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 forming a microlens having high reliability in terms of long-term heat resistance and light resistance by photolithography; a microlens formed from a cured product of the photosensitive resin composition; and a method for producing a microlens using the photosensitive resin composition. And a resin contained in the photosensitive resin composition. [Solution] A photosensitive resin composition which contains a resin (A), the solubility of which in a base can be increased by the action of an acid, and an acid generator (B) that generates an acid by irradiation with activated light or radiation, and which can be crosslinked by heating using a reaction between a hydroxyl group and an isocyanate group, a resin containing a unit (a1) containing a carboxyl group protected by an optionally substituted tertiary alkyl group, a hydroxyl group-donating unit (a2), and a unit (a3) containing a blocked isocyanate group is used.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition containing a structural unit of a specific structure, a microlens formed from a cured product of the photosensitive resin composition, a method for producing a microlens using the photosensitive resin composition, and a resin containing a structural unit of a specific structure. Background Art

[0002] Conventionally, solid-state imaging devices have been used in cameras and camcorders. In such solid-state imaging devices, CCD (charge-coupled device) image sensors and CMOS (complementary metal-oxide semiconductor) image sensors are used. The image sensor is provided with a fine focusing lens (hereinafter referred to as a microlens) for the purpose of increasing the light focusing rate.

[0003] As a method for forming the microlens, a method called a thermal flow method is widely used in the industry.

[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 location where the microlens is to be formed. Each dot constituting the dot pattern has a roughly cylindrical shape or a roughly truncated cone shape. The dot pattern is heated at a temperature above the glass transition temperature of the resin material constituting the dots, so that the resin material constituting the dots flows, and the shape of each dot changes into a hemispherical lens shape by using surface tension. A pattern of microlenses is formed as described above (for example, see Patent Document 1).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2009-15245 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The photosensitive resin composition described in Patent Document 1 comprises a copolymer including a structural unit of a (meth)acrylate having a phenolic hydroxyl group and a structural unit derived from a (meth)acrylate having a thermally crosslinkable group such as an epoxy group, and a photosensitizer such as a quinonediazide group-containing compound.

[0010] When the photosensitive resin composition described in Patent Document 1 is used, a dot pattern can be formed by photolithography. The formed dots are deformed into a lens shape by heating and cured by a crosslinking reaction between phenolic hydroxyl groups and epoxy groups.

[0011] However, the photosensitive resin composition described in Patent Document 1 has room for improvement in terms of the reliability of long-term heat resistance and light resistance of the produced microlens.

[0012] The present invention has been made in view of such actual conditions, and its object is to provide a photosensitive resin composition capable of forming a microlens with high reliability of long-term heat resistance and light resistance by photolithography, a microlens formed from a cured product of the photosensitive resin composition, a method for producing a microlens using the photosensitive resin composition, and a resin contained in the photosensitive resin composition.

[0013] Means for solving problems

[0014] The inventors of the present application have found that the above-mentioned problems can be solved by using, as the resin (A), a resin containing a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group-donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group in a photosensitive resin composition which contains a resin (A) whose solubility in an alkali can be increased by the action of an acid and an acid generator (B) which generates an acid by irradiation with activating light or radiation and which can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating, thereby completing the present invention. Specifically, the present invention provides the following aspects.

[0015] A first aspect of the present invention is a photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) that generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating.

[0016] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group-donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group.

[0017] A second aspect of the present invention is a photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) that generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating.

[0018] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a hydroxyl group donating unit (a2).

[0019] The photosensitive resin composition further contains a compound (C) having two or more blocked isocyanate groups.

[0020] A third aspect of the present invention is a photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) that generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating.

[0021] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a unit (a3) ​​containing a blocked isocyanate group.

[0022] The photosensitive resin composition further contains a compound (D) having two or more hydroxyl groups.

[0023] A fourth aspect of the present invention is a microlens formed of a cured product of the photosensitive resin composition according to the first aspect, the second aspect, or the third aspect.

[0024] A fifth aspect of the present invention is a method for manufacturing a microlens, comprising the following steps:

[0025] A step of applying the photosensitive resin composition according to the first aspect, the second aspect or the third aspect on a substrate to form a coating film;

[0026] A step of selectively exposing the coating film to light in such a manner that dots are formed at positions on the substrate where microlenses are to be formed;

[0027] A step of developing the exposed coating film to obtain a patterned resin film including a plurality of dots in which dots are arranged at positions where microlenses are to be formed; and

[0028] A step of heating a resin film to deform dots by heat to form microlenses.

[0029] A sixth aspect of the present invention is a resin comprising a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group.

[0030] Effects of the Invention

[0031] According to the present invention, there can be provided a photosensitive resin composition capable of forming a microlens having long-term heat resistance and high light resistance reliability by photolithography, a microlens formed from a cured product of the photosensitive resin composition, a method for producing a microlens using the photosensitive resin composition, and a resin contained in the photosensitive resin composition. DETAILED DESCRIPTION

[0032] <<Photosensitive resin composition>>

[0033] Examples of the photosensitive resin composition include the photosensitive resin composition according to the first embodiment described above, the photosensitive resin composition according to the second embodiment, and the photosensitive resin composition according to the third embodiment described above.

[0034] Hereinafter, in the specification of the present application, the photosensitive resin composition according to the first embodiment is also described as a “first composition”. The photosensitive resin composition according to the second embodiment is also described as a “second composition”. The photosensitive resin composition according to the third embodiment is also described as a “third composition”.

[0035] <First Composition>

[0036] The first composition contains a resin (A) whose solubility in an alkali can be increased by the action of an acid (hereinafter, also simply referred to as "resin (A)"), and an acid generator (B) that generates an acid by irradiation with active light or radiation (hereinafter, also simply referred to as "acid generator (B)").

[0037] The first composition can be cross-linked by the reaction between the hydroxyl group and the isocyanate group by heating.

[0038] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group-donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group.

[0039] Hereinafter, essential or optional components that may be contained in the first composition will be described.

[0040] [Resin (A) whose solubility in alkali can be increased by the action of acid]

[0041] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group-donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group.

[0042] Hereinafter, the "hydroxyl group-donating unit (a2)" is also described as "unit (a2)". The "blocked isocyanate group-containing unit (a3)" is also described as "unit (a3)".

[0043] In addition, in the specification of the present application, "unit" means a "structural unit".

[0044] Furthermore, the resin (A) may contain other units (a4) in addition to the units (a1), the units (a2), and the units (a3) ​​within a range not impairing the intended purpose.

[0045] These units may be present in the resin in a block form or may be present randomly. From the viewpoint of the reactivity of the resin (A), it is preferred that each unit constituting the resin (A) is present randomly in the resin (A).

[0046] [Unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent]

[0047] When the resin (A) is an acrylic resin, the unit (a1) is preferably a structural unit derived from an acid-dissociable (meth)acrylate. An oxygen atom other than the carbonyl oxygen in the ester group of the acid-dissociable (meth)acrylate bonds to a tertiary carbon atom in the tertiary alkyl group to form a CO bond.

[0048] The tertiary alkyl group may contain an aliphatic hydrocarbon ring in its structure. The aliphatic hydrocarbon ring may be a cycloalkane ring or a polycycloalkane ring, preferably a cycloalkane ring. When the tertiary alkyl group contains an aliphatic hydrocarbon ring, it is preferred that the tertiary alkyl group only contains a cycloalkane ring.

[0049] As the unit (a1), there can be mentioned a structural unit represented by the following formula (a1-1).

[0050] [Chemical formula 1]

[0051]

[0052] (In formula (a1-1), R a11 is a hydrogen atom or a methyl group, R a12 , R a13 and R a14 Each independently represents an alkyl group having 1 to 12 carbon atoms, R a12 , R a13 and R a14 Two of them may be bonded to each other to form a polycycloalkane ring or a cycloalkane ring. a12 , R a13 and R a14 When two of them are bonded to each other to form a ring, a cycloalkane ring is preferred. )

[0053] About R a12 , R a13 and R a14The alkyl group having 1 to 12 carbon atoms includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl and n-decyl.

[0054] In formula (a1-1), R a12 , R a13 and R a14 The ring formed by two of the bonds in is a polycycloalkane ring or a cycloalkane ring. The polycycloalkane ring or the cycloalkane ring preferably has 5 or more and 20 or less carbon atoms.

[0055] Specific examples of the polycycloalkane ring include an adamantane ring, an isobornane ring, a tricyclodecane ring, and a tetracyclodecane ring.

[0056] Specific examples of the cycloalkane ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring.

[0057] Preferred specific examples of the unit represented by formula (a1-1) include the following units. a11 A hydrogen atom or a methyl group.

[0058] [Chemical formula 2]

[0059]

[0060] The ratio of the number of moles of the unit (a1) to the number of moles of all the structural units of the resin (A) is not particularly limited within the range that does not impair the desired effect. The ratio of the number of moles of the unit (a1) to the number of moles of all the structural units of the resin (A) is preferably 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol%.

[0061] The number of moles of all structural units of the resin (A) contained in the first composition is the total number of moles of the unit (a1), the number of moles of the unit (a2), the number of moles of the unit (a3), and the number of moles of other units (a4).

[0062] [Hydroxy-donating unit (a2)]

[0063] When the resin (A) is an acrylic resin, the hydroxyl-donating unit (a2) is preferably a unit derived from an acrylic acid ester having a hydroxyl group. The hydroxyl-donating unit (a2) has a hydroxyl group or can generate a hydroxyl group by a chemical reaction under the action of light or heat.

[0064] For example, a lactone ring such as a γ-butyrolactone ring can be opened by a chemical reaction based on the action of light or heat to generate a hydroxyl group.

[0065] The unit (a2) is preferably a unit represented by the following formula (a2-1).

[0066] [Chemical formula 3]

[0067]

[0068] (In formula (a2-1), R a21 is a hydrogen atom or a methyl group, R a22 is an organic group or a lactone cyclic group having a hydroxyl group.)

[0069] R a22 In the case of an organic group having a hydroxyl group, the organic group may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. a22 The number of hydroxyl groups in the organic group having a hydroxyl group is not particularly limited as long as the desired effect is not impaired. a22 The number of hydroxyl groups contained in the organic group having a hydroxyl group is typically preferably 1 or more and 4 or less, more preferably 1 or 2, and even more preferably 1.

[0070] As R a22 , preferably a hydrocarbon group substituted by a hydroxyl group. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. As the hydrocarbon group, an aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be a straight chain, a branched chain, a cyclic chain, or a combination of these structures. As the aliphatic hydrocarbon group, a straight chain aliphatic hydrocarbon group is preferred.

[0071] R a22 In the case of a hydrocarbon group substituted by a hydroxyl group, the number of carbon atoms of the hydrocarbon group substituted by a hydroxyl group is not particularly limited. In the case of an aliphatic hydrocarbon group, the number of carbon atoms of the hydrocarbon group substituted by a hydroxyl group is preferably 1 to 20, more preferably 2 to 10, and particularly preferably 2 to 6.

[0072] When the hydrocarbon group in the hydrocarbon group substituted with a hydroxyl group is an aromatic hydrocarbon group or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, the number of carbon atoms in the hydrocarbon group substituted with a hydroxyl group is preferably 6 to 20, more preferably 6 to 12.

[0073] Specific examples of the aliphatic hydrocarbon group substituted with a hydroxy group include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 1-hydroxypropyl group, a 4-hydroxybutyl group, a 5-hydroxypentyl group, a 6-hydroxyhexyl group, a 7-hydroxyheptyl group, a 8-hydroxyoctyl group, a 9-hydroxynonyl group, a 10-hydroxydecyl group, a 11-hydroxyundecyl group, a 12-hydroxydodecyl group, a 13-hydroxytridecyl group, a 14-hydroxytetradecyl group, a 15-hydroxypentadecyl group, a 16-hydroxyhexadecyl group, a 17-hydroxyheptadecyl group, a 18-hydroxyoctadecyl group, a 19-hydroxynonadecyl group, and a 20-hydroxyeicosyl group.

[0074] Among them, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxyoctadecyl, 19-hydroxynonadecyl and 20-hydroxyeicosyl are preferred.

[0075] Among them, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl and 10-hydroxydecyl are more preferred.

[0076] Among them, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyhexyl are more preferred.

[0077] Specific examples of the aromatic hydrocarbon group substituted with a hydroxy group include 4-hydroxyphenyl, 3-hydroxyphenyl, 2-hydroxyphenyl, 4-hydroxynaphth-1-yl, 6-hydroxynaphth-2-yl, and 7-hydroxynaphth-2-yl.

[0078] Among them, 4-hydroxyphenyl and 3-hydroxyphenyl are preferred, and 4-hydroxyphenyl is more preferred.

[0079] As the lactone cyclic group, there is no particular limitation as long as it is a group that can generate a hydroxyl group by hydrolysis. The number of carbon atoms of the lactone cyclic group is preferably 3 or more and 8 or less, more preferably 4 or more and 6 or less. The lactone cyclic group is preferably bonded to the non-carbonyl oxygen atom in formula (a2-1) at a position adjacent to the carbonyl in the lactone ring.

[0080] Preferred specific examples of the lactone cyclic group include 4-oxooxetan-3-yl (propiolactonyl), 5-oxotetrahydrofuran-4-yl (butyrolactonyl), and 6-oxotetrahydropyran-5-yl (valerolactonyl).

[0081] Preferred specific examples of the (meth)acrylate providing the unit represented by formula (a2-1) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl acrylate, 3-hydroxyphenyl methacrylate, 4-oxooxetane-3-yl acrylate, 4-oxooxetane-3-yl methacrylate, 5-oxotetrahydrofuran-4-yl acrylate, 5-oxotetrahydrofuran-4-yl methacrylate, 6-oxotetrahydropyran-5-yl acrylate, and 6-oxotetrahydropyran-5-yl methacrylate.

[0082] Among them, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 5-oxotetrahydrofuran-4-yl acrylate, and 5-oxotetrahydrofuran-4-yl methacrylate are preferred.

[0083] In the first composition, the total ratio of the number of moles of hydroxyl groups possessed by all components other than the solvent (S) to the number of moles of blocked isocyanate groups possessed by all components other than the solvent (S) is preferably 30 mol% to 95 mol%, based on the total of the following i) to iii).

[0084] i) the number of moles of all structural units of the resin (A),

[0085] ii) the total number of moles of blocked isocyanate groups in the components other than the resin (A) and the solvent (S), and

[0086] iii) The total number of moles of hydroxyl groups in components other than the resin (A) and the solvent (S)

[0087] By making the above ratio 30 mol% or more, the first composition is well cured by the reaction of the hydroxyl group and the isocyanate group. The above ratio is more preferably 40 mol% or more and 90 mol% or less, further preferably 45 mol% or more and 80 mol% or less, and particularly preferably 50 mol% or more and 70 mol% or less.

[0088] The number of moles of hydroxyl groups in all components other than the solvent (S) contained in the first composition is M: H The number of moles M of the blocked isocyanate groups in all components other than the solvent (S) contained in the first composition BI The ratio is M H :M BI The ratio is preferably 30:70 to 70:30, more preferably 40:60 to 60:40, and still more preferably 45:55 to 55:45.

[0089] [Units containing blocked isocyanate groups (a3)]

[0090] When the resin (A) is an acrylic resin, the unit (a3) ​​containing a blocked isocyanate group is preferably a unit derived from an acrylate having a blocked isocyanate group. The unit derived from an acrylate having a blocked isocyanate group is preferably a unit represented by the following formula (a3-1).

[0091] [Chemical formula 4]

[0092]

[0093] (In formula (a3-1), R a31 is a hydrogen atom or a methyl group, R a32 is a single bond or an alkylene group having 1 to 5 carbon atoms, R a33 is a blocked isocyanate group.)

[0094] In formula (a3-1), R a32 is a single bond or an alkylene group having 1 to 5 carbon atoms. The alkylene group may be linear or branched, but is preferably linear. a32 Specific examples of the alkylene group include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group.

[0095] Among these groups, a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group are preferred, a methylene group, an ethane-1,2-diyl group, and a propane-1,3-diyl group are more preferred, and an ethane-1,2-diyl group is particularly preferred.

[0096] In formula (a3-1), R a33 The blocked isocyanate group is a group formed by blocking an isocyanate group with a thermally dissociable protective group.

[0097] The thermally dissociable protecting group can be formed by reacting an isocyanate group with a blocking agent that provides a protecting group.

[0098] Examples of the end-capping agent include alcohol compounds, phenol compounds, compounds containing a hydroxyl group other than alcohol compounds and phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, carbamic acid compounds, urea compounds, amide (lactam) compounds, imide compounds, triazole compounds, pyrazole compounds, pyrrole compounds, thiol compounds, and hydrogen sulfite.

[0099] Examples of the alcohol compound include methanol, ethanol, isopropanol, n-butanol, sec-butanol, 2-ethylhexanol, 1-octanol, 2-octanol, cyclohexanol, ethylene glycol, benzyl alcohol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2-(hydroxymethyl)furan, 2-methoxyethanol, 2-methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-(2-ethoxyethoxy)ethanol, 2-(4-ethoxybutoxy)ethanol, 2-(2-butoxyethoxy)ethanol, N,N-dibutyl-2-hydroxyacetamide, N-morpholinoethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12-hydroxystearic acid, and 2-hydroxyethyl methacrylate.

[0100] Examples of the phenolic compound include phenol, o-cresol, m-cresol, p-cresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-n-propylphenol, 3-n-propylphenol, 4-n-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-n-butylphenol, 3-n-butylphenol, 4-n-butylphenol, 2-sec-butylphenol, 3-sec-butylphenol, 4-sec-butylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-n-hexylphenol, 3-n-hexylphenol, 4-n-hexylphenol, 2-(2-ethylhexyl)phenol, 3-(2-ethylhexyl)phenol, 4-(2-ethylhexyl)phenol, 2-n-octylphenol, 3-n-octylphenol, Phenol, 4-n-octylphenol, 2-n-nonylphenol, 3-n-nonylphenol, 4-n-nonylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3-di-n-propylphenol, 2,4-di-n-propylphenol, 2,5-di-n-propylphenol, 2,6-di-n-propylphenol, 3,4-di-n-propylphenol, 3,5-di-n-propylphenol, 2,3-diisopropylphenol, 2,4-diisopropylphenol, 2,5-diisopropylphenol, 2,6-diisopropylphenol, 3,4-diisopropylphenol, 3,5-diisopropylphenol, 3-isopropyl-2-methylphenol, 4-isopropyl-2 -Methylphenol, 5-isopropyl-2-methylphenol, 6-isopropyl-2-methylphenol, 2-isopropyl-3-methylphenol, 4-isopropyl-3-methylphenol, 5-isopropyl-3-methylphenol, 6-isopropyl-3-methylphenol, 2-isopropyl-4-methylphenol, 3-isopropyl-4-methylphenol, 5-isopropyl-4-methylphenol, 6-isopropyl-4-methylphenol, 2,3-di-n-butylphenol, 2,4-di-n-butylphenol, 2,5-di-n-butylphenol, 2,6-di-n-butylphenol, 3,4-di-n-butylphenol, 3,5-di-n-butylphenol, 2,3-di-sec-butylphenol, 2,4-di-sec-butylphenol, 2,5-di-sec-butylphenol, 2,6-di-sec-butylphenol, 3,4-di-sec-butylphenol, 3,5-di-sec-butylphenol, 2,3-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, 3,4-di-tert-butylphenol, 3,5-di-tert-butylphenol, 2,3-di-n-octylphenol, 2,4-di-n-octylphenol, 2,5-di-n-octylphenol, 2,6-di-n-octylphenol, 3,4-di-n-octylphenol, 3,5-di-n-octylphenol, 2,3-di-2-ethylhexylphenol, 2,4-di-2-ethylhexylphenol, 2,5-di-2-ethylhexylphenol, 2,6-di-2-ethylhexylphenol, 3,4-di-2-ethylhexylphenol, 3,5-di-2-ethylhexylphenol, 2,3

[0101] -Di-n-nonylphenol, 2,4-di-n-nonylphenol, 2,5-di-n-nonylphenol, 2,6-di-n-nonylphenol, 3,4-di-n-nonylphenol, 3,5-di-n-nonylphenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, styrenated benzene Phenol (mono-, di- or tri-substituted phenol obtained by using α-methylbenzyl group), methyl salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl 4-hydroxybenzoate, 4-[(dimethylamino)methyl]phenol, 4-[(dimethylamino)methyl]nonylphenol, bis(4-hydroxyphenyl)acetic acid, 2-hydroxypyridine, 2-hydroxyquinoline, 8-hydroxyquinoline and 2-chloropyridin-3-ol.

[0102] Examples of the hydroxyl group-containing compound other than the alcohol compound and the phenol compound include N-hydroxysuccinimide and triphenylsilanol.

[0103] Examples of the active methylene compound include Meldrum's acid, dialkyl malonates (e.g., dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-tert-butyl malonate, di-2-ethylhexyl malonate, methyl n-butyl malonate, ethyl n-butyl malonate, methyl sec-butyl malonate, ethyl sec-butyl malonate, methyl tert-butyl malonate, ethyl tert-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzyl methyl malonate, ethyl phenyl malonate, tert-butylphenyl malonate, and isopropylidene malonate), alkyl acetoacetates (e.g., methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, tert-butyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate), 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate.

[0104] Examples of the amine compound include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis(2,2,6,6-tetramethylpiperidinyl)amine, di-n-propylamine, diisopropylamine, isopropylethylamine, 2,2,4-trimethylhexamethyleneamine, 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis(3,5,5-trimethylcyclohexyl)amine, piperidinylamine, Piperidine, 2,6-dimethylpiperidine, tert-butylmethylamine, tert-butylethylamine, tert-butyl-n-propylamine, tert-butyl-n-butylamine, tert-butylbenzylamine, tert-butylphenylamine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino)-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6-methyl-2-piperidine and 6-aminohexanoic acid, etc.

[0105] Examples of the imine compound include ethylenimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, and guanidine.

[0106] Examples of the oxime compound include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, diacetyl monoxime, benzophenone oxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropyl ketone oxime, methyl tert-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylamyl ketone oxime, methyl 3-ethylheptyl ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monoxime, 4,4′-dimethoxybenzophenone oxime, and 2-heptanone oxime.

[0107] Examples of the carbamic acid compound include phenyl N-phenylcarbamate and the like.

[0108] Examples of the urea compound include urea, thiourea, and ethylene urea.

[0109] Examples of the amide (lactam) compound include acetanilide, N-methylacetamide, acetamide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, and laurolactam.

[0110] Examples of the imide compound include succinimide, maleimide, and phthalimide.

[0111] Examples of the triazole compound include 1,2,4-triazole and benzotriazole.

[0112] Examples of the pyrazole compound include pyrazole, 3,5-dimethylpyrazole, 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-di-tert-butylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole.

[0113] Examples of the pyrrole-based compound include pyrrole, 2-methylpyrrole, 3-methylpyrrole, and 2,4-dimethylpyrrole.

[0114] Examples of the thiol compound include n-butyl mercaptan, n-dodecyl mercaptan, n-hexyl mercaptan, thiophenol, and pyridine-2-thiol.

[0115] Examples of the hydrogen sulfite include sodium hydrogen sulfite and the like.

[0116] Among these terminal blocking agents, amide compounds, alcohol compounds, or oxime compounds are preferred from the viewpoint of not deactivating the acid generated by the acid generator (B) and obtaining good patterning properties. As the amide compound, a lactam compound is preferred.

[0117] As the lactam compound, it is preferred to provide a group represented by the following formula (a3-2) as R a33 of compounds.

[0118] -NH-CO-R a34 ···(a3-2)

[0119] (In formula (a3-2), R a34 is a lactam ring group. The lactam ring group is a group obtained by removing a hydrogen atom from a nitrogen atom in a lactam ring. The nitrogen atom in the lactam ring group is bonded to a carbon atom in a carbonyl group.

[0120] As the alcohol compound, it is preferred to provide a group represented by the following formula (a3-3) as R a33 of compounds.

[0121] -NH-CO-R a35 ···(a3-3)

[0122] (In formula (a3-3), R a35 is an alkoxy group. The oxygen atom in the alkoxy group is bonded to the carbon atom in the carbonyl group. The alkoxy group may contain a heteroatom in addition to the oxygen atom of the alkoxy group. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.)

[0123] As the oxime compound, it is preferred to provide a group represented by the following formula (a3-4) as R a33 of compounds.

[0124] -NH-CO-R a36 ···(a3-4)

[0125] (In formula (a3-4), R a36 The oxime group is a group obtained by removing a hydrogen atom from an oxygen atom in an oxime structure. The oxygen atom in the oxime group is bonded to the carbon atom in the carbonyl group.

[0126] The content of the units (a3) ​​in the resin (A) is preferably 10 mol% or more, more preferably 20 mol% or more, based on the number of moles of all structural units of the resin (A).

[0127] The number of moles of all structural units of the resin (A) is the total number of moles of the unit (a1), the number of moles of the unit (a2), the number of moles of the unit (a3), and the number of moles of other units (a4) described below.

[0128] In the first composition, the total ratio of the number of moles of the units (a3) ​​of the resin (A) to the total number of moles of the blocked isocyanate groups possessed by the components other than the resin (A) and the solvent (S) is preferably 10 mol% or more, more preferably 20 mol% or more, relative to the total of the following i) to iii).

[0129] i) the number of moles of all structural units of the resin (A),

[0130] ii) the total number of moles of blocked isocyanate groups in the components other than the resin (A) and the solvent (S), and

[0131] iii) The total number of moles of hydroxyl groups in components other than the resin (A) and the solvent (S)

[0132] In the first composition, it is preferred that the content of the unit (a3) ​​is 10 mol% or more relative to the molar number of all structural units of the resin (A), and that the total ratio of the molar number of the unit (a3) ​​of the resin (A) to the total molar number of the blocked isocyanate groups possessed by the components other than the resin (A) and the solvent (S) is 10 mol% or more relative to the total of i) to iii) above.

[0133] 〔Other units (a4)〕

[0134] The resin (A) may further contain other units (a4) in addition to the above-mentioned units (a1), units (a2), and units (a3) ​​within a range not impairing the desired effects.

[0135] When the resin (A) is an acrylic resin, examples of the other units (a4) include units derived from (meth)acrylates. As the (meth)acrylate, a compound represented by the following formula (a4-1) is preferred.

[0136] [Chemical formula 5]

[0137]

[0138] In the above formula (a4-1), R a41 is a hydrogen atom or a methyl group. a42 It is an organic group having no group containing active hydrogen that can react with an isocyanate group.

[0139] As the group containing active hydrogen, for example, hydroxyl, mercapto, amino, carboxyl, etc. can be cited. For the organic group, the organic group may contain a bond or a substituent other than a hydrocarbon group such as a heteroatom. In addition, the structure of the organic group may be any structure in a straight chain, a branched chain, a ring, or a combination of these structures.

[0140] As R a42 The substituents other than the hydrocarbon group in the organic group are not particularly limited as long as they do not impair the effects of the present invention, and include halogen atoms, alkylthio groups, arylthio groups, cyano groups, silyl groups, alkoxy groups, alkoxycarbonyl groups, nitro groups, nitroso groups, acyl groups, acyloxy groups, alkoxyalkyl groups, alkylthioalkyl groups, aryloxyalkyl groups, arylthioalkyl groups, N,N-disubstituted amino groups (-NRR': R and R' each independently represent a hydrocarbon group), etc. The hydrogen atoms contained in the above substituents may be substituted with hydrocarbon groups. In addition, the structure of the hydrocarbon group contained in the above substituents may be any structure selected from the group consisting of linear, branched, cyclic, and combinations thereof.

[0141] As R a42 , preferably an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. These groups may be substituted by a halogen atom, an alkyl group or a heterocyclic group. In addition, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond or an ester bond.

[0142] When the alkyl group is linear or branched, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Preferred examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl.

[0143] R a42In the case of an aryl group, preferred examples of the aryl group include phenyl, naphth-1-yl, naphth-2-yl, 4-phenylphenyl, 3-phenylphenyl and 2-phenylphenyl.

[0144] R a42 In the case of an alicyclic group or a group containing an alicyclic group, preferred alicyclic groups include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, and polycyclic alicyclic groups such as adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecanyl and tetracyclododecyl.

[0145] Examples of the monomers other than the (meth)acrylates which provide the unit (a4) include allyl compounds, vinyl ethers, vinyl esters, styrenes, etc. These monomers may be used alone or in combination of two or more.

[0146] Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and the like.

[0147] Examples of the vinyl ethers include alkyl 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, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; and the like.

[0148] Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β-phenylbutyrate, vinyl benzoate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

[0149] Examples of the styrenes include styrene; alkyl styrenes such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, and acetoxymethyl styrene; alkoxy styrenes such as methoxy styrene, 4-methoxy-3-methyl styrene, and dimethoxy styrene; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and the like.

[0150] The content of other units (a4) in resin (A) is not particularly limited within the range that does not impair the desired effect. When resin (A) comprises the aforementioned units (a1), units (a2) and units (a3), the total of the molar ratio of units (a1), the molar ratio of units (a2) and the molar ratio of units (a3) ​​relative to all structural units of resin (A) is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, further more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0151] Therefore, the molar ratio of unit (a4) relative to all structural units of resin (A) is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, further more preferably 20 mol% or less, and particularly preferably 10 mol% or less.

[0152] [Acid generator (B) that generates acid by irradiation with activating light or radiation]

[0153] The first composition contains an acid generator (B). The acid generated by the acid generator (B) deprotects the unit (a1) in the resin (A) by irradiation with activating light or radiation. As a result, a carboxyl group is generated in the resin (A). Therefore, the first composition becomes soluble in an alkaline developer by irradiation with activating light or radiation.

[0154] The acid generator (B) is not particularly limited, and any acid generator previously blended in a photosensitive resin composition can be used without particular limitation.

[0155] As the acid generator (B), an onium salt-based acid generator such as iodonium salt and sulfonium salt is preferred.

[0156] In addition, oxime sulfonate acid generators; diazomethane acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes; nonionic acid generators such as nitrobenzylsulfonate acid generators, imidosulfonate acid generators and disulfone acid generators are also preferred.

[0157] As these acid generators, those having a fluorine atom are preferred.

[0158] Onium salt acid generators and imidosulfonate acid generators are preferred because a first composition having excellent lithographic properties can be easily obtained and a microlens having excellent long-term heat resistance and light resistance can be easily formed using the first composition.

[0159] 〔Onium salt acid generator〕

[0160] Preferred examples of onium salt-based acid generators include compounds represented by the following formula (b-1) or compounds represented by the following formula (b-2). Hereinafter, the compound represented by the following formula (b-1) is also referred to as "component (b-1)". The compound represented by the following formula (b-2) is also referred to as "component (b-2)".

[0161] [Chemical formula 6]

[0162]

[0163] (In formula (b-1) and formula (b-2), R 101 and R 104 ~R 105 Each is independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, R 104 With R 105 can be bonded to each other to form a ring, R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom, Y 101 is a divalent linking group or a single bond containing an oxygen atom, V 101 ~V 103 are each independently a single bond, an alkylene group or a fluoroalkylene group, L 101 ~L 102 Each independently represents a single bond or an oxygen atom. m is an integer greater than 1, M' m+ is an m-valent onium cation. )

[0164] (Anion part)

[0165] Next, the anion part constituting the component (b-1) will be described.

[0166] In formula (b-1), R 101It is a cyclic group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.

[0167] R 101 In the case of a cyclic group which may have a substituent, the cyclic group is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or an alicyclic hydrocarbon group. The alicyclic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0168] As R 101 The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, further preferably 6 to 15, and particularly preferably 6 to 10. However, when the aromatic hydrocarbon group has a substituent, the above-mentioned number of carbon atoms does not include the number of carbon atoms of the substituent.

[0169] About R 101 Specific examples of the aromatic hydrocarbon ring contained in the aromatic hydrocarbon group include a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and a biphenyl ring.

[0170] As R 101 The cyclic group may include an aromatic heterocycle in which a portion of the carbon atoms constituting the aromatic hydrocarbon ring is replaced by a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0171] About R 101 Specific examples of the aromatic hydrocarbon group include phenyl, naphth-1-yl, naphth-2-yl, 4-phenylphenyl, 3-phenylphenyl and 2-phenylphenyl.

[0172] About R 101 The alicyclic hydrocarbon group includes an aliphatic hydrocarbon group containing a ring in the structure.

[0173] Examples of the aliphatic hydrocarbon group containing a ring in its structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), a group obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched aliphatic hydrocarbon group.

[0174] The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less.

[0175] The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The number of carbon atoms of the monocycloalkane is preferably 3 or more and 6 or less. Specific examples of the monocycloalkane include cyclopentane and cyclohexane.

[0176] The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane. The number of carbon atoms in the polycyclic alkane is preferably 7 or more and 30 or less. Specific examples of the polycyclic alkane include polycyclic alkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane; and polycyclic alkanes having a polycyclic skeleton of a fused ring system such as a cyclic group having a steroidal skeleton.

[0177] About R 101 The alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably a group obtained by removing one hydrogen atom from a polycycloalkane, particularly preferably an adamantyl group and a norbornyl group, and most preferably an adamantyl group.

[0178] The number of carbon atoms of the linear aliphatic hydrocarbon group that can be bonded to the alicyclic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group. Preferred specific examples of the linear alkylene group include methylene, ethane-1,2-diyl (ethylene), propane-1,3-diyl (1,3-propylene), butane-1,4-diyl (1,4-butylene), and pentane-1,5-diyl (1,5-pentylene).

[0179] The number of carbon atoms of the branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group is preferably 2 to 10, more preferably 3 to 6, further preferably 3 or 4, and most preferably 3. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include -CH(CH 3 )-、-CH(CH 2 CH 3 )-、-C(CH 3 ) 2 -、-C(CH 3 )(CH 2 CH 3 )-、-C(CH 3 )(CH 2 CH 2 CH 3 )-、-C(CH 2 CH 3 ) 2 -alkylmethylene; -CH(CH 3 )CH 2 -、-CH(CH 3 )CH(CH 3 )-、-C(CH 3 ) 2 CH2 -、-CH(CH 2 CH 3 )CH 2 -、-C(CH 2 CH 3 ) 2 -CH 2 -alkylethylene; -CH(CH 3 )CH 2 CH 2 -、-CH 2 CH(CH 3 )CH 2 -isoalkyl-1,3-propylene; -CH(CH 3 )CH 2 CH 2 CH 2 -、-CH 2 CH(CH 3 )CH 2 CH 2 -alkyl-1,4-butylene and the like. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0180] About R 101 Examples of the cyclic group include a lactone-containing cyclic group, and a -SO-containing cyclic group represented by the formulas (b-r2-1) to (b-r2-4) described later. 2 -cyclic groups, other heterocyclic groups.

[0181] The so-called "containing -SO 2 -cyclic group" refers to a group containing -SO in its ring skeleton 2 - a cyclic group containing a ring with a -SO 2 -The cyclic group may be a monocyclic group or a polycyclic group. 2 -The cyclic group consists only of 2 - In the case of ring formation, the 2 - is a monocyclic group. 2 -The cyclic group consists of 2 or more -SO 2 - ring formation, or in the presence of -SO 2 -Ring also has -SO 2 - In the case of a ring structure other than a ring structure, the ring containing -SO 2 - is a polycyclic group.

[0182] As containing -SO 2 -, particularly preferably a cyclic group containing -O-SO in its ring skeleton2 Such a cyclic group contains a sultone ring.

[0183] As containing -SO 2 -, more specifically, groups represented by the following formulae (b-r2-1) to (b-r2-4) are mentioned.

[0184] [Chemical formula 7]

[0185]

[0186] (In formulas (b-r2-1) to (b-r2-4), R b21 Each is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R" is a hydrogen atom, an alkyl group, a cyclic group containing a lactone, a cyclic group containing a carbonate or a cyclic group containing -SO 2 -cyclic group; B" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom, an alkylene group having 1 to 5 carbon atoms which may contain a sulfur atom, an oxygen atom or a sulfur atom; n' is 0, 1 or 2.)

[0187] In formulas (b-r2-1) to (b-r2-4), regarding R b21 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl. Among them, methyl and ethyl are preferred, and methyl is particularly preferred.

[0188] About R b21 The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group may be linear or branched. Specific examples of the alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, neopentyloxy, and n-hexyloxy. Among them, methoxy and ethoxy are preferred, and methoxy is particularly preferred.

[0189] About R b21 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom is preferred.

[0190] About R b21 The haloalkyl group of R b21A group in which a part or all of the hydrogen atoms of an alkyl group are substituted by the aforementioned halogen atoms. The halogenated alkyl group is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.

[0191] As R b21 In the "-COOR" and "-OC(=O)R", R" is a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, a cyclic group containing a lactone, a cyclic group containing a carbonate, or a cyclic group containing -SO 2 The alicyclic hydrocarbon group as R" may be substituted with a fluorine atom or a fluoroalkyl group.

[0192] In formulas (b-r2-1) to (b-r2-4), the alkylene group having 1 to 5 carbon atoms as B" may be linear or branched. Specific examples of the alkylene group include methylene, ethylene, n-propylene, isopropylene, and the like. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups having -O- or -S- at the end of the alkylene group or between carbon atoms, such as -O-CH 2 -、-CH 2 -O-CH 2 -、-S-CH 2 -、-CH 2 -S-CH 2 - etc. As B", preferably, it is an alkylene group having 1 to 5 carbon atoms or -O-, more preferably, it is an alkylene group having 1 to 5 carbon atoms, and most preferably, it is a methylene group.

[0193] Specific examples of the groups represented by formulae (b-r2-1) to (b-r2-4) are given below: "Ac" in the formulae represents an acetyl group.

[0194] [Chemical formula 8]

[0195]

[0196] [Chemical formula 9]

[0197]

[0198] [Chemical formula 10]

[0199]

[0200] In formula (b-1), regarding R 101 Examples of the substituent that the cyclic group may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.

[0201] The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

[0202] The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, isopropyloxy group, n-butyloxy group, or tert-butyloxy group, and most preferably a methoxy group or ethoxy group.

[0203] As the halogen atom as a substituent, a fluorine atom is preferred.

[0204] The haloalkyl group as a substituent is preferably a haloalkyl group having 1 to 5 carbon atoms, and more preferably a halomethyl group, a haloethyl group, a halopropyl group, a halo-n-butyl group, or a halo-tert-butyl group. The haloalkyl group may be a group in which a part of the hydrogen atoms in the alkyl group are substituted by halogen atoms, or a group in which all the hydrogen atoms in the alkyl group are substituted by halogen atoms.

[0205] The carbonyl group as a substituent is a methylene group (-CH 2 -) to be substituted.

[0206] As R 101 The chain alkyl group may be linear or branched.

[0207] The number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10.

[0208] Preferred specific examples of the straight-chain alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

[0209] The number of carbon atoms in the branched alkyl group is preferably 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Preferred specific examples of the branched alkyl group include 1-methylethyl (isopropyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1-methylbutyl (sec-pentyl), 2-methylbutyl, 3-methylbutyl (isobutyl), 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0210] The chain alkenyl group which may have a substituent:

[0211] As R 101The chain alkenyl group may be straight-chain or branched. The number of carbon atoms in the chain alkenyl group is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Preferred specific examples of straight-chain alkenyl groups include, for example, vinyl, 1-propenyl, 2-propenyl (allyl) and butenyl. Preferred specific examples of branched alkenyl groups include, for example, 1-methylvinyl, 1-methylpropenyl and 2-methylpropenyl.

[0212] Among the above alkenyl groups, a linear alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

[0213] About R 101 The substituents that the chain alkyl or chain alkenyl may have include, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the substituents mentioned above as R 101 Cyclic groups, etc.

[0214] As R 101 , preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, preferably a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, a cyclic group containing a lactone, and a group containing -SO represented by formula (b-r2-1) to (b-r2-4) 2 -cyclic groups, etc.

[0215] In formula (b-1), Y 101 It is a single bond or a divalent linking group containing an oxygen atom.

[0216] Y 101 In the case of a divalent linking group containing an oxygen atom, the Y 101 Atoms other than oxygen atoms may be contained. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.

[0217] Examples of the divalent linking group containing an oxygen atom include an oxygen atom (—O—), —C(═O)—, —OC(═O)—, —C(═O)—NH—, a carbonyl group, and a linking group containing an oxygen atom such as —OC(═O)—O—; and combinations of the linking group containing an oxygen atom and an alkylene group. A sulfonyl group (—SO 2 -). Examples of the divalent linking group containing an oxygen atom include linking groups represented by the following formulae (by-1) to (by-7).

[0218] [Chemical formula 11]

[0219]

[0220] -V′ 101 -O- (by-4)

[0221]

[0222] (In formulas (by-1) to (by-7), V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms, V' 102 It is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.

[0223] As V' 102 The divalent saturated hydrocarbon group may be a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, or a combination of a chain saturated hydrocarbon group and a cyclic saturated hydrocarbon group. 102 The divalent saturated hydrocarbon group is preferably an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 10, and even more preferably 1 to 5.

[0224] As V' 101 and V' 102 The alkylene group may be linear or branched, but is preferably linear.

[0225] About being V' 101 and V' 102 Specific examples of the alkylene group include methylene; -CH(CH 3 )-、-CH(CH 2 CH 3 )-、-C(CH 3 ) 2 -、-C(CH 3 )(CH 2 CH 3 )-、-C(CH 3 )(CH 2 CH 2 CH 3 )- and -C(CH 2 CH 3 ) 2 -Alkylmethylene; Ethylene (-CH 2 CH 2 -); -CH(CH 3 )CH 2 -、-CH(CH 3 )CH(CH 3 )-、-C(CH 3 ) 2 CH 2 - and -CH(CH 2 CH 3 )CH2 -alkylethylene; 1,3-propylene (-CH 2 CH 2 CH 2 -); -CH(CH 3 )CH 2 CH 2 - and - CH 2 CH(CH 3 )CH 2 - isoalkyl-1,3-propylene; 1,4-butylene (-CH 2 CH 2 CH 2 CH 2 -); -CH(CH 3 )CH 2 CH 2 CH 2 - and - CH 2 CH(CH 3 )CH 2 CH 2 -alkyl-1,4-butylene; 1,5-pentylene (-CH 2 CH 2 CH 2 CH 2 CH 2 -)wait.

[0226] In addition, as V' 101 or V' 102 In the alkylene group, a part of the methylene groups may be replaced by a divalent aliphatic cyclic group having a carbon number of 5 to 10. The aliphatic cyclic group may be a monocyclic group or a polycyclic group.

[0227] The aliphatic hydrocarbon group which is a monocyclic group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The number of carbon atoms of the monocycloalkane is preferably 3 or more and 6 or less. As the group obtained by removing two hydrogen atoms from a monocycloalkane, cyclopentylene and cyclohexylene can be mentioned. Among them, cyclohexylene is more preferred.

[0228] The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The number of carbon atoms of the polycyclic alkane is preferably 7 or more and 12 or less. As the group obtained by removing two hydrogen atoms from a polycyclic alkane, there can be mentioned adamantanediyl, norbornanediyl, isobornanediyl, tricyclodecanediyl and tetracyclododecanediyl. Among them, adamantane-1,5-diyl and adamantane-2,6-diyl are more preferred.

[0229] The aliphatic cyclic group may have a substituent. As the substituent, for example, -R P1, -R P2 -OR P1 , -R P2 -CO-R P1 , -R P2 -CO-OR P1 , -R P2 -O-CO-R P1 , -R P2

[0230] -OH, -R P2 -CN and -R P2 -COOH, etc.

[0231] R P1 It is an alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms. P2 It is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0232] R P1 and R P2 The above-mentioned chain saturated hydrocarbon group, cyclic saturated hydrocarbon group and aromatic hydrocarbon group may be a group in which a part or all of the hydrogen atoms in the group are substituted with fluorine atoms.

[0233] The above-mentioned cyclic hydrocarbon group may have one or more of the above-mentioned substituents alone, or may have one or more of the above-mentioned substituents each.

[0234] Examples of the monovalent alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups.

[0235] Examples of the monovalent cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl; bicyclo[2.2.2]octyl, tricyclo[5.2.1.0 2,6 ]decyl, tricyclic [3.3.1.1 3,7 ]decyl, tetracyclic [6.2.1.1 3,6 .0 2,7 ] polycyclic saturated hydrocarbon groups such as dodecyl and adamantyl.

[0236] Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

[0237] As Y 101, preferably a divalent linking group containing a carboxylate bond or a divalent linking group containing an ether bond, and more preferably a linking group represented by each of the above formulae (by-1) to (by-5).

[0238] In formula (b-1), V 101 is a single bond, an alkylene group or a fluoroalkylene group. 101 The number of carbon atoms in the alkylene group and the fluoroalkylene group is preferably 1 or more and 4 or less. 101 The fluoroalkylene group includes V 101 A group in which a part or all of the hydrogen atoms of an alkylene group are replaced by fluorine atoms. 101 , preferably a single bond and a fluorinated alkylene group having 1 to 4 carbon atoms.

[0239] In formula (b-1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. 102 , preferably a fluorine atom and a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

[0240] Y 101 When Y is a single bond, specific examples of the anion moiety represented by formula (b-1) include fluoroalkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion. 101 In the case of a divalent linking group containing an oxygen atom, specific examples of the anion part represented by formula (b-1) include anions represented by the following formulae (ba-1) to (ba-3).

[0241] [Chemical formula 12]

[0242]

[0243] (In formula (ba-1)~(ba-3), R” 101 is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group or an alkyl group which may have a substituent. R" 102 is an aliphatic cyclic group which may have a substituent, a lactone-containing cyclic group, or a -SO-containing group represented by formula (b-r2-1) to (b-r2-4) 2 -cyclic group. R" 103 It is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or an alkenyl group which may have a substituent. V" 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. 102is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v" is each independently an integer from 0 to 3, q" is each independently an integer from 0 to 20, and n" is 0 or 1.)

[0244] As R" 101 , R” 102 and R” 103 The aliphatic cyclic group which may have a substituent is preferably 101 As the substituent, there can be mentioned groups which can be used as R in formula (b-1): 101 The substituents for substituting the alicyclic hydrocarbon group are the same groups.

[0245] As R" 103 The aromatic cyclic group which may have a substituent is preferably 101 , Groups exemplified as aromatic hydrocarbon groups as cyclic hydrocarbon groups. As substituents, there can be mentioned groups which can be used to form R in formula (b-1): 101 The substituents which substitute the aromatic hydrocarbon group are the same as the substituents.

[0246] As R" 101 The chain alkyl group which may have a substituent is preferably about R in formula (b-1) 101 The group exemplified by the chain alkyl group.

[0247] As R" 103 The chain alkenyl group which may have a substituent is preferably about R in formula (b-1) 101 The group exemplified by the chain alkenyl group.

[0248] Next, the anion part constituting the component (b-2) will be described.

[0249] In formula (b-2), R 104 and R 105 Each is independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. Examples of these groups include the following: 101 The same group. 104 With R 105 They may be bonded to each other to form a ring.

[0250] As R 104 and R 105 , preferably an alkyl group which may have a substituent, more preferably an alkyl group or a fluoroalkyl group. The alkyl group and the fluoroalkyl group may be linear or branched.

[0251] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. 104 and R 105 The smaller the number of carbon atoms in the alkyl group, the more preferred. 104 and R 105 For a fluoroalkyl group, the more hydrogen atoms are replaced by fluorine atoms, the more preferred it is, from the perspective of strong acid strength and high transparency to high-energy light and electron beams with a wavelength of less than 250 nm. The ratio of fluorine atoms in the fluoroalkyl group, i.e., the fluorination rate, is preferably 70 to 100%, and more preferably 90 to 100%. The most preferred is a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0252] In formula (b-2), V 102 、V 103 Each independently represents a single bond, an alkylene group or a fluoroalkylene group, and each of them can be exemplified by the same group as V in formula (b-1): 101 Same bond or group.

[0253] In formula (b-2), L 101 , L 102 Each is independently a single bond or an oxygen atom.

[0254] (Cation part)

[0255] In formula (b-1), formula (b-2), and formula (b-3), M' m+ represents an m-valent onium cation. The onium cation is preferably a sulfonium cation.

[0256] m is an integer greater than or equal to 1.

[0257] As M' m+ The organic cation represented by is not particularly limited, and organic cations known as cation parts constituting conventionally known onium salt-based acid generators can be appropriately used. The cation part is preferably a sulfonium cation.

[0258] Specific examples include sulfonium cations represented by the following formula (bc-1) or (bc-2).

[0259] [Chemical formula 13]

[0260]

[0261] (In formula (bc-1) and (bc-2), R bc1 ~R bc8 Each independently represents an aryl group, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. bc1 ~R bc5They may be bonded to each other to form a ring together with the sulfur atom in the formula. bc6 ~R bc7 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. bc8 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO-containing group which may have a substituent 2 -cyclic group. bc1 represents -C(=O)- or -C(=O)-O-. )

[0262] In formula (bc-1) and (bc-2), regarding R bc1 ~R bc5 The aryl group includes an unsubstituted aryl group having a carbon number of 6 to 20. The unsubstituted aryl group is preferably a phenyl group or a naphthyl group.

[0263] As R bc1 ~R bc5 The alkyl group preferably has 1 to 30 carbon atoms.

[0264] As R bc1 ~R bc5 The cycloalkyl group preferably has 3 or more and 30 or less carbon atoms.

[0265] As R bc1 ~R bc5 The number of carbon atoms of the alkenyl group is preferably 2 or more and 10 or less.

[0266] As R bc1 ~R bc5 and R bc8 Examples of the substituent that may be possessed include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following formulae (bc-r-1) to (bc-r-7).

[0267] [Chemical formula 14]

[0268]

[0269] (In formula (bc-r-1) to (bc-r-7), R' b11 Each is independently a hydrogen atom, a cyclic group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.)

[0270] About being R' b11 The cyclic group is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. The alicyclic hydrocarbon group may be saturated or unsaturated. The alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group.

[0271] As R' b11 The number of carbon atoms of the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms of the substituent.

[0272] About being R' b11 Specific examples of the aromatic hydrocarbon ring contained in the aromatic hydrocarbon group include a benzene ring, a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and a biphenyl ring.

[0273] As R' b11 The cyclic group may include an aromatic heterocycle in which a portion of the carbon atoms constituting the aromatic hydrocarbon ring is replaced by a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0274] About being R' b11 Specific examples of the aromatic hydrocarbon group include phenyl, naphth-1-yl, naphth-2-yl, 4-phenylphenyl, 3-phenylphenyl and 2-phenylphenyl.

[0275] As R' b11 The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0276] The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is a cycloalkyl group. The number of carbon atoms of the cycloalkyl group is preferably 3 or more and 6 or less. Preferred specific examples of the cycloalkyl group include cyclopentyl and cyclohexyl. As a polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a polycyclic alkane is preferred. The number of carbon atoms of the polycyclic alkane is preferably 7 or more and 30 or less. Preferred specific examples of polycyclic alkanes include polycyclic alkanes with polycyclic skeletons of bridged ring systems such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane; polycyclic alkanes with polycyclic skeletons of fused ring systems such as cyclic groups with steroidal skeletons.

[0277] Among them, regarding R' b11 The alicyclic hydrocarbon group is preferably adamantyl and norbornyl, and more preferably adamantyl.

[0278] As R' b11 The cyclic hydrocarbon group may be a heterocyclic ring containing a heteroatom. Specifically, there can be mentioned a lactone-containing cyclic group, a -SO 2 -cyclic groups, other heterocyclic groups.

[0279] Regarding R' in formulas (bc-r-1) to (bc-r-7) b11 Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.

[0280] The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

[0281] The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and still more preferably a methoxy group and an ethoxy group.

[0282] As the halogen atom as a substituent, a fluorine atom is preferred.

[0283] Examples of the haloalkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which a part or all of the hydrogen atoms are substituted with halogen atoms.

[0284] The carbonyl group as a substituent is a methylene group (-CH 2 -) to be substituted.

[0285] As R' b11 The alkyl group may be linear or branched.

[0286] The number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.

[0287] The branched alkyl group preferably has 3 or more and 20 or less carbon atoms, more preferably 3 or more and 15 or less carbon atoms, and even more preferably 3 or more and 10 or less carbon atoms.

[0288] Specific examples of the branched alkyl group include isopropyl, sec-butyl, isobutyl, sec-pentyl, 2-methylbutyl, isopentyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl and 4-methylpentyl.

[0289] As R' b11 The alkenyl group may be linear or branched.

[0290] The number of carbon atoms in the linear alkenyl group is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, particularly preferably 3.

[0291] Specific examples of the straight-chain alkenyl group include vinyl, 1-propenyl, 2-propenyl (allyl), and butenyl.

[0292] Specific examples of the branched alkenyl group include 1-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0293] The alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group and a propenyl group, and particularly preferably a vinyl group.

[0294] About being R' b11 The substituents that the alkyl and alkenyl groups may have include, for example, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above-mentioned R' b11 Cyclic groups, etc.

[0295] Among them, as R' b11 , preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, preferably a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, a cyclic group containing a lactone, a -SO- 2 -cyclic groups, etc.

[0296] R in formula (bc-1) or (bc-2) bc1 ~R bc3 When two of the groups are bonded to each other to form a ring together with the sulfur atom in the formula, the ring may be mediated by a sulfur atom, an oxygen atom, a nitrogen atom or other hetero atom, a carbonyl group, -SO-, -SO 2 -、-SO 3 -, -COO-, -CONH- or -N(RN)- (wherein RN is an alkyl group having 1 to 5 carbon atoms). As the formed ring, the one ring containing the sulfur atom in the formula in its ring skeleton is preferably a 3-10-membered ring including the sulfur atom, and particularly preferably a 5-7-membered ring. Specific examples of the ring include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a thiophenethiothiol ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0297] R bc6 ~R bc7 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. bc6 ~R bc7 It is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. bc6 and R bc7 When both are alkyl groups, R bc6 and R bc7 They may be bonded to each other to form a ring.

[0298] R bc8 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO-containing group which may have a substituent 2 -cyclic group.

[0299] R bc8 In the case of an aryl group, the aryl group is preferably an unsubstituted aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthyl-1-yl group, and a naphthyl-2-yl group.

[0300] R bc8 In the case of an alkyl group, the alkyl group may be a chain or cyclic alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 30.

[0301] R bc8 In the case of an alkenyl group, the number of carbon atoms of the alkenyl group is preferably 2 or more and 10 or less.

[0302] As R bc8 The substituents may contain -SO 2 - is preferably a cyclic group containing -SO 2 -polycyclic group".

[0303] Preferred cations represented by formula (bc-1) are shown below.

[0304] [Chemical formula 15]

[0305]

[0306] [Chemical formula 16]

[0307]

[0308] [Chemical formula 17]

[0309]

[0310] (In formulas (bc-1-35) to (bc-1-37), g1, g2, and g3 represent the number of repetitions of the group in parentheses, g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.) [Chemical Formula 18]

[0311]

[0312] [Chemical formula 19]

[0313]

[0314] [Chemical formula 20]

[0315]

[0316] [Chemical formula 21]

[0317]

[0318] (Where R” b11 is a hydrogen atom or a substituent, the substituent is bc1 ~R bc5 and R bc8 The substituents that may be possessed are similar.)

[0319] [Chemical formula 22]

[0320]

[0321] Preferred specific examples of the cation represented by the formula (bc-2) include cations represented by the following formulae (bc-2-1) to (bc-2-6).

[0322] [Chemical formula 23]

[0323]

[0324] The cation part of the acid generator (B) is represented by the formula (bc-1) and (bc-2). Among them, the cations represented by the formulas (bc-1-1) to (bc-1-6) and (bc-1-52) to (bc-1-60) are preferred.

[0325] Among the above-mentioned acid generators (B), compounds represented by the following formula (b-1-1) are preferred.

[0326] [Chemical formula 24]

[0327]

[0328] (In formula (b-1-1), R b1 ~R b3 Each independently represents an aryl group which may have a substituent. b1 ~R b3 Any two of R may be bonded to each other to form a ring together with the sulfur atom in the formula. 101 is a cyclic group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. 101 is a divalent linking group or a single bond containing an oxygen atom. 101 is a single bond or an oxygen atom. )

[0329] In formula (b-1-1), R 101 , Y 101、V 101 and R 102 With R in formula (b-1) 101 , Y 101 、V 101 and R 102 same.

[0330] R b1 ~R b3 Each is independently an aryl group which may have a substituent. b1 ~R b3 Any two of R may be bonded to each other to form a ring together with the sulfur atom in the formula. b1 ~R b3 The aryl group in the formula (bc-1) and R bc1 ~R bc3 The substituents that the aryl group may have are the same as those in R of the above formula (bc-1). bc1 ~R bc3 The aryl group in may have the same substituents.

[0331] As R b1 ~R b3 Any two of the above are bonded to each other to form a ring together with the sulfur atom in the formula, and examples thereof include R bc1 ~R bc3 The rings are the same as the rings formed by bonding to each other together with the sulfur atom in the formula.

[0332] In the first composition, the acid generator (B) may be used alone or in combination of two or more.

[0333] In the first composition, the content of the acid generator (B) is 0.5 to 30 parts by mass, preferably 1 to 10 parts by mass, and more preferably 3 to 7 parts by mass, based on 100 parts by mass of the resin (A).

[0334] When the content of the acid generator (B) is within the above range, the first composition having excellent lithography characteristics can be easily obtained.

[0335] 〔Non-ionic acid generator〕

[0336] Among the preferred examples of the nonionic acid generator described above, oxime sulfonate acid generators and imide sulfonate acid generators are preferred.

[0337] Examples of the oxime sulfonate acid generator include compounds represented by the following formula (b-3).

[0338] [Chemical formula 25]

[0339]

[0340] In the above formula (b-3), R b200 represents a monovalent, divalent or trivalent organic group. b201 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic group. n represents an integer of 1 to 3.

[0341] In the above formula (b-3), the aromatic group includes, for example, aryl groups such as phenyl and naphthyl, and heteroaryl groups such as furyl and thienyl. These may have one or more appropriate substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, etc.

[0342] In addition, as R b201 , particularly preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent, and examples thereof include methyl, ethyl, propyl, butyl and trifluoromethyl. b200 is an aromatic group and R b201 A compound which is an alkyl group having 1 to 4 carbon atoms which may have a substituent.

[0343] In the above formula (b-3), when n=1, R is preferably b200 is phenyl, methylphenyl or methoxyphenyl, and R b201 In this case, specific examples of the compound represented by formula (b-3) include α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, and α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile.

[0344] In the formula (b-3), when n=2, specific examples of the compound represented by the above formula (a1) include compounds represented by the following formulas.

[0345] [Chemical formula 26]

[0346]

[0347] Examples of the imidosulfonate acid generator include compounds represented by the following formula (b-4).

[0348] [Chemical formula 27]

[0349]

[0350] In the above formula (b-4), R b202 is a monovalent organic group. b203 , R b204 , R b205 and R b206 Each independently represents a hydrogen atom or a monovalent organic group. b203 With R b204 , Rb204 With R b205 , R b205 With R b206 , R b206 With R b207 , or R b207 With R b208 Each may be bonded to each other to form a ring.

[0351] As R b202 The organic group is not particularly limited within the scope of not hindering the purpose of the present invention. The organic group may be a hydrocarbon group, or may contain heteroatoms such as O, N, S, P, or halogen atoms. In addition, the structure of the organic group may be linear, branched, cyclic, or a combination of these structures.

[0352] About R b202 Preferred organic groups include aliphatic hydrocarbon groups having 1 to 18 carbon atoms which may be substituted with halogen atoms and / or alkylthio groups, aryl groups having 6 to 20 carbon atoms which may have substituents, aralkyl groups having 7 to 20 carbon atoms which may have substituents, alkylaryl groups having 7 to 20 carbon atoms which may have substituents, camphor-10-yl groups, and groups represented by the following formula (b-4-1).

[0353] -R b209 -(O) a -R b210 -(O) b -Y 1 -R b211 ···(b-4-1)

[0354] In the above formula (b-4-1), Y 1 It is a single bond or an alkanediyl group having 1 to 4 carbon atoms. b209 and R b210 Each is an alkanediyl group having 2 to 6 carbon atoms which may be substituted by a halogen atom, or an arylene group having 6 to 20 carbon atoms which may be substituted by a halogen atom. b211 It is an alkyl group having 1 to 18 carbon atoms which may be substituted by a halogen atom, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, or an aralkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom. a and b are each 0 or 1, and at least one of a and b is 1.

[0355] As R b202 When the organic group has a halogen atom as a substituent, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

[0356] As Rb202 When the organic group is an alkyl group having 1 to 18 carbon atoms substituted with an alkylthio group, the alkylthio group preferably has 1 to 18 carbon atoms.

[0357] Examples of the alkylthio group having 1 to 18 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a sec-butylthio group, a tert-butylthio group, an isobutylthio group, an n-pentylthio group, an isopentylthio group, a tert-pentylthio group, an n-hexylthio group, an n-heptylthio group, an isoheptylthio group, a tert-heptylthio group, an n-octylthio group, an isooctylthio group, a tert-octylthio group, a 2-ethylhexylthio group, an n-nonylthio group, an n-decylthio group, an n-undecylthio group, an n-dodecylthio group, an n-tridecylthio group, an n-tetradecylthio group, an n-pentadecylthio group, an n-hexadecylthio group, an n-heptadecylthio group and an n-octadecylthio group.

[0358] As R b202 When the organic group is an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, the aliphatic hydrocarbon group may contain an unsaturated double bond.

[0359] The structure of the aliphatic hydrocarbon group is not particularly limited, and may be linear, branched, cyclic, or a combination of these structures.

[0360] About R b202 When the organic group is an alkenyl group, preferred examples include an allyl group and a 2-methyl-2-propenyl group.

[0361] About R b202 Preferred examples of the organic group in the case where it is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-hexane-2-yl, n-hexane-3-yl, n-heptyl, n-heptane-2-yl, n-heptane-3-yl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl.

[0362] As R b202 When the organic group is an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

[0363] About R b202 Preferred examples of the organic group in the case where it is an aliphatic hydrocarbon group substituted with a halogen atom include trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoro-n-propyl, 3-bromopropyl, nonafluoro-n-butyl, tridecafluoro-n-hexyl, heptadecafluoro-n-octyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoro-n-propyl, 1,1,2,2-tetrafluoro-n-propyl, 3,3,3-trifluoro-n-propyl, 2,2,3,3,3-pentafluoro-n-propyl, 2-norbornyl-1,1-difluoroethyl, 2-norbornyltetrafluoroethyl and 3-adamantyl-1,1,2,2-tetrafluoropropyl.

[0364] About R b202 Preferred examples when the organic group is an aliphatic hydrocarbon group substituted with an alkylthio group include 2-methylthioethyl, 4-methylthio-n-butyl and 2-n-butylthioethyl.

[0365] About R b202 Preferred examples of the organic group in the case where the organic group is an aliphatic hydrocarbon group substituted with a halogen atom or an alkylthio group include 3-methylthio-1,1,2,2-tetrafluoro-n-propyl group.

[0366] About R b202 When the organic group is an aryl group, preferred examples include phenyl, naphthyl and biphenyl.

[0367] About R b202 Preferred examples when the organic group is an aryl group substituted with a halogen atom include pentafluorophenyl, chlorophenyl, dichlorophenyl and trichlorophenyl.

[0368] About R b202 Preferred examples when the organic group is an aryl group substituted with an alkylthio group include 4-methylthiophenyl, 4-n-butylthiophenyl, 4-n-octylthiophenyl and 4-n-dodecylthiophenyl.

[0369] About R b202 Preferred examples when the organic group is an aryl group substituted with a halogen atom or an alkylthio group include 1,2,5,6-tetrafluoro-4-methylthiophenyl, 1,2,5,6-tetrafluoro-4-n-butylthiophenyl and 1,2,5,6-tetrafluoro-4-n-dodecylthiophenyl.

[0370] About R b202 Preferred examples when the organic group is an aralkyl group include a benzyl group, a phenethyl group, a 2-phenylpropane-2-yl group, a diphenylmethyl group, and a triphenylmethyl group.

[0371] About Rb202 Preferred examples when the organic group is an aralkyl group substituted with a halogen atom include pentafluorophenylmethyl, phenyldifluoromethyl, 2-phenyltetrafluoroethyl and 2-(pentafluorophenyl)ethyl.

[0372] About R b202 When the organic group is an aralkyl group substituted with an alkylthio group, a preferred example is p-methylthiobenzyl.

[0373] About R b202 Preferred examples of the organic group in the case where the organic group is an aralkyl group substituted with a halogen atom or an alkylthio group include 2-(2,3,5,6-tetrafluoro-4-methylthiophenyl)ethyl.

[0374] About R b202 Preferred examples of the organic group in the case where the alkylaryl group is an alkyl aryl group include 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-n-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-n-hexylphenyl, 4-cyclohexylphenyl, 4-n-octylphenyl, 4-(2-ethyl-n-hexyl)phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6 -dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-pentylphenyl, 2,5-di-tert-octylphenyl, 2-cyclohexylphenyl, 3-cyclohexylphenyl, 4-cyclohexylphenyl, 2,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl.

[0375] The group represented by the formula (b-4-1) is a group containing an ether group.

[0376] In the formula (b-4-1), Y 1 Examples of the alkane diyl group having 1 to 4 carbon atoms include methylene, ethane-1,2-diyl, ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-2,3-diyl and butane-1,2-diyl.

[0377] In the formula (b-4-1), R b209 or R b210The alkane diyl group having 2 to 6 carbon atoms represented by alkylene diyl group includes ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,2-diyl, pentane-1,5-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-2,3-diyl, hexane-1,6-diyl, hexane-1,2-diyl, hexane-1,3-diyl, hexane-1,4-diyl, hexane-2,5-diyl, hexane-2,4-diyl and hexane-3,4-diyl.

[0378] In formula (b-4-1), R b209 or R b210 In the case of an alkane diyl group having 2 to 6 carbon atoms substituted by a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the alkane diyl group substituted by a halogen atom include tetrafluoroethane-1,2-diyl, 1,1-difluoroethane-1,2-diyl, 1-fluoroethane-1,2-diyl, 1,2-difluoroethane-1,2-diyl, hexafluoropropane-1,3-diyl, 1,1,2,2,-tetrafluoropropane-1,3-diyl, and 1,1,2,2,-tetrafluoropentane-1,5-diyl.

[0379] In the formula (b-4-1), R b209 or R b210 Examples of the arylene group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,5-dimethyl-1,4-phenylene, biphenyl-4,4'-diyl, diphenylmethane-4,4'-diyl, 2,2-diphenylpropane-4,4'-diyl, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl and naphthalene-2,7-diyl.

[0380] In formula (b-4-1), R b209 or R b210 In the case of an arylene group substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom. Examples of the arylene group substituted with a halogen atom include 2,3,5,6-tetrafluoro-1,4-phenylene.

[0381] In the formula (b-4-1), R b211The alkyl group having 1 to 18 carbon atoms and which may have a branch may be represented by methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-hexane-2-yl, n-hexane-3-yl, n-heptyl, n-heptane-2-yl, n-heptane-3-yl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl.

[0382] In formula (b-4-1), R b211 In the case of an alkyl group having 1 to 18 carbon atoms substituted by a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the alkyl group substituted by a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a nonafluoro-n-butyl group, a tridecafluoro-n-hexyl group, a heptadecafluoro-n-octyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoro-n-propyl group, a 1,1,2,2-tetrafluoro-n-propyl group, a 3,3,3-trifluoro-n-propyl group, a 2,2,3,3,3-pentafluoro-n-propyl group, and a 1,1,2,2-tetrafluoro-tetradecyl group.

[0383] In formula (b-4-1), R b211 In the case of an alicyclic hydrocarbon group having 3 or more and 12 or less carbon atoms, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

[0384] In formula (b-4-1), R b211 In the case of an aryl group, a halogenated aryl group, an aralkyl group, or a halogenated aralkyl group, preferred examples of these groups are the same as those of R 22a The same is true for these groups.

[0385] Among the groups represented by formula (b-4-1), the preferred group is R b209 A group in which the carbon atom bonded to the sulfur atom in the group represented by is substituted with a fluorine atom. The number of carbon atoms in this preferred group is preferably 2 or more and 18 or less.

[0386] As R b202 , preferably a perfluoroalkyl group having 1 to 8 carbon atoms. In addition, from the perspective of easily forming a high-definition resist pattern, a camphor-10-yl group is also preferred as R b202 .

[0387] In formula (b-4), R b203 ~R b208 is a hydrogen atom or a monovalent organic group. b203 With R b204 , R b204 With R b205 , R b205 With R b206 , R b206 With R b207 , or R b207 With R b208 Each of them may be bonded to each other to form a ring. b205 With R b206 It can be bonded to form a 5-membered ring together with a naphthalene ring to form an acenaphthene skeleton.

[0388] The monovalent organic group is preferably: an alkyl group or alkoxy group which may be substituted by an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom and may have a branch and has 4 to 18 carbon atoms; a heterocyclyloxy group; an alkylthio group which may be substituted by an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom and may have a branch and has 4 to 18 carbon atoms; and a heterocyclylthio group.

[0389] Furthermore, a group in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is replaced with -CO- is also preferred.

[0390] The alkoxy group is preferably a group interrupted by an -O-CO- bond or an -O-CO-NH- bond. The left end of the -O-CO- bond and the -O-CO-NH- bond is the side of the alkoxy group that is close to the naphthalene dicarboxylic acid core.

[0391] In addition, an alkylthio group having 4 to 18 carbon atoms which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom and may have a branch is also preferred as R. b203 ~R b208 .

[0392] A group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is replaced with -CO- is also preferred.

[0393] The alkylthio group is preferably a group interrupted by an -O-CO- bond or an -O-CO-NH- bond. The left end of the -O-CO- bond and the -O-CO-NH- bond is the side of the alkylthio group that is close to the naphthalene dicarboxylic acid core.

[0394] As R b203 ~R b208 , preferably, Rb204 is an organic group and R b203 and R b205 ~R b208 is a hydrogen atom, or, R b205 is an organic group and R b203 , R b204 and R b206 ~R b208 is a hydrogen atom. b203 ~R b208 All may be hydrogen atoms.

[0395] As R b203 ~R b208 Examples of the unsubstituted alkyl group include n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl.

[0396] As R b203 ~R b208 Examples of the unsubstituted alkoxy group include n-butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, n-pentyloxy, isopentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyl, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy and n-octadecyloxy.

[0397] As R b203 ~R b208 Examples of the unsubstituted alkylthio group include n-butylthio, sec-butylthio, tert-butylthio, isobutylthio, n-pentylthio, isopentylthio, tert-pentylthio, n-hexylthio, n-heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecylthio, n-hexadecylthio, n-heptadecylthio and n-octadecylthio.

[0398] R b203 ~R b208In the case of an alkyl group, an alkoxy group or an alkylthio group substituted with an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo[2.1.1]hexane, bicyclo[2.2.1]heptane, bicyclo[3.2.1]octane, bicyclo[2.2.2]octane and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

[0399] In R b203 ~R b208 In the case of an alkyl group, an alkoxy group or an alkylthio group substituted by a heterocyclic group, or R 23a ~R 28a In the case of a heterocyclic group, examples of the heterocyclic ring constituting the main skeleton of the heterocyclic group or the heterocyclic group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, 4-nitrogen Indene (pyrindine), indolizine, indole, indazole, purine, quinolizine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, benzimidazole, phenanthroline, carbazole, carboline, phenazine, triazaanthracene (anthyridine), thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofurazan, naphthyimidazole, benzotriazole, tetraazaindene. In addition, saturated heterocyclic rings obtained by hydrogenating the rings having conjugated bonds in these heterocyclic rings are also preferred.

[0400] As the heterocyclic group or the heterocyclic group contained in the heterocyclic group substituted with the alkyl group, the alkoxy group or the alkylthio group, preferably a group obtained by removing one hydrogen atom from the above heterocyclic ring.

[0401] As R b203 ~R b208Examples of the alkoxy group containing an alicyclic hydrocarbon group include a cyclopentyloxy group, a methylcyclopentyloxy group, a cyclohexyloxy group, a fluorocyclohexyloxy group, a chlorocyclohexyloxy group, a cyclohexylmethyloxy group, a methylcyclohexyloxy group, a norbornyloxy group, an ethylcyclohexyloxy group, a cyclohexylethyloxy group, a dimethylcyclohexyloxy group, a methylcyclohexylmethyloxy group, a norbornylmethyloxy group, a trimethylcyclohexyloxy group, a 1-cyclohexylbutyloxy group, an adamantyloxy group, a menthyloxy group, an n-butylcyclohexyloxy group, a tert-butylcyclohexyloxy group, a bornyloxy group, an isobornyloxy group, a decahydronaphthyloxy group, a dicyclopentadienyloxy group, a 1-cyclohexylpentyloxy group, a methyladamantyloxy group, an adamantylmethyloxy group, a 4-pentylcyclohexyloxy group, a cyclohexylcyclohexyloxy group, an adamantylethyloxy group, and a dimethyladamantyloxy group.

[0402] As R b203 ~R b208 Examples of the heterocyclyloxy group include tetrahydrofuranyloxy, furfuryloxy, tetrahydrofurfuryloxy, tetrahydropyranyloxy, butyrolactonyloxy and indolyloxy.

[0403] As R b203 ~R b208 Examples of the alkylthio group containing an alicyclic hydrocarbon group include a cyclopentylthio group, a cyclohexylthio group, a cyclohexylmethylthio group, a norbornylthio group and an isonorbornylthio group.

[0404] As R b203 ~R b208 In the case of a heterocyclic thio group, examples include a furfurylthio group and a tetrahydrofuranylthio group.

[0405] As R b203 ~R b208 Examples of groups in which a methylene group at any position not adjacent to the oxygen atom of an alkoxy group is replaced with -CO- include 2-oxobutyl-1-oxy, 2-oxopentyl-1-oxy, 2-oxohexyl-1-oxy, 2-oxoheptyl-1-oxy, 2-oxooctyl-1-oxy, 3-oxobutyl-1-oxy, 4-oxopentyl-1-oxy, 5-oxohexyl-1-oxy, 6-oxoheptyl-1-oxy, 7-oxooctyl-1-oxy, 3-methyl-2-oxopentane-4-oxy, 2-oxopentane-4-oxy, 2-methyl-2-oxopentane-4-oxy, 3-oxoheptane-5-oxy, and 2-adamantanone-5-oxy.

[0406] As R b203 ~R b208Examples of the group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is replaced with -CO- include 2-oxobutyl-1-thio, 2-oxopentyl-1-thio, 2-oxohexyl-1-thio, 2-oxoheptyl-1-thio, 2-oxooctyl-1-thio, 3-oxobutyl-1-thio, 4-oxopentyl-1-thio, 5-oxohexyl-1-thio, 6-oxoheptyl-1-thio, 7-oxooctyl-1-thio, 3-methyl-2-oxopentane-4-thio, 2-oxopentane-4-thio, 2-methyl-2-oxopentane-4-thio and 3-oxoheptane-5-thio.

[0407] Specific examples of the compound represented by formula (b-4) include the following compounds.

[0408] [Chemical formula 28]

[0409]

[0410] [Chemical formula 29]

[0411]

[0412] [Chemical formula 30]

[0413]

[0414] [Chemical formula 31]

[0415]

[0416] [Chemical formula 32]

[0417]

[0418] [Chemical formula 33]

[0419]

[0420] [Chemical formula 34]

[0421]

[0422] [Chemical formula 35]

[0423]

[0424] [Chemical formula 36]

[0425]

[0426] [Chemical formula 37]

[0427]

[0428] [Compound having a blocked isocyanate group (C)]

[0429] The first composition may include a compound (C) having an isocyanate group blocked by a blocking agent. The compound (C) may be obtained by allowing a blocking agent to act on a compound having an isocyanate group. As the compound (C), preferably, a compound (c1) having two or more blocked isocyanate groups.

[0430] Examples of the compound having an isocyanate group include chain aliphatic isocyanates such as hexyl isocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; alicyclic isocyanates such as cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated toluene diisocyanate; phenyl isocyanate; , naphthyl isocyanate, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylenediisocyanate, dimethyldiaminobiphenyl diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate and other aromatic isocyanates; dicyclohexylmethane-4,4'-diisocyanate, their biuret bodies, isocyanurate bodies, trimethylolpropane adducts, etc.

[0431] The compound having an isocyanate group may also be a polymer compound having an isocyanate group. As the polymer compound having an isocyanate group, a polymer of a (meth)acrylate having an isocyanate group is preferred. As the (meth)acrylate having an isocyanate group, 2-methacryloyloxyethyl isocyanate and 2-acryloyloxyethyl isocyanate are preferred.

[0432] The terminal blocking agent is as described above with respect to the unit (a3) ​​contained in the resin (A).

[0433] As the compound (C), a homopolymer consisting only of the unit (a3) ​​described above for the resin (A) or a copolymer containing the aforementioned unit (a3) ​​and not belonging to the resin (A) may be used.

[0434] Regarding the amount of compound (C) used, the total ratio of the number of moles of hydroxyl groups possessed by all components other than the solvent (S) contained in the first composition to the number of moles of blocked isocyanate groups possessed by all components other than the solvent (S) contained in the first composition is 30 mol% or more and 95 mol% or less, relative to the total number of moles of all structural units of the resin (A), the number of moles of hydroxyl groups possessed by components other than the resin (A) and the solvent (S), and the number of moles of blocked isocyanate groups possessed by components other than the resin (A) and the solvent (S).

[0435] [Compound having two or more hydroxyl groups (D)]

[0436] The first composition may include a compound (D) having two or more hydroxyl groups. The compound (D) is not particularly limited as long as it is a compound having two or more hydroxyl groups. As the compound (D), various known polyols can be used as long as the desired effect is not impaired. The polyol may also include an aromatic group.

[0437] Examples of the polyol containing no aromatic group include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, mannitol, sorbitan, sucrose, glucose, mannose, methyl glucoside, tris(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)isocyanurate, and methyl glucoside. acid), polyvinyl alcohol, partial hydrolyzate of polyvinyl acetate, etc.

[0438] Examples of the aromatic polyol include hydroquinone, resorcinol, and catechol; pyrogallol, 1,2,4-pyrogallol, and other pyrogallols; 1,2-naphthalene diol, 1,3-naphthalene diol, 1,4-naphthalene diol, 1,5-naphthalene diol, 1,6-naphthalene diol, 1,7-naphthalene diol, 2,3-naphthalene diol, 2,6-naphthalene diol, and 2,7-naphthalene diol; 1,4,5-naphthalene diol, 1,2,4-naphthalene diol, 1,5-naphthalene diol, 1,6-naphthalene diol, 1,7-naphthalene diol, 2,3-naphthalene diol, 2,6-naphthalene diol, and 2,7-naphthalene diol; ,3,8-naphthalenetriol and 1,2,7-naphthalenetriol and other naphthalenetriols; bisphenols such as bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol S and bisphenol Z; tetrahydroxybiphenyls such as 3,3',4,4'-tetrahydroxybiphenyl and 3,3',5,5'-tetrahydroxybiphenyl; calixarene; Novolac resins such as phenol Novolac, cresol Novolac and naphthol Novolac.

[0439] Regarding the amount of compound (D) used, the total ratio of the number of moles of hydroxyl groups possessed by all components other than the solvent (S) contained in the first composition to the number of moles of blocked isocyanate groups possessed by all components other than the solvent (S) contained in the first composition is 30 mol% or more and 95 mol% or less, relative to the total number of moles of all structural units of the resin (A), the number of moles of hydroxyl groups possessed by components other than the resin (A) and the solvent (S), and the number of moles of blocked isocyanate groups possessed by components other than the resin (A) and the solvent (S).

[0440] [Solvent (S)]

[0441] The first composition may contain a solvent (S) for purposes such as coating properties and viscosity adjustment. Typically, an organic solvent can be used as the solvent (S). The type of the organic solvent is not particularly limited as long as it can uniformly dissolve or disperse the components contained in the first composition.

[0442] The solvent (S) preferably does not have a group containing active hydrogen that is reactive with an isocyanate group. Examples of the group containing active hydrogen include a hydroxyl group, a mercapto group, an amino group, and a carboxyl group.

[0443] Specific examples of the solvent (S) that can be incorporated into the first composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, (Poly) alkylene glycol monoalkyl ethers such as propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, Ketones such as cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-propyl acetate Butyl ester, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; nitrogen-containing polar organic solvents such as N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N,N',N'-tetramethylurea, etc.

[0444] Among them, from the aspect of not having a group containing active hydrogen, preferred are (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl ethoxyacetate. , 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; nitrogen-containing polar organic solvents such as N-methylpyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N,N',N'-tetramethylurea, etc.

[0445] The solvent (S) can be used alone or in combination of two or more.

[0446] The amount of the solvent (S) used is not particularly limited within the range that does not impair the desired effect. From the perspective of film forming properties, the solvent (S) is used so that the solid content concentration of the first composition is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.

[0447] [Other ingredients (E)]

[0448] The first composition may contain additives as needed. Examples of such additives include stabilizers, adhesion enhancers, crosslinking agents, curing accelerators, surfactants, quenchers, antioxidants, adhesion aids, defoamers, polymerization inhibitors such as thermal polymerization inhibitors, etc. These additives may be used alone or in combination of two or more.

[0449] As the quencher, a low molecular weight compound (non-polymer) is generally used. As the quencher, for example, amines such as aliphatic amines and aromatic amines can be cited. As the quencher, 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 of the aliphatic amine is preferably 1 or more and 20 or less.

[0450] Examples of the aliphatic amine include ammonia (NH3 ) in which at least one of the hydrogen atoms is replaced by an alkyl group having 20 or less carbon atoms, ammonia (NH 3 ) is substituted with a hydroxyalkyl group at least one of the hydrogen atoms of the alkanolamine, and a cyclic amine.

[0451] Specific examples of alkylamines and alkanolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; 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, stearyldiethanolamine, and lauryldiethanolamine. Among these, trialkylamines and alkanolamines are preferred.

[0452] Examples of the cyclic amine include nitrogen-containing heterocyclic compounds. The nitrogen-containing heterocyclic compound may be a monocyclic aliphatic amine or a polycyclic aliphatic amine.

[0453] Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. The number of carbon atoms in the aliphatic polycyclic amine is preferably 6 or more and 10 or less. Specific examples of the aliphatic polycyclic amine include 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.

[0454] Specific examples of other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, and tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine.

[0455] Specific examples of the aromatic amine include aniline, pyridine, 2,6-diphenylpyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, 2,2′-bipyridine, and 4,4′-bipyridine.

[0456] These quenchers may be used alone or in combination of two or more. The amount of the quencher contained in the first composition is usually 0.01 parts by mass or more and 5.0 parts by mass or less relative to 100 parts by mass of the resin (A).

[0457] [Method for producing the first composition]

[0458] After mixing the components described above in predetermined amounts, the mixture is stirred until uniform, thereby obtaining the first composition.

[0459] <Second Composition>

[0460] The second composition contains a resin (A) whose solubility in an alkali can be increased by the action of an acid (hereinafter, also referred to as "resin (A)"), an acid generator (B) that generates an acid by irradiation with activating light or radiation (hereinafter, also referred to as "acid generator (B)"), and a compound (C) having a blocked isocyanate group.

[0461] The second composition can be cross-linked by the reaction between the hydroxyl group and the isocyanate group by heating.

[0462] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a hydroxyl-donating unit (a2). The resin (A) may also comprise a unit (a3) ​​containing a blocked isocyanate group and / or other units (a4).

[0463] In the second composition, the total ratio of the number of moles of hydroxyl groups possessed by all components other than the solvent (S) to the number of moles of blocked isocyanate groups possessed by all components other than the solvent (S) is preferably 30 mol% to 95 mol%, based on the total of the following i) to iii).

[0464] i) the number of moles of all structural units of the resin (A),

[0465] ii) the total number of moles of blocked isocyanate groups in the components other than the resin (A) and the solvent (S), and

[0466] iii) The total number of moles of hydroxyl groups in components other than the resin (A) and the solvent (S)

[0467] The number of moles of all structural units of the resin (A) contained in the second composition is the total number of moles of the unit (a1), the number of moles of the unit (a2), the number of moles of the unit (a3), and the number of moles of other units (a4).

[0468] By making the above ratio 30 mol% or more, the second composition is well cured by the reaction of the hydroxyl group and the isocyanate group. The above ratio is more preferably 40 mol% or more and 90 mol% or less, further preferably 45 mol% or more and 80 mol% or less, and particularly preferably 50 mol% or more and 70 mol% or less.

[0469] In the second composition, the total ratio of the number of moles of the units (a3) ​​of the resin (A) to the total number of moles of the blocked isocyanate groups possessed by the components other than the resin (A) and the solvent (S) is preferably 10 mol% or more, more preferably 20 mol% or more, relative to the total of the following i) to iii).

[0470] i) the number of moles of all structural units of the resin (A),

[0471] ii) the total number of moles of blocked isocyanate groups in the components other than the resin (A) and the solvent (S), and

[0472] iii) The total number of moles of hydroxyl groups in components other than the resin (A) and the solvent (S)

[0473] Hereinafter, regarding the components that may be included in the second composition, the resin (A) will be described. It should be noted that regarding the components that may be included in the second composition, the acid generator (B), the compound (C), the compound (D), the solvent (S) and the other components (E) are the same as described above for the first composition.

[0474] [Resin (A)]

[0475] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a hydroxyl-donating unit (a2). The resin (A) may also comprise a unit (a3) ​​containing a blocked isocyanate group and / or other units (a4).

[0476] These units (a1), units (a2), units (a3) ​​and units (a4) are respectively as described above for the first composition.

[0477] The ratio of the number of moles of the unit (a1) contained in the second composition to the number of moles of all the structural units of the resin (A) is not particularly limited within the range that does not impair the desired effect. The ratio of the number of moles of the unit (a1) contained in the second composition to the number of moles of all the structural units of the resin (A) is preferably 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol%.

[0478] When the resin (A) contains the aforementioned units (a1) and units (a2), the total of the molar ratio of the units (a1) and the molar ratio of the units (a2) relative to all the structural units of the resin (A) is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, further more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0479] Therefore, the total of the molar ratio of unit (a3) ​​and the molar ratio of unit (a4) relative to all structural units of resin (A) is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, further more preferably 20 mol% or less, and particularly preferably 10 mol% or less.

[0480] [Method for producing the second composition]

[0481] After mixing the components described above in predetermined amounts, the mixture is stirred until uniform, thereby obtaining the second composition.

[0482] <Third Composition>

[0483] The third composition comprises a resin (A) whose solubility in an alkali can be increased by the action of an acid (hereinafter, also referred to as “resin (A)”), an acid generator (B) that generates an acid by irradiation with activating light or radiation (hereinafter, also referred to as “acid generator (B)”), and a compound (D) having two or more hydroxyl groups.

[0484] The third composition can be cross-linked by the reaction between the hydroxyl group and the isocyanate group by heating.

[0485] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a unit (a3) ​​containing a blocked isocyanate group. The resin (A) may also comprise a hydroxyl group-donating unit (a2) and / or other units (a4).

[0486] In the third composition, the total ratio of the number of moles of hydroxyl groups possessed by all components excluding the solvent (S) to the number of moles of blocked isocyanate groups possessed by all components excluding the solvent (S) is 30 mol% to 95 mol% with respect to the total of the following i) to iii).

[0487] i) the number of moles of all structural units of the resin (A),

[0488] ii) the total number of moles of blocked isocyanate groups in the components other than the resin (A) and the solvent (S), and

[0489] iii) The total number of moles of hydroxyl groups in components other than the resin (A) and the solvent (S)

[0490] The number of moles of all structural units of the resin (A) contained in the third composition is the total number of moles of the unit (a1), the number of moles of the unit (a2), the number of moles of the unit (a3), and the number of moles of other units (a4).

[0491] By making the above ratio 30 mol% or more, the third composition is well cured by the reaction of the hydroxyl group and the isocyanate group. The above ratio is preferably 40 mol% or more and 90 mol% or less, more preferably 45 mol% or more and 80 mol% or less, and further preferably 50 mol% or more and 70 mol% or less.

[0492] In the third composition, the total ratio of the number of moles of the units (a3) ​​of the resin (A) to the total number of moles of the blocked isocyanate groups possessed by the components other than the resin (A) and the solvent (S) is preferably 10 mol% or more, more preferably 20 mol% or more, relative to the total of the following i) to iii).

[0493] i) the number of moles of all structural units of the resin (A),

[0494] ii) the total number of moles of blocked isocyanate groups in the components other than the resin (A) and the solvent (S), and

[0495] iii) The total number of moles of hydroxyl groups in components other than the resin (A) and the solvent (S)

[0496] Hereinafter, regarding the components that may be included in the third composition, the resin (A) will be described. It should be noted that regarding the components that may be included in the third composition, the acid generator (B), the compound (C), the compound (D), the solvent (S) and the other components (E) are the same as described above for the first composition.

[0497] [Resin (A)]

[0498] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a unit (a3) ​​containing a blocked isocyanate group. The resin (A) may also comprise a hydroxyl group-donating unit (a2) and / or other units (a4).

[0499] These units (a1), units (a2), units (a3) ​​and units (a4) are respectively as described above for the first composition.

[0500] The ratio of the number of moles of the units (a1) contained in the third composition to the number of moles of all the structural units of the resin (A) is not particularly limited within the range that does not impair the desired effect. The ratio of the number of moles of the units (a1) contained in the third composition to the number of moles of all the structural units of the resin (A) is preferably 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol%.

[0501] When the resin (A) contains the aforementioned units (a1) and units (a3), the total of the molar ratio of the units (a1) and the molar ratio of the units (a3) ​​relative to all the structural units of the resin (A) is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, further more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0502] Therefore, the total of the molar ratio of unit (a2) and the molar ratio of unit (a4) relative to all structural units of resin (A) is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, further more preferably 20 mol% or less, and particularly preferably 10 mol% or less.

[0503] [Method for producing the third composition]

[0504] After mixing the components described above in predetermined amounts, the mixture is stirred until uniform, thereby obtaining a third composition.

[0505] <<Method for manufacturing microlens>>

[0506] A microlens can be produced using the first composition, the second composition, or the third composition described above as a photosensitive resin composition.

[0507] Specifically, the microlens can be manufactured by a method including the following steps:

[0508] A step of coating the photosensitive resin composition on a substrate to form a coating film;

[0509] A step of selectively exposing the coating film to light in such a manner that dots are formed at positions on the substrate where microlenses are to be formed;

[0510] A step of developing the exposed coating film to obtain a patterned resin film including a plurality of dots in which dots are arranged at positions where microlenses are to be formed; and

[0511] A step of heating a resin film to deform dots by heat to form microlenses.

[0512] The substrate is not particularly limited, but a preferred substrate includes a silicon wafer on which an image element including a photodiode and the like and a color filter layer are provided.

[0513] The method for coating the photosensitive resin composition on the substrate is not particularly limited. As the coating method, for example, there can be mentioned a method using a contact transfer type coating device such as a roll coater, a reverse roll coater, a rod coater, a slit coater, a spin coater (rotary coating device), a curtain coating flow coater, and other non-contact type coating devices.

[0514] The photosensitive resin composition is applied on a substrate to a desired film thickness, and then the applied photosensitive resin composition is appropriately subjected to a heat treatment (pre-baking (post-apply bake, PAB) treatment) to form a coating film.

[0515] The prebaking method is not particularly limited. For example, it may be any of the following methods: (i) a method of drying at a temperature of 80°C to 120°C for 60 seconds to 120 seconds using a hot plate; (ii) a method of leaving the substrate at room temperature for several hours to several days; (iii) a method of placing the substrate in a warm air heater or an infrared heater for tens of minutes to several hours to remove the solvent from the coating film. The prebaking temperature is preferably 80°C to 250°C, more preferably 85°C to 220°C.

[0516] When the substrate includes a member having low heat resistance such as an organic photodiode, the prebaking can be performed at a temperature of, for example, 80° C. to 150° C., preferably 80° C. to 120° C.

[0517] The thickness of the coating film formed as described above is not particularly limited. The thickness of the coating film can be appropriately set according to the size of the microlens. Typically, the thickness of the coating film is preferably 30 nm to 1500 nm, and more preferably 50 nm to 500 nm.

[0518] Next, the coating film is exposed selectively so as to form dots at positions on the substrate where microlenses are to be formed.

[0519] The photosensitive resin composition is a positive photosensitive composition that becomes soluble in an alkaline developer by exposure. Therefore, exposure is performed through a photomask that does not transmit exposure light at the position where dots are to be formed.

[0520] Specifically, the exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer lasers. The amount of energy rays irradiated also varies depending on the composition of the photosensitive resin composition, but is preferably 30 to 2000 mJ / cm 2 about.

[0521] PEB (post exposure bake) may be performed, that is, heating the coating film after exposure and before development. PEB is performed at, for example, 80° C. to 180° C. for 30 seconds to 120 seconds.

[0522] The exposed coating film is developed, thereby forming a patterned resin film including a plurality of dots in which dots are arranged at positions where microlenses are to be formed.

[0523] Examples of the developer include organic developers such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

[0524] When a development treatment is performed, it is preferable to sufficiently remove the developer by a method such as drying by heating after development.

[0525] By heating the resin film patterned with a plurality of dots formed as described above, the dots are deformed by heat, thereby forming microlenses.

[0526] The heating temperature is, for example, preferably 120° C. to 240° C., more preferably 140° C. to 200° C. The heating time is, for example, preferably 2 minutes to 15 minutes, more preferably 5 minutes to 10 minutes.

[0527] As described above, the inventors of the present application provided the following (1) to (8).

[0528] (1) A photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) which generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating,

[0529] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group-donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group.

[0530] (2) a photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) which generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating,

[0531] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a hydroxyl group donating unit (a2).

[0532] The photosensitive resin composition further contains a compound (C) having a blocked isocyanate group.

[0533] (3) A photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) which generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating,

[0534] The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a unit (a3) ​​containing a blocked isocyanate group.

[0535] The photosensitive resin composition further contains a compound (D) having two or more hydroxyl groups.

[0536] (4) The photosensitive resin composition according to any one of (1) to (3), wherein the acid generator (B) has a fluorine atom.

[0537] (5) The photosensitive resin composition according to any one of (1) to (4), wherein the blocked isocyanate group-containing unit (a3) ​​or compound (C) has a group represented by the following formula (a3-2).

[0538] -NH-CO-R a34 ···(a3-2)

[0539] (In formula (a3-2), R a34 For lactam ring group, -OR a341 -CHR a342 -OR a343 or-ON=CR a344 2 The lactam ring group is a group obtained by removing a hydrogen atom from a nitrogen atom in a lactam ring. The nitrogen atom in the lactam ring group is bonded to a carbon atom in a carbonyl group. a341 is a divalent hydrocarbon group, R a342 is a hydrocarbon group having 1 to 5 carbon atoms, R a343 is a hydrocarbon group having 1 to 5 carbon atoms, R a344 Each independently represents a hydrocarbon group having 1 to 5 carbon atoms.)

[0540] (6) A microlens formed from a cured product of the photosensitive resin composition according to any one of (1) to (5).

[0541] (7) A method for manufacturing a microlens, comprising the following steps:

[0542] A step of coating the photosensitive resin composition according to any one of (1) to (5) on a substrate to form a coating film;

[0543] A step of selectively exposing the coating film to light in such a manner that dots are formed at positions on the substrate where microlenses are to be formed;

[0544] A step of developing the exposed coating film to obtain a patterned resin film including a plurality of dots in which dots are arranged at positions where microlenses are to be formed; and

[0545] A step of heating a resin film to deform dots by heat to form microlenses.

[0546] (8) A resin comprising a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group-donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group.

[0547] Example

[0548] Hereinafter, the present invention will be described in more detail using examples and comparative examples, but the present invention is not limited to these examples.

[0549] [Preparation of photosensitive resin composition]

[0550] As the resin (A), resins 1 to 11 described in Table 1 were used. Compositions A-1 to A-10 of the structural units of the resin (A) described in Table 1 are as follows.

[0551] In each of the following A-1 to A-10, the number attached to each structural unit is the ratio (mol %) of each unit relative to all the structural units contained in the resin (A).

[0552] [Chemical formula 38]

[0553]

[0554] [Chemical formula 39]

[0555]

[0556] [Chemical formula 40]

[0557]

[0558] [Chemical formula 41]

[0559]

[0560] [Chemical formula 42]

[0561]

[0562] The structural unit, weight average molecular weight (Mw), and dispersion degree (Mw / Mn) of the resin (A) used in Examples and Comparative Examples are as follows.

[0563] [Table 1]

[0564]

[0565] As the acid generator (B), the following B-1 to B-3 were used.

[0566] [Chemical formula 43]

[0567]

[0568] As the solvent (S), propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 50 / 50 (mass ratio) was used.

[0569] As the quencher, the following Q-1 and Q-2 were used.

[0570] Q-1: 2,6-diphenylpyridine

[0571] Q-2: Tri-n-pentylamine

[0572] As the compound (C), a homopolymer of an acrylate compound represented by the following formula (C-1) was used.

[0573] [Chemical formula 44]

[0574]

[0575] As the other component (E) other than the quencher, a cross-linking agent represented by the following formula (E-1) was used.

[0576] [Chemical formula 45]

[0577]

[0578] The resin (A), acid generator (B) and quencher of the type described in Table 2 were dispersed and dissolved in a solvent (S) at the ratio described in Table 2, respectively, to prepare a photosensitive resin composition. It should be noted that in Example 9, a compound (C) was also used. In Comparative Example 2, other components (E) other than the quencher were also used. The solvent (S) was used in such a way that the solid content concentration of the photosensitive resin composition became 10%.

[0579] [Table 2]

[0580]

[0581] Using the obtained photosensitive resin compositions of the respective Examples and Comparative Examples, the items described in Table 3 were evaluated by the following methods.

[0582] <Production of a Substrate with a Resin Film>

[0583] The photosensitive resin composition obtained in each Example and each Comparative Example was applied on a 100×100 mm, 0.7 mm thick silicon substrate using a spin coater, and then the coating film was pre-baked at 100° C. for 60 seconds.

[0584] Then, at 60 mJ / cm2 The coating film was irradiated with i-ray (365 nm) at an exposure amount of .

[0585] After the exposure, development was performed at room temperature (23° C.) for 60 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass as a developer.

[0586] The exposed coating film after development was post-baked at 200° C. for 10 minutes to obtain a substrate having a resin film with a film thickness of 6 μm.

[0587] <Evaluation of Solvent Resistance>

[0588] The silicon substrate provided with the resin film was immersed in the solvent at room temperature (23° C.) for 10 minutes.

[0589] After being immersed in acetone or PGMEA, the substrate was rinsed with pure water for 30 seconds and then heated using a hot plate at 100° C. for 1 minute.

[0590] The film thickness of the resin film was measured before and after immersion in acetone or before and after immersion in PGMEA. The film thickness before immersion was defined as Th1, and the film thickness after immersion was defined as Th2.

[0591] Based on the measured value of the film thickness, the change rate of the film thickness of the resin film was calculated according to the following formula.

[0592] Film thickness change rate (%) = Th2 / Th1×100

[0593] Based on the calculated value of the film thickness change rate, the solvent resistance was evaluated according to the following criteria.

[0594] A: The film thickness change rate is greater than 99% and less than 101%

[0595] B: The film thickness change rate is greater than 95% and less than 99%, or greater than 101% and less than 105%

[0596] C: Film thickness change rate is less than 95% or more than 105%

[0597] <Preparation of a Substrate Having a Patterned Resin Film>

[0598] The photosensitive resin composition obtained in each example and each comparative example was applied onto a silicon substrate of 100 mm×100 mm×0.7 mm using a spin coater, and the coating film was pre-baked at 100° C. for 60 seconds.

[0599] Next, the photosensitive resin was applied through a photomask (spot diameter: 40 μm) at 60 mJ / cm 2 The coating film is irradiated with i-ray (365 nm) at an exposure amount of .

[0600] After the exposure, the coating film was heated at 110° C. for 90 seconds.

[0601] After heating, the exposed coating film was developed using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38 mass % as a developer at room temperature (23° C.) for 60 seconds to obtain a substrate having a patterned resin film having a film thickness of 6 μm.

[0602] <Evaluation of pattern shape>

[0603] The resin film in the dot pattern formed on the silicon substrate was visually observed using a scanning electron microscope S-9220 (manufactured by Hitachi, Ltd.), and the pattern shape was evaluated based on the following criteria.

[0604] A: The shape of the dot viewed from the vertical direction of the substrate is a rectangle or a substantially rectangle.

[0605] B: The shape of the dot viewed from the vertical direction of the substrate is not a rectangle or a substantially rectangle.

[0606] <Preparation of a Substrate with a Resin Film for Reliability Testing>

[0607] The photosensitive resin composition obtained in each of Examples and Comparative Example 4 was applied onto a glass substrate having a size of 100×100 mm and a thickness of 0.7 mm using a spin coater, and the coating film was pre-baked at 100° C. for 60 seconds.

[0608] Then, at 60 mJ / cm 2 The coating film was irradiated with i-ray (365 nm) at an exposure amount of .

[0609] After the exposure, development was performed at room temperature (23° C.) for 60 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass as a developer.

[0610] For the coating film of Comparative Example 4, after development, the coating film was exposed to 500 mJ / cm 2 The exposure dose was 365 nm ultraviolet light for bleaching.

[0611] The exposed coating film after development was post-baked at 200° C. for 10 minutes to obtain a substrate having a resin film with a film thickness of 6 μm.

[0612] <Reliability Evaluation>

[0613] The glass substrate provided with the resin film was heated in an oven at 150° C. for 500 hours. After heating, the transmittance was measured at a wavelength of 400 nm and evaluated based on the following criteria. The results are shown in Table 3.

[0614] A: Transmittance greater than 90% and less than 100%

[0615] B: Transmittance greater than 80% and less than 90%

[0616] C: Transmittance is less than 80%

[0617] [Table 3]

[0618]

[0619] As can be seen from Table 3, when the photosensitive resin compositions of Examples 1 to 8 and 10 (using the resin (A) comprising a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group) and the photosensitive resin composition of Example 9 (using the resin (A) comprising a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group donating unit (a2), and a compound (C) having two or more blocked isocyanate groups) are used, a resin film having excellent solvent resistance and reliability can be formed, and a pattern of a good shape can be formed.

[0620] On the other hand, when the photosensitive resin compositions of Comparative Examples 1 and 2 were used, since the photosensitive resin compositions contained a resin that did not contain the blocked isocyanate group-containing unit (a3), a pattern having a good shape could not be formed, or a resin film having excellent solvent resistance could not be formed.

[0621] In addition, when the photosensitive resin compositions of Comparative Examples 3 and 4 were used, since the photosensitive resin compositions contained a resin including a structural unit having an epoxy group, a pattern having a good shape could not be formed, or a resin film having excellent transmittance, long-term heat resistance, and light resistance could not be formed.

Claims

1. A photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) which generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating, The resin (A) includes a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group-donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group.

2. A photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) which generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating, The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a hydroxyl group donating unit (a2), The photosensitive resin composition further includes a compound (C) having a blocked isocyanate group.

3. A photosensitive resin composition comprising a resin (A) whose solubility in an alkali can be increased by the action of an acid, and an acid generator (B) which generates an acid by irradiation with activating light or radiation, wherein the photosensitive resin composition can be crosslinked by a reaction between a hydroxyl group and an isocyanate group by heating, The resin (A) comprises a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent and a unit (a3) ​​containing a blocked isocyanate group. The photosensitive resin composition further includes a compound (D) having two or more hydroxyl groups.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein The acid generator (B) has a fluorine atom.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein The blocked isocyanate group-containing unit (a3) ​​or the compound (C) has a group represented by the following formula (a3-2): -NH-CO-R a34 ···(a3-2) In formula (a3-2), R a34 For lactam ring group, -OR a341 -CHR a342 -OR a343 or-ON=CR a344 2; The lactam ring group is a group obtained by removing a hydrogen atom from a nitrogen atom in a lactam ring; the nitrogen atom in the lactam ring group is bonded to a carbon atom in a carbonyl group; R a341 is a divalent hydrocarbon group, R a342 is a hydrocarbon group having 1 to 5 carbon atoms, R a343 is a hydrocarbon group having 1 to 5 carbon atoms, R a344 Each independently is a hydrocarbon group having 1 to 5 carbon atoms. 6 . A microlens formed from a cured product of the photosensitive resin composition according to claim 1 .

7. A method for manufacturing a microlens, comprising the following steps: A step of applying the photosensitive resin composition according to any one of claims 1 to 3 on a substrate to form a coating film; A step of selectively exposing the coating film to light in a manner that dots are formed at positions on the substrate where microlenses are to be formed; A step of developing the exposed coating film to obtain a patterned resin film including a plurality of dots in which dots are arranged at positions where microlenses are to be formed; as well as The resin film is heated to deform the dots by heat to form microlenses.

8. A resin comprising a unit (a1) containing a carboxyl group protected by a tertiary alkyl group which may have a substituent, a hydroxyl group-donating unit (a2), and a unit (a3) ​​containing a blocked isocyanate group.

Images