliphatic group possessed by the aliphatic amine is preferably 1 or more and 20 or less.

[0329] As the aliphatic amine, for example, it can be cited that at least one of the hydrogen atoms of ammonia (NH 3 ) is replaced by an alkyl group having 20 or less carbon atoms to form an alkylamine, at least one of the hydrogen atoms of ammonia (NH 3 ) is replaced by a hydroxyalkyl group to form an alkanolamine, and cyclic amines.

[0330] As specific examples of the alkylamine and alkanolamine, monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine can be cited; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, stearyl diethanolamine, and lauryl diethanolamine. Among them, trialkylamines and alkanolamines are preferred.

[0331] As the cyclic amine, for example, nitrogen-containing heterocyclic compounds can be cited. As the nitrogen-containing heterocyclic compound, it can be a monocyclic aliphatic amine or a polycyclic aliphatic amine.

[0332] As the aliphatic monocyclic amine, specifically, piperidine and piperazine can be cited. The number of carbon atoms of the aliphatic polycyclic amine is preferably 6 or more and 10 or less. As the aliphatic polycyclic amine, specifically, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane can be cited.

[0333] As other aliphatic amines, specifically, 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}ethyl]amine, etc. can be cited.

[0334] As aromatic amines, specifically, aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, 2,2'-bipyridine, 4,4'-bipyridine, etc. can be cited.

[0335] The quencher (D) can be used alone or in combination of two or more. With respect to 100 parts by mass of the polyhydroxystyrene resin (A), the amount of the quencher (D) contained in the photosensitive resin composition is preferably 0.01 part by mass or more and 5.0 parts by mass or less.

[0336] <Organic solvent (S)>

[0337] The photosensitive resin composition may contain an organic solvent (S). By making the photosensitive resin composition contain the organic solvent (S), the coatability of the photosensitive resin composition and the film thickness of the positive photosensitive resin composition layer formed using the photosensitive resin composition can be easily adjusted. The organic solvent (S) can be used alone or in combination of two or more.

[0338] Specific examples of the organic solvent (S) can include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isopentyl ketone, 2-heptanone; polyhydric alcohols and their derivatives such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate, and their monomethyl ethers (for example, propylene glycol monomethyl ether acetate), monoethyl ethers, monopropyl ethers, monobutyl ethers or monophenyl ethers; cyclic ethers such as dioxane; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene, xylene; and so on.

[0339] In the photosensitive resin composition, the content of the organic solvent (S) is preferably 50 parts by mass or more and 3000 parts by mass or less, more preferably 100 parts by mass or more and 2000 parts by mass or less, based on 100 parts by mass of the polyhydroxystyrene resin (A). If the content is within the above range, it is easy to improve the coatability of the photosensitive resin composition and to adjust the film thickness of the coating film formed using the photosensitive resin composition.

[0340] <Other components>

[0341] The photosensitive resin composition may contain various additives together with the above components within a range that does not impair the desired effects. The additives can be appropriately selected from various additives conventionally incorporated into the photosensitive resin composition. Specific examples of other components include polyvinyl resin, surfactants, and acids or acid anhydrides.

[0342] To improve the plasticity of the formed film, the photosensitive resin composition may contain polyvinyl resin. Specific examples of polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof.

[0343] To improve the adhesiveness to the support, the photosensitive resin composition may contain an adhesion promoter.

[0344] In order to improve coatability, defoaming property, leveling property, etc., the photosensitive resin composition may contain a surfactant. Specific examples of the surfactant include BM-1000, BM-1100 (both manufactured by BM CHEMI), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (all manufactured by DIC), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone), PolyFox PF-136A, PolyFox PF-156A, PolyFox PF-151N, PolyFox PF-636, PolyFox PF-656, PolyFox PF-6520 (all manufactured by OMNOVA Solutions), etc. These are commercially available fluorosurfactants, but are not limited thereto.

[0345] In order to finely adjust the solubility in the developer, the photosensitive resin composition may contain an acid or an acid anhydride.

[0346] Specific examples of the acid and the acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, cinnamic acid; hydroxy monocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 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; polycarboxylic acids such as 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, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, malonic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis(trimellitic anhydride), glycerol tris(trimellitic anhydride); and so on.

[0347] <Method for manufacturing photosensitive resin composition>

[0348] The photosensitive resin composition can be prepared by mixing and stirring the above-mentioned respective components using a conventional method. If necessary, a disperser such as a dissolver, a homogenizer, or a three-roll mill can also be used for dispersion and mixing. In addition, after mixing, it can also be further filtered using a sieve, a membrane filter, etc.

[0349] <<Cured product>>

[0350] By heating the aforementioned photosensitive resin composition, the polyhydroxystyrene resin (A) is crosslinked using the crosslinking agent (C) to form a cured product. Such a cured product has excellent chemical resistance.

[0351] It should be noted that before the photosensitive resin composition is cured by heating, the photosensitive resin composition can be exposed. In this case, the acid generated by the photoacid generator (B) through exposure promotes the reaction between the polyhydroxystyrene resin (A) and the crosslinking agent (C).

[0352] <<Method for manufacturing optical element>>

[0353] Through the following method, an optical element having a plurality of microlenses on a substrate can be manufactured.

[0354] Specifically, this method includes the following steps:

[0355] A step of coating the aforementioned photosensitive resin composition on a substrate to form a coating film;

[0356] A step of selectively exposing the coating film at positions where a plurality of microlenses are to be formed on the substrate in a point-by-point manner;

[0357] A step of developing the exposed coating film to form a plurality of points at positions where a plurality of microlenses are to be formed; and

[0358] A step of heating the plurality of points, thereby deforming the plurality of points by heat to form a plurality of microlenses.

[0359] In this method, before heating the plurality of points, the plurality of points are exposed.

[0360] The method of coating the photosensitive resin composition on the substrate is not particularly limited. For example, a contact transfer type coating device such as a roll coater, a reverse roll coater, a bar coater, or a slot coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain coater can be used to coat the photosensitive resin composition in such a manner as to achieve a desired film thickness, thereby forming a coating film.

[0361] For the formed coating film, a heat treatment (pre-baking (front baking (PAB)) treatment) can be appropriately performed to remove the solvent in the coating film.

[0362] The conditions of the above heat treatment vary depending on the types, mixing ratios, coating film thicknesses, etc. of the components of the photosensitive resin composition. The heating temperature is preferably, for example, 60°C or higher and 150°C or lower, more preferably 70°C or higher and 140°C or lower. The heating time is preferably, for example, 0.5 minutes or longer and 60 minutes or shorter, more preferably 1 minute or longer and 50 minutes or shorter.

[0363] The film thickness of the coating film can be appropriately selected according to the size of the formed microlenses.

[0364] The film thickness of the coating film is preferably in the range of 100 nm or more and 50 μm or less, more preferably in the range of 400 nm or more and 30 μm or less.

[0365] Next, the coating film is selectively exposed at positions where a plurality of microlenses are to be formed on the substrate in a manner of forming a plurality of dots.

[0366] The position-selective exposure can be performed, for example, through a desired mask pattern. The wavelength of the light used in the exposure is not particularly limited. The exposure can be performed using radiation such as KrF excimer laser, ArF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc.

[0367] After the exposure, if necessary, a PEB (post-exposure baking) treatment (post-exposure heat treatment) is performed on the coating film. The conditions of the PEB treatment vary depending on the types, mixing ratios, coating film thicknesses, etc. of the components in the first coating film. For example, 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 preferably, for example, 0.5 minutes or longer and 60 minutes or shorter, more preferably 1 minute or longer and 50 minutes or shorter.

[0368] Next, the coating film is developed. Thereby, the unnecessary portions are dissolved and removed, and a plurality of dots are formed at positions where a plurality of microlenses are to be formed.

[0369] As a developer, for example, aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, 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 [4.3.0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or a surfactant to the aqueous solution of the above-mentioned alkali can also be used as a developer. As a developer, an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.1% by mass or more and 10% by mass or less is preferred.

[0370] The development time also varies depending on the composition of the photosensitive resin composition, the thickness of the coating film, etc., but is generally 1 to 30 minutes. The development method may be any of an effusion method, an immersion method, a spin immersion method, a spray development method, and the like.

[0371] The developed coating film is washed with running water or the like as necessary, and then dried. As described above, a plurality of dots are formed at positions where a plurality of microlenses are to be formed.

[0372] Next, the multiple dots are heated to deform the dots by heat, thereby forming multiple microlenses. In this way, the dots are deformed and the polyhydroxystyrene resin (A) contained in each dot is crosslinked by the crosslinking agent (C), thereby forming microlenses with excellent chemical resistance.

[0373] It should be noted that the plurality of points are exposed before heating. The exposure is performed in the same manner as in the above method. The acid generated by the photoacid generator (B) by the exposure promotes the crosslinking of the polyhydroxystyrene resin (A) and the crosslinking agent (C).

[0374] The heating conditions vary depending on the type, proportion, coating thickness, etc. of each component in the photosensitive resin composition. For example, the heating temperature is preferably 170° C. to 250° C., more preferably 180° C. to 230° C. The heating time is, for example, preferably 1 minute to 30 minutes, more preferably 3 minutes to 10 minutes.

[0375] By operating as described above, an optical element including a plurality of microlenses on a substrate can be formed.

[0376] As described above, the inventors of the present application provided the following (1) to (8).

[0377] (1) A photosensitive resin composition comprising a polyhydroxystyrene resin (A), a photoacid generator (B) that generates an acid upon irradiation with activated light or radiation, and a crosslinking agent (C).

[0378] In the polyhydroxystyrene resin (A), a part of the phenolic hydroxyl groups is protected with an acetal-type protecting group.

[0379] The photosensitive resin composition can provide a cured product having a refractive index of 1.50 or more at a wavelength of 550 nm.

[0380] (2) The photosensitive resin composition according to (1), wherein the crosslinking agent (C) comprises a heterocyclic compound having a crosslinkable group.

[0381] (3) The photosensitive resin composition according to (2), wherein the heterocyclic compound is a nitrogen-containing heterocyclic compound.

[0382] (4) The photosensitive resin composition according to (3), wherein the nitrogen-containing heterocyclic compound has a 1,3,5-triazine-2,4,6-trione-1,3,5-triyl group.

[0383] (5) The photosensitive resin composition according to any one of (1) to (4), wherein the photoacid generator (B) comprises a sulfonate-type photoacid generator (B1) and / or an onium salt-type photoacid generator (B2).

[0384] (6) A cured product of the photosensitive resin composition according to any one of (1) to (4).

[0385] (7) A microlens formed from the cured product according to (6).

[0386] (8) A method for manufacturing an optical element having a plurality of microlenses on a substrate, the manufacturing method comprising the following steps:

[0387] A step of coating the substrate with the photosensitive resin composition according to any one of (1) to (4) to form a coating film;

[0388] A step of selectively exposing the coating film at positions where a plurality of microlenses are to be formed on the substrate in such a manner as to form a plurality of dots;

[0389] A step of developing the exposed coating film to form a plurality of dots at positions where a plurality of microlenses are to be formed; and

[0390] A step of heating the plurality of dots to deform the plurality of dots by heat to form a plurality of microlenses,

[0391] In the manufacturing method, the plurality of dots are exposed before heating the plurality of dots.

[0392] Example

[0393] Hereinafter, the present invention will be described in more detail using examples and comparative examples. The present invention is not limited to these examples.

[0394] [Examples 1 to 5 and Comparative Example 1]

[0395] In the examples and comparative examples, as the polyhydroxystyrene resin (A), resin A-1 formed of the following units was used.

[0396] In the following formulas, the numbers attached to each repeating unit are the ratios (mol%) of each unit with respect to all the units contained in the resin (A). The weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of resin A-1 was 20,000.

[0397] [Chemical Formula 34]

[0398]

[0399] In the examples and comparative examples, as the photoacid generator (B), the following B1 to B3 were used.

[0400] [Chemical Formula 35]

[0401]

[0402] In the examples and comparative examples, as the crosslinking agent (C), the following C1 to C3 were used.

[0403] [Chemical Formula 36]

[0404]

[0405] The resin (A) of the type described in Table 1, the photoacid generator (B) of the type described in Table 1, the crosslinking agent (C) of the type described in Table 1, salicylic acid (SA), tri-n-amylamine (TPA), and a surfactant (BYK-310, manufactured by BYK-Chemie) were respectively dissolved in propylene glycol monomethyl ether acetate (PM) so as to have the compositions described in Table 1, to obtain the photosensitive resin compositions of the respective examples and comparative examples.

[0406] It should be noted that propylene glycol monomethyl ether acetate (PM) was used in an amount such that the solid content concentration of the photosensitive resin composition was 50% by mass.

[0407] In addition, in Comparative Example 1, the crosslinking agent (C) was not used.

[0408] Using the obtained photosensitive resin composition, the chemical resistance, refractive index, transmittance of the cured film, and the patterning characteristics (pattern shape) of the photosensitive resin composition were evaluated according to the following methods. The evaluation results are shown in Table 1.

[0409] <Chemical resistance>

[0410] On a silicon substrate, the photosensitive resin compositions of each example and each comparative example were coated using a spin coater. The photosensitive resin composition coated on the silicon substrate was baked at 100 °C for 180 seconds to obtain a coating film with a film thickness of about 20 μm.

[0411] The obtained coating film was immersed 3 times in an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38% by mass for 60 seconds.

[0412] The immersed coating film was rinsed with pure water, dried, and then exposed using a g-line exposure machine with an exposure dose of 999 mJ / cm 2 The exposed coating film was baked at 200 °C for 5 minutes to obtain a cured film.

[0413] The formed cured film was immersed in acetone or propylene glycol monomethyl ether acetate (PM) at 25 °C for 5 minutes respectively.

[0414] Based on the film thickness T1 before immersion and the film thickness T2 after immersion, the film thickness change rate was calculated according to the following formula.

[0415] Film thickness change rate (%) = │100 - (T2 / T1 × 100)│

[0416] Based on the calculated film thickness change rate, the chemical resistance was evaluated according to the following criteria.

[0417] A: The film thickness change rate is 1% or less.

[0418] B: The film thickness change rate is greater than 1% and 3% or less.

[0419] C: The film thickness change rate is greater than 3%.

[0420] <Refractive index and transmittance>

[0421] For a cured film with a film thickness of 1 μm formed by the same operation as the evaluation method of chemical resistance, the refractive index at a light wavelength of 550 nm was evaluated using an ellipsometer M-2000 manufactured by J.A. Woollam Co., Ltd.

[0422] In addition, for the cured film formed by operating in the same manner as the evaluation method for transmittance, measurement was performed using a measuring device with the trade name "MCPD-3000" manufactured by Otsuka Electronics Co., Ltd., and the light transmittance was thereby obtained. The light transmittance is the value at a light wavelength of 380 nm to 780 nm.

[0423] <Patterning property evaluation (pattern shape)>

[0424] On a silicon substrate, the photosensitive resin compositions of the respective examples and comparative examples were applied using a spin coater. The photosensitive resin composition coated on the silicon substrate was baked at 100 °C for 180 seconds to obtain a coating film with a film thickness of approximately 20 μm.

[0425] Through a mask for forming a dot pattern (which is configured by arranging 40-μm × 40-μm rectangular dots at intervals of 40 μm with a rectangular groove (interval) therebetween), the obtained coating film was exposed using an i-line exposure machine under the condition of NA / σ = 0.18 / 0.75.

[0426] The exposed coating film was immersed 3 times in an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38% by mass for 60 seconds each, and developed to form a dot pattern.

[0427] The obtained dot pattern was rinsed with pure water, dried, and then exposed using a ghi-line exposure machine with an exposure dose of 999 mJ / cm 2 of the dot pattern.

[0428] The exposed dot pattern was baked at 200 °C for 5 minutes to cause thermal flow, and a microlens pattern composed of microlenses formed from the cured product of the photosensitive resin composition was obtained.

[0429] Regarding the formed microlens pattern, microscopic observation was performed from a direction perpendicular to the plane direction of the silicon substrate, and the patterning property (pattern shape) was evaluated according to the following criteria.

[0430] A: The dots are deformed into a good lens shape with a diameter of 44 μm or less.

[0431] B: The dots are deformed into a lens shape with a diameter greater than 44 μm and 48 μm or less.

[0432] C: The dot pattern was not formed after development, or the dots were deformed such that the deformed diameter was greater than 48 μm.

[0433] [Table 1]

[0434]

[0435] As can be seen from Examples 1 to 5, by using a polyhydroxystyrene resin (A) in which a part of the phenolic hydroxyl groups is protected with an acetal-type protecting group in a photosensitive resin composition containing a polyhydroxystyrene resin (A), a photoacid generator (B), and a crosslinking agent (C), it is possible to form a microlens having excellent chemical resistance using the photosensitive resin composition.

Claims

1. A photosensitive resin composition comprising a polyhydroxystyrene resin (A), a photoacid generator (B) that generates an acid by irradiation with activating light or radiation, and a crosslinking agent (C), In the polyhydroxystyrene resin (A), a part of the phenolic hydroxyl groups are protected by acetal type protecting groups. The photosensitive resin composition can provide a cured product having a refractive index of 1.50 or more at a wavelength of 550 nm.

2. The photosensitive resin composition according to claim 1, wherein The crosslinking agent (C) includes a heterocyclic compound having a crosslinkable group.

3. The photosensitive resin composition according to claim 2, wherein The heterocyclic compound is a nitrogen-containing heterocyclic compound.

4. The photosensitive resin composition according to claim 3, wherein The nitrogen-containing heterocyclic compound has a 1,3,5-triazine-2,4,6-trione-1,3,5-triyl group.

5. The photosensitive resin composition according to claim 1 or 2, wherein The photoacid generator (B) includes a sulfonate-type photoacid generator (B1) and / or an onium salt-type photoacid generator (B2).

6. A cured product of the photosensitive resin composition according to claim 1 or 2.

7. A microlens formed from the cured product according to claim 6.

8. A method for manufacturing an optical element, wherein the optical element comprises a plurality of microlenses on a substrate, the method comprising the following steps: A step of coating the photosensitive resin composition according to claim 1 or 2 on a substrate to form a coating film; A step of position-selectively exposing the coating film to light in such a manner that a plurality of points are formed at positions on the substrate where the plurality of microlenses are to be formed; The process of developing the exposed coating film to form the plurality of dots at positions where the plurality of microlenses are to be formed; and The process of heating the plurality of points to deform the plurality of points by heat to form the plurality of microlenses, In the manufacturing method, the plurality of points are exposed to light before the plurality of points are heated.

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