Photosensitive composition used for producing light detection device, transfer film, laminate and method for producing the same, and light detection device

Abstract

To provide a biosensor and a light detection device allowing a film having excellent light-shielding properties to be patterned with high resolution and high aspect ratio and exhibiting high-resolution.SOLUTION: There are provided a photosensitive composition used for a light detection device, the composition containing a colorant precursor exhibiting light absorptivity upon stimulation, and a transfer film, a laminate, a method for producing the laminate, and a light detection device, each obtained using the photosensitive composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive composition, a transfer film, a laminate, a method for producing the same, and a photodetector. [Background technology]

[0002] In recent years, optical biosensors have become known as biosensors used for personal authentication, etc. Optical biosensors are configured by arranging multiple light-receiving elements, such as photodiodes, on a substrate, each of which outputs a signal that changes depending on the amount of light received. Summary of the Invention [Problem to be solved by the invention]

[0003] Optical detection devices, including biosensors, require light to be guided to a light-receiving element. It is important to properly guide light so that it does not accidentally reach an adjacent light-receiving element. Japanese Patent Application Laid-Open No. 2020-184208 proposes a structure in which cylindrical light-guiding sections are patterned and arranged within a light-shielding layer to properly guide light to the light-receiving element. In order to increase the resolution of the detection device, the resolution of the light-guiding section pattern must also be increased, but this has been difficult to achieve using conventional methods.

[0004] An object of one embodiment of the present disclosure is to provide a photosensitive composition, a transfer film, a laminate and a manufacturing method thereof, a photodetector, and a biometric authentication device, which are capable of patterning a film having excellent light-blocking properties with high resolution and a high aspect ratio. [Means for solving the problem]

[0005] Specific means for solving the above problems include the following embodiments. <1> A photosensitive composition containing a colorant precursor that exhibits light absorption in response to a stimulus, the photosensitive composition being used in a light guide member of a light detection device. <2> The stimulus is at least one selected from the group consisting of heat, light, acid, base, and radical. <1> The photosensitive composition according to claim 1. <3> Further, the composition contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator. <1> or <2> The photosensitive composition according to claim 1. <4> The light detection device is a biometric authentication device. <1> ~ <3> 1. The photosensitive composition according to any one of the above items. <5> A temporary support; <1> ~ <4> and a photosensitive composition layer containing the photosensitive composition according to any one of the above items. <6> A method for manufacturing a laminate having a light-shielding pattern, comprising: On the substrate, <1> ~ <4> forming a photosensitive composition layer containing the photosensitive composition according to any one of the above; patternwise exposing the photosensitive composition layer; and developing the photosensitive composition layer, a step of causing the colorant precursor to exhibit light absorbing properties after the step of patterned exposure. <7> A laminate having a light-shielding pattern, <6> A laminate manufactured by the manufacturing method described in 1. <8> <7> A photodetector comprising the laminate according to claim 1. <9> <7> A biometric authentication device having the laminate according to claim 1. [Effects of the Invention]

[0006] According to one embodiment of the present disclosure, there are provided a photosensitive composition capable of patterning a film with excellent light-blocking properties at high resolution and high aspect ratio, a transfer film, a laminate and a manufacturing method thereof, a photodetector, and a biometric authentication device. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram illustrating a detection device according to an embodiment of the present disclosure. [Figure 2] 1 is a schematic diagram of a light guide according to the present disclosure. [Figure 3] 1 is a schematic diagram of a light guide according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure will be described in detail below. The following description of the requirements may be based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments and can be implemented by making appropriate modifications within the scope of the purpose of the present disclosure.

[0009] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0010] In the present disclosure, when referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, it means the total amount of the multiple components present in the composition, unless otherwise specified.

[0011] In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0012] In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0013] In the present disclosure, "transparent" means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more, and preferably 90% or more. In the present disclosure, "transmittance" is a value measured using a spectrophotometer. As the spectrophotometer, for example, a spectrophotometer (model number: U-3310) manufactured by Hitachi, Ltd. can be used. However, the spectrophotometer is not limited to this.

[0014] In the present disclosure, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw; the same applies hereinafter) unless otherwise specified.

[0015] In the present disclosure, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) unless otherwise specified. The GPC measurement was carried out using a TSKgel (registered trademark) GMHxL, TSKgel (registered trademark) G4000HxL, or TSKgel (registered trademark) G2000HxL (all of which are trade names manufactured by Tosoh Corporation) as a column, tetrahydrofuran (THF) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, and the polystyrene equivalent values ​​were measured using a GPC analyzer.

[0016] In the present disclosure, the ratio of the constituent units of a polymer compound is a mass ratio unless otherwise specified.

[0017] In this disclosure, "(meth)acrylic" is a term that encompasses both "acrylic" and "methacrylic," "(meth)acrylate" is a term that encompasses both "acrylate" and "methacrylate," and "(meth)acryloxy" is a term that encompasses both "acryloxy" and "methacryloxy."

[0018] In the present disclosure, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more.

[0019] In the present disclosure, "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 and a liquid temperature of 22°C is 0.1 g or more. For example, "water-soluble resin" means a resin that satisfies the above solubility conditions.

[0020] In the present disclosure, the "solid content" of a composition refers to the components that form a composition layer formed using the composition, and in the case where the composition contains a solvent, refers to all components excluding the solvent. Furthermore, liquid components other than the solvent are also considered to be solids as long as they form a composition layer. In the present disclosure, the "solvent" refers to water and organic solvents.

[0021] In this disclosure, "n-" means normal, "s-" means secondary, and "t-" means tertiary.

[0022] In this disclosure, "light" refers to, for example, ultraviolet light, visible light, and infrared light. In this disclosure, "ultraviolet light" refers to light in the wavelength range of 200 nm or more and less than 400 nm, "visible light" refers to light in the wavelength range of 400 nm or more and less than 780 nm, and "infrared light" refers to light in the wavelength range of 780 nm or more and less than 1000 nm.

[0023] In the description of groups (atomic groups) in the present disclosure, descriptions that do not specify whether they are substituted or unsubstituted include those that have a substituent as well as those that do not have a substituent. For example, the term "alkyl group" includes not only alkyl groups that do not have a substituent (also referred to as "unsubstituted alkyl groups"), but also alkyl groups that have a substituent (also referred to as "substituted alkyl groups").

[0024] The "substituent" in the present disclosure is not particularly limited, and examples thereof include a halogen group, a hydroxy group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a sulfo group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, a carbamoyl group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a cyano group, a nitro group, an amino group (including an anilino group), an acylamino group, an amino The substituent can be arbitrarily selected from the group consisting of a carbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an arylazo group, a heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, and a phosphinylamino group.

[0025] More specifically, examples of the substituent in the present disclosure include a halogen group (e.g., a fluoro group, a chloro group, a bromo group, and an iodo group), an alkyl group (a linear, branched, or cyclic alkyl group having 1 to 10, preferably 1 to 6, carbon atoms; e.g., a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-octyl group, a 2-chloroethyl group, a 2-cyanoethyl group, and a 2-ethylhexyl group), a cycloalkyl group (e.g., a cyclopropyl group, and a cyclohexyl group), a cyclopropyl group, a cyclohexyl ... pentyl group), alkenyl group (a straight-chain, branched, or cyclic alkenyl group having 2 to 10, preferably 2 to 6 carbon atoms; for example, a vinyl group, an allyl group, and a prenyl group), cycloalkenyl group (for example, a cyclopenten-1-yl group), alkynyl group (an alkynyl group having 2 to 10, preferably 2 to 6 carbon atoms; for example, an ethynyl group and a propargyl group), aryl group (an aryl group having 6 to 12, preferably 6 to 8 carbon atoms; for example, a phenyl group), a phenyl group, a p-tolyl group, a naphthyl group, a 3-chlorophenyl group, and a 2-aminophenyl group), a heterocyclic group (a monovalent group having 1 to 12, preferably 2 to 6, carbon atoms obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound; for example, a 1-pyrazolyl group, a 1-imidazolyl group, a 2-furyl group, a 2-thienyl group, a 4-pyrimidinyl group, and a 2-benzothiazolyl group), a cyano group, a hydroxy group, a nitro group, an alkoxy group (a linear, branched, or cyclic alkoxy group having 1 to 10, preferably 1 to 6, carbon atoms; for example, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, a cyclopentyloxy group, a 2-buten-1-yloxy group, and a 2-methoxyethoxy group), an aryloxy group (an aryloxy group having 6 to 12, preferably 6 to 8, carbon atoms; for example, a phenoxy group, a 2-methylphenoxy group, a 4-t-butylphenoxy group, and a 3-nitrophenoxy group),

[0026] Heterocyclic oxy groups (heterocyclic oxy groups having 1 to 12, preferably 2 to 6 carbon atoms; for example, 1-phenyltetrazole-5-oxy-2-tetrahydropyranyloxy group), acyloxy groups (acyloxy groups having 1 to 12, preferably 1 to 8 carbon atoms; for example, formyloxy group, acetyloxy group, pivaloyloxy group, benzoyloxy group, and p-methoxyphenylcarbonyloxy group), carbamoyloxy groups (heterocyclic oxy groups having 1 to 10, preferably 1 to 6 carbon atoms; for example, 1-phenyltetrazole-5-oxy-2-tetrahydropyranyloxy group), carbamoyloxy groups having a carbon atom; for example, an N,N-dimethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, a morpholinocarbonyloxy group, and an N,N-octylcarbamoyloxy group), alkoxycarbonyloxy groups (alkoxycarbonyloxy groups having 2 to 10, preferably 2 to 6, carbon atoms; for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and an n-octyloxycarbonyloxy group), ), an aryloxycarbonyloxy group (an aryloxycarbonyloxy group having 7 to 12, preferably 7 to 10, carbon atoms; for example, a phenoxycarbonyloxy group and a p-methoxyphenoxycarbonyloxy group), an amino group (an amino group; an alkylamino group having 1 to 10, preferably 1 to 6, carbon atoms; an anilino group having 6 to 12, preferably 6 to 8, carbon atoms; or a heterocyclic amino group having 1 to 12, preferably 2 to 6, carbon atoms; For example, an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, an imidazol-2-ylamino group, and a pyrazol-3-ylamino group), an acylamino group (an alkylcarbonylamino group having 1 to 10, preferably 1 to 6, carbon atoms; an arylcarbonylamino group having 6 to 12, preferably 6 to 8, carbon atoms; or a heterocyclic carbonylamino group having 2 to 12, preferably 2 to 6, carbon atoms;For example, a formylamino group, an acetylamino group, a pivaloylamino group, a benzoylamino group, a pyridine-4-carbonylamino group, and a thiophene-2-carbonylamino group), an aminocarbonylamino group (an aminocarbonylamino group having 1 to 12, preferably 1 to 6 carbon atoms; for example, a carbamoylamino group, an N,N-dimethylaminocarbonylamino group, an N,N-diethylaminocarbonylamino group, and a morpholin-4-ylcarbonylamino group), an alkoxycarbonylamino group (an alkoxycarbonylamino group having 2 to 10, preferably 2 to 6 carbon atoms; for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, and a t-butoxycarbonylamino group);

[0027] Aryloxycarbonylamino groups (aryloxycarbonylamino groups having 7 to 12, preferably 7 to 9, carbon atoms; for example, phenoxycarbonylamino groups, p-chlorophenoxycarbonylamino groups, and 4-methoxyphenoxycarbonylamino groups), sulfamoylamino groups (sulfamoylamino groups having 0 to 10, preferably 0 to 6, carbon atoms; for example, sulfamoylamino groups, N,N-dimethylaminosulfonylamino groups, and N-(2-hydroxyethyl)sulfamoyl amino group), alkylsulfonylamino group (an alkylsulfonylamino group having 1 to 10, preferably 1 to 6, carbon atoms; for example, a methylsulfonylamino group and a butylsulfonylamino group), arylsulfonylamino group (an arylsulfonylamino group having 6 to 12, preferably 6 to 8, carbon atoms; for example, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, and a p-methylphenylsulfonylamino group), a mercapto group, an alkylthio group (1 to 10, alkylthio groups preferably having 1 to 6 carbon atoms; for example, a methylthio group, an ethylthio group, and a butylthio group), arylthio groups (arylthio groups having 6 to 12, preferably 6 to 8 carbon atoms; for example, a phenylthio group, a p-chlorophenylthio group, and a m-methoxythio group), heterocyclic thio groups (heterocyclic thio groups having 2 to 10, preferably 1 to 6 carbon atoms; for example, a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group), sulfamoyl groups (0 to 10, preferably Preferably, a sulfamoyl group having 0 to 6 carbon atoms; for example, a sulfamoyl group, an N-ethylsulfamoyl group, an N,N-dimethylsulfamoyl group, an N-acetylsulfamoyl group, and an N-benzoylsulfamoyl group), an alkylsulfinyl group (an alkylsulfinyl group having 1 to 10, preferably 1 to 6, carbon atoms; for example, a methylsulfinyl group and an ethylsulfinyl group), an arylsulfinyl group (an arylsulfinyl group having 6 to 12, preferably 6 to 8, carbon atoms;For example, a phenylsulfinyl group and a p-methylphenylsulfinyl group), an alkylsulfonyl group (an alkylsulfonyl group having 1 to 10, preferably 1 to 6 carbon atoms; for example, a methylsulfonyl group and an ethylsulfonyl group), an arylsulfonyl group (an arylsulfonyl group having 6 to 12, preferably 6 to 8 carbon atoms; for example, a phenylsulfonyl group and a p-chlorophenylsulfonyl group), a sulfo group, an acyl group (a formyl group; an alkylcarbonyl group having 2 to 10, preferably 2 to 6 carbon atoms; or an arylcarbonyl group having 7 to 12, preferably 7 to 9 carbon atoms; for example, an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a benzoyl group, and a 2,4-dichlorobenzoyl group);

[0028] Alkoxycarbonyl groups (alkoxycarbonyl groups having 2 to 10, preferably 2 to 6, carbon atoms; for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and isobutyloxycarbonyl groups), aryloxycarbonyl groups (aryloxycarbonyl groups having 7 to 12, preferably 7 to 9, carbon atoms; for example, phenoxycarbonyl-2-chlorophenoxycarbonyl, 3-nitrophenoxycarbonyl, and 4-t-butylphen ... a carbamoyl group (a carbamoyl group having 1 to 10, preferably 1 to 6, carbon atoms; for example, a carbamoyl group, an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N-(2-hydroxyethyl)carbamoyl group, and an N-(methylsulfonyl)carbamoyl group), an arylazo group (an arylazo group having 6 to 12, preferably 6 to 8, carbon atoms; for example, a phenylazo group and a p-chlorophenylazo group), a heterocyclic azo group (a heterocyclic azo group having 1 to 10, preferably 1 to 6, carbon atoms), for example, a pyrazol-3-ylazo group, a thiazol-2-ylazo group, and a 5-methylthio-1,3,4-thiadiazol-2-ylazo group), an imido group (an imido group having 2 to 10, preferably 4 to 8 carbon atoms; for example, a succinimido group and a phthalimido group), a phosphino group (a phosphino group having 2 to 12, preferably 2 to 6 carbon atoms; for example, a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group), a phosphinyl group (a phosphinyl group having 2 to 12, preferably 2 to 6 carbon atoms; for example, a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group), a phosphinyl group (a phosphinyl group having 2 to 12, preferably 2 to 6 carbon atoms; for example, a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group), a phosphinyl group (a phosphinyl group having 2 to 12 carbon atoms ... and phosphinyl groups having 2 to 12, preferably 2 to 6, carbon atoms; for example, a phosphinyl group and a diethoxyphosphinyl group, phosphinyloxy groups having 2 to 12, preferably 2 to 6, carbon atoms; for example, a diphenoxyphosphinyloxy group and a dibutoxyphosphinyloxy group, and phosphinylamino groups having 2 to 12, preferably 2 to 6, carbon atoms; for example, a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group.

[0029] When these groups are groups that can be further substituted, these groups can further contain substituents. When these groups are substituted with two or more substituents, these substituents may be the same or different.

[0030] [Photosensitive composition] The photosensitive composition of the present disclosure includes a colorant precursor that exhibits light absorption upon stimulation. In the present disclosure, the “colorant precursor that exhibits light absorption in response to a stimulus” is also referred to as a “specific colorant precursor.” The photosensitive composition of the present disclosure contains the specific colorant precursor, and therefore can form a film with excellent light-blocking properties and has excellent patterning properties.

[0031] Carbon black is known as a colorant used in forming a black matrix. However, when a composition containing carbon black as a colorant is used to form, for example, a negative-pattern black matrix, the carbon black absorbs the exposed light (e.g., ultraviolet light), and the incident light gradually attenuates in the thickness direction of the composition layer used to form the pattern, resulting in insufficient polymerization and curing, making it difficult to obtain a pattern with a good shape after development. In contrast, the photosensitive composition of the present disclosure contains a colorant precursor that exhibits light absorption in response to a stimulus, and the timing of color development can be controlled by the timing of the stimulus. For example, patterned exposure can be performed before the colorant precursor exhibits light absorption, and then the colorant precursor can be made light-absorbent by applying a stimulus after the patterned exposure. According to the photosensitive composition of the present disclosure, by performing patterned exposure before the colorant precursor develops a black color, absorption of incident light can be suppressed during patterned exposure, allowing the incident light to be transmitted, resulting in a pattern with a good shape after development. Furthermore, by applying a stimulus after patterned exposure to impart light absorption to the colorant precursor, excellent light-blocking properties can be imparted to the pattern.

[0032] <Specific colorant precursor> The photosensitive composition of the present disclosure contains a colorant precursor (i.e., a specific colorant precursor) that exhibits light absorption upon stimulation. In the present disclosure, light absorption preferably refers to absorption of visible light and near-infrared light, for example, visible light refers to 400 to 700 nm, and near-infrared light refers to 700 to 950 nm. The "colorant precursor that exhibits light absorption upon stimulation" in the present disclosure is preferably a compound that satisfies the following requirements A, B, and C.

[0033] (Requirement A) In the absorption spectrum measured using a spectrophotometer for a solution of 1.1 mg of the compound before color development in 50 mL of tetrahydrofuran (THF), the average value of the molar absorption coefficient (ε) at any consecutive 100 nm wavelengths within the wavelength range of 400 nm to 700 nm (so-called average molar absorption coefficient) must be 400 L / (mol cm) or less.

[0034] The average molar extinction coefficient in requirement A is preferably 200 L / (mol·cm) or less, and more preferably 100 L / (mol·cm) or less.

[0035] The average value of the molar absorption coefficient (ε) at successive 100 nm wavelengths within the wavelength range of 400 nm to 700 nm can be determined by calculating the molar absorption coefficient at each wavelength in 1 nm increments and then arithmetically averaging the molar absorption coefficients in successive 100 nm ranges (e.g., 421 nm to 520 nm, 560 nm to 659 nm, etc.). The same applies to requirement C described below.

[0036] "The average molar absorption coefficient (ε) over any consecutive 100 nm wavelength range from 400 nm to 700 nm is 400 L / (mol cm) or less" means that, regardless of which consecutive 100 nm range is selected within the wavelength range from 400 nm to 700 nm, the average molar absorption coefficient over that consecutive 100 nm range is 400 L / (mol cm) or less.

[0037] (Requirement B) In the absorption spectrum measured using a spectrophotometer for a solution prepared by dissolving 1.1 mg of the color-developed compound in 50 mL of tetrahydrofuran (THF), the maximum absorption wavelength is within the wavelength range of 400 nm to 700 nm.

[0038] The number of the maximum absorption wavelengths within the wavelength range of 400 nm to 700 nm is preferably two or more. The upper limit of the number of the maximum absorption wavelengths within the wavelength range of 400 nm to 700 nm is not particularly limited, and examples thereof include 10 or less, 5 or less, 3 or less, and the like.

[0039] When there are two or more absorption maxima within the wavelength range of 400 nm to 700 nm, the absorption maxima are preferably spaced apart by 100 nm or more, and more preferably spaced apart by 200 nm or more.

[0040] Of the maximum absorption wavelengths within the wavelength range of 400 nm to 700 nm, the molar absorption coefficient (ε) at the wavelength at which absorption is maximum is preferably 3000 L / (mol cm) or more, more preferably 4000 L / (mol cm) or more, and even more preferably 5000 L / (mol cm) or more. Furthermore, among the maximum absorption wavelengths within the wavelength range of 400 nm to 700 nm, the molar absorption coefficient (ε) at the wavelength at which absorption is maximum is preferably 100,000 L / (mol cm) or less, more preferably 40,000 L / (mol cm) or less, and even more preferably 20,000 L / (mol cm) or less.

[0041] (Requirement C) In the absorption spectrum measured using a spectrophotometer for a solution prepared by dissolving 1.1 mg of the color-developed compound in 50 mL of tetrahydrofuran (THF), the average molar absorption coefficient (ε) at any consecutive 100 nm wavelengths within the wavelength range of 400 nm to 700 nm (i.e., the average molar absorption coefficient) must be 2000 L / (mol cm) or more.

[0042] In requirement C, the average molar extinction coefficient is preferably 3000 L / (mol·cm) or more, and more preferably 4000 L / (mol·cm) or more.

[0043] "The average molar absorption coefficient (ε) over any consecutive 100 nm wavelength range from 400 nm to 700 nm is 2000 L / (mol cm) or greater" means that, regardless of which consecutive 100 nm range is selected within the wavelength range from 400 nm to 700 nm, the average molar absorption coefficient over that consecutive 100 nm range is 2000 L / (mol cm) or greater.

[0044] The "stimulus" in the present disclosure encompasses both direct and indirect factors that cause the colorant precursor to exhibit light absorption. That is, the stimulus may act directly on the colorant precursor to change the structure of the colorant precursor, thereby imparting light absorption to the colorant precursor, or it may act as a trigger for changing the structure of the colorant precursor, but the stimulus itself does not act directly on the colorant precursor to change the structure of the colorant precursor.

[0045] The stimulus is not particularly limited as long as it can directly or indirectly impart light absorption to the colorant precursor. The stimulus is preferably at least one selected from the group consisting of heat, light, acid, base and radical, more preferably heat or acid, and even more preferably heat.

[0046] The type of the specific colorant precursor is not particularly limited. As the specific colorant precursor, a compound that exhibits light absorption by an acid or a compound that exhibits light absorption by heat is preferred, a compound that exhibits light absorption by heat is more preferred, and a compound that exhibits light absorption by oxidation by heat (so-called thermal oxidation) is even more preferred. A compound that becomes light-absorbing when heated is preferable to a compound that becomes light-absorbing when acidized, in that when the film formed is applied to a device, problems caused by acid are unlikely to occur.

[0047] Examples of the specific colorant precursor include leuco coloring matter compounds (so-called leuco dyes). Leuco dyes are compounds that develop color in the presence of an acid or the like. Specifically, the lactone ring in the molecule is opened by reacting with an acid, thereby developing color. The above reaction in the leuco dye is a reversible reaction, and when the open lactone ring is brought into contact with a base, the ring is closed and the dye is decolorized.

[0048] Any known leuco dye can be used without any particular limitation as long as it exhibits light absorption properties. Examples of light-absorbing leuco dyes include 2'-anilino-6'-(dibutylamino)-3'-methylfluoran, 2'-anilino-3'-methyl-6'-(dipentylamino)spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 2'-anilino-6'-dibutylamino-3'-methylspiro[phthalide-3,9'-[9H]xanthene], 2'-anilino-6'-(N-ethyl-N-isopentylamino)-3'-methylspiro[phthalide-3,9'-[9H]xanthene], and 2-(phenylamino)-3-methyl-6-[ethyl(p-tolyl)amino]spiro[9H-xanthene-9,1'(3'H)-isobenzofuran]-3'-one. Among these, 2'-anilino-3'-methyl-6'-(dipentylamino)spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one is preferred as the leuco dye.

[0049] Commercially available leuco dyes include BLACK 305 (CAS No. 129473-78-5), BLACK 400 (CAS No. 89331-94-2), S-205 (CAS No. 70516-41-5), and ETAC (CAS No. 59129-79-2) manufactured by Fukui Yamada Chemical Co., Ltd., and 2'-anilino-6'-(dibutylamino)-3'-methylfluoran manufactured by Tokyo Chemical Industry Co., Ltd.

[0050] When the photosensitive composition according to the present disclosure contains a leuco dye as a specific colorant precursor, it preferably contains a compound that absorbs red and / or green light, from the viewpoint of forming a film with superior light-blocking properties. Examples of such compounds include the EX Color series manufactured by Nippon Shokubai Co., Ltd., and the FDG series and FDR series manufactured by Fukui Yamada Chemical Co., Ltd. When the photosensitive composition according to the present disclosure contains the above-mentioned compound, the content of the above-mentioned compound in the photosensitive composition is not particularly limited and can be set appropriately depending on the purpose. For example, it is preferable to adjust the content so that the average absorbance of the film formed at a wavelength of 400 nm to 700 nm is 2.0 or more.

[0051] An example of the specific colorant precursor is a compound represented by the following formula (1).

[0052] [ka]

[0053] In formula (1), X 1 , X 2 , X 3 , X 4 , Y 1 and Y 2 are each independently an oxygen atom, a sulfur atom, or NL 1 Represents L 1 represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, or an aminocarbonyl group. 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, -OL 2 , -OCO-L 3 , -SL 2 or -OSO-L 3 Represents L 2 represents a hydrogen atom or an alkyl group, and L 3 represents an alkyl group or an amino group. 1 and R 2 At least one of represents a hydrogen atom, and R 3 and R 4At least one of A, B and C represents a hydrogen atom. A, B and C each independently represent an aromatic ring.

[0054] The compound represented by formula (1) is a compound that develops a black color when heated (specifically, by thermal oxidation). The mechanism by which the compound represented by formula (1) develops a black color is not clear, but the present inventors believe it to be as follows. It is believed that when the compound represented by formula (1) is heated, it reacts with oxygen in the air, and its structure changes to an oxidized form, resulting in a black color. In other words, it is believed that the oxidized form exhibits a black color. Specifically, for example, the compound represented by formula (1) reacts with oxygen in the air to form a black compound, where R in formula (1) 1 , R 2 , R 3 and R 4 is eliminated (e.g., dehydration, dealcoholization, etc.), and R 1 and R 2 Between R 3 and R 4 It is thought that the single bond between the two becomes a double bond, and the conjugation extends, resulting in a change to a structure that absorbs visible light.

[0055] The reaction of the compound represented by formula (1) is an irreversible reaction, unlike that of the leuco dye, and therefore color fading is unlikely to occur. Therefore, from the viewpoint of reducing the risk of color fading of the pattern, the compound represented by formula (1) is more preferable as the specific colorant precursor.

[0056] The compound represented by formula (1) will be described in detail below.

[0057] X 1 , X 2 , X 3 and X 4 is preferably an oxygen atom.

[0058] In equation (1), there are two Y 1 may be the same or different, but are preferably the same. Y 1 is preferably an oxygen atom.

[0059] In equation (1), there are two Y 2 may be the same or different, but are preferably the same. Y 2 NL 1 It is preferable that: L 1 is preferably a hydrogen atom, an alkyl group, an acyl group, or an alkoxycarbonyl group, and more preferably an alkyl group, an acyl group, or an alkoxycarbonyl group.

[0060] L 1 The alkyl group represented by the formula (I) may or may not have a substituent. 1 The alkyl group represented by the formula (I) may be a straight-chain alkyl group, a branched alkyl group, or an alkyl group having a cyclic structure. L 1 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. L 1 The alkyl group represented by the formula (I) is preferably, for example, an s-butyl group, an n-hexyl group, a 2-ethoxyethyl group, a methoxycarbonylmethyl group, an isopropyl group, an n-pentyl group or a 2-ethylhexyl group.

[0061] L 1 The acyl group represented by the formula (I) is preferably an acyl group having 2 to 30 carbon atoms, and more preferably an acyl group having 2 to 15 carbon atoms. L 1 The acyl group represented by the formula (I) is preferably, for example, an acetyl group, a 2-ethylhexanoyl group, a 3,3,5-trimethylhexanoyl group, a propionyl group, a butyryl group, an isobutyryl group or a pivaloyl group.

[0062] L 1 The alkoxycarbonyl group represented by the following formula is preferably an alkoxycarbonyl group having 1 to 30 carbon atoms in the alkoxy moiety. L 1The alkoxycarbonyl group represented by the formula (I) is preferably, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a t-butoxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, a benzyloxycarbonyl group, or a 2,2,2-trichloroethyloxycarbonyl group.

[0063] R 1 and R 2 When one of the groups is a hydrogen atom, the other group is a hydrogen atom or a hydroxy group (i.e., L 2 -OL is a hydrogen atom 2 ), and more preferably a hydrogen atom. R 3 and R 4 When one of the groups is a hydrogen atom, the other group is a hydrogen atom or a hydroxy group (i.e., L 2 -OL is a hydrogen atom 2 ), and more preferably a hydrogen atom.

[0064] L 2 is preferably a hydrogen atom. L 2 The alkyl group represented by the formula (I) may or may not have a substituent. 2 The alkyl group represented by the formula (I) may be a straight-chain alkyl group, a branched alkyl group, or an alkyl group having a cyclic structure. L 2 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. L 2 The alkyl group represented by the formula (I) is preferably, for example, a methyl group, an ethyl group, a propyl group or a 2-ethylhexyl group.

[0065] L 3 The alkyl group represented by the formula (I) may or may not have a substituent. 3The alkyl group represented by the formula (I) may be a straight-chain alkyl group, a branched alkyl group, or an alkyl group having a cyclic structure. L 3 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. L 3 The alkyl group represented by the formula (I) is preferably, for example, a methyl group, an ethyl group, a propyl group or a 2-ethylhexyl group.

[0066] The aromatic ring represented by A and the aromatic ring represented by B may be the same or different. The aromatic rings represented by A and B may or may not have a substituent. The aromatic rings represented by A and B may be, for example, an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring thereof.

[0067] When the aromatic rings represented by A and B are aromatic hydrocarbon rings, the aromatic hydrocarbon rings represented by A and B are preferably 5- or 6-membered rings, and more preferably 6-membered rings. When the aromatic rings represented by A and B are aromatic hydrocarbon rings, the aromatic hydrocarbon rings represented by A and B are preferably aromatic hydrocarbon rings having 6 to 30 carbon atoms, more preferably aromatic hydrocarbon rings having 6 to 20 carbon atoms, and even more preferably aromatic hydrocarbon rings having 6 to 10 carbon atoms. When the aromatic rings represented by A and B are aromatic hydrocarbon rings, the aromatic hydrocarbon ring represented by A is preferably, for example, a benzene ring, a naphthalene ring or an anthracene ring, and more preferably a benzene ring.

[0068] When the aromatic rings represented by A and B are aromatic heterocycles, the aromatic heterocycles represented by A and B are preferably 5- or 6-membered rings, and more preferably 5-membered rings. When the aromatic rings represented by A and B are aromatic heterocycles, the aromatic heterocycles represented by A and B are preferably aromatic heterocycles containing one or more heteroatoms selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms in the ring. The number of heteroatoms in the aromatic heterocycle is preferably 1 or 2, and more preferably 1. When the aromatic rings represented by A and B are aromatic heterocycles, the aromatic heterocycles represented by A and B are, for example, preferably a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, or a pyridine ring, and more preferably a thiophene ring.

[0069] The aromatic ring represented by C may or may not have a substituent. Examples of the aromatic ring represented by C include a benzene ring and a hetero ring. Examples of the heterocycle include a pyridine ring and a pyrazine ring. The aromatic ring represented by C is preferably a benzene ring.

[0070] In formula (1), X 1 , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 and R 4 For example, the following mode A is preferred, and mode B is more preferred. Aspect A:X 1 , X 2 , X 3 and X 4 is an oxygen atom, and R 1 and R 2 is a hydrogen atom on one side and a hydroxy group on the other side, and R 3 and R 4 is an embodiment in which one is a hydrogen atom and the other is a hydroxy group. Aspect B:X 1 , X 2 , X 3 and X 4 is an oxygen atom, and R 1 , R 2 , R3 and R 4 is a hydrogen atom.

[0071] A preferred embodiment of the compound represented by formula (1) is X 1 , X 2 , X 3 and X 4 is an oxygen atom, and Y 1 and Y 2 each independently represents an oxygen atom, a sulfur atom, or NL 1 and L 1 is a hydrogen atom, an alkyl group, an acyl group, or an alkoxycarbonyl group, and R 1 or R 2 one of which is a hydrogen atom and the other is a hydroxy group, and R 3 or R 4 is a hydrogen atom and the other is a hydroxy group, A and B are each independently a benzene ring or a thiophene ring, and C is a benzene ring. A more preferred embodiment of the compound represented by formula (1) is X 1 , X 2 , X 3 and X 4 is an oxygen atom, and Y 1 is an oxygen atom, and Y 2 But NL 1 and L 1 is an alkyl group, an acyl group, or an alkoxycarbonyl group, and R 1 , R 2 , R 3 and R 4 is a hydrogen atom, A and B are benzene rings, and C is a benzene ring.

[0072] Specific examples of the compound represented by formula (1) are listed below. However, the compound represented by formula (1) is not limited to the following specific examples. Note that "Me" represents methyl.

[0073] [ka]

[0074]

change

[0075]

change

[0076]

change

[0077]

change

[0078]

change

[0079]

change

[0080]

change

[0081]

change

[0082] As the compound represented by formula (1), among the above specific examples, at least one selected from the group consisting of compounds (1) to (16), compounds (25) to (32), and compound (65) is preferred, at least one selected from the group consisting of compounds (1) to (16), and compound (65) is more preferred, at least one selected from the group consisting of compounds (1) to (3), compounds (5), compounds (7), and compound (8) is even more preferred, and at least one selected from the group consisting of compounds (1) to (3), compounds (5), compounds (7), and compound (8) is particularly preferred.

[0083] The heating temperature for imparting light absorption properties to the compound represented by formula (1) is preferably, for example, 80°C to 260°C.

[0084] The method for producing the compound represented by formula (1) is not particularly limited. The compound represented by formula (1) can be produced by referring to a known method. The compound represented by formula (1) can be produced, for example, by synthesizing an isatin derivative using isatin as a starting material with reference to known literature, then reacting the synthesized isatin derivative with 3,7-Dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione in an organic solvent in the presence of an acid catalyst, and reducing the compound obtained by the reaction. Methods for synthesizing isatin derivatives are described in, for example, J. Am. Chem. Soc. 2015, 137, 15947-15956, Journal of Medicinal Chemistry, 2008, 51, 4932-4947, Chemistry-A European Journal, 2021, 27, 4302-4306, Org. Lett., 2021, 23, 2273-2278, etc. The descriptions in these documents are incorporated herein by reference. Examples of the organic solvent include ether-based organic solvents, preferably tetrahydrofuran (THF) and / or 1,4-dioxane, and more preferably tetrahydrofuran (THF). The compound obtained by the reaction can be reduced, for example, by a method using a reducing agent such as zinc powder, trifluoroacetic acid, acetic acid, or hydrochloric acid. Alternatively, the reduction may be catalytic reduction using a palladium catalyst. Reduction using zinc powder (so-called zinc reduction) or catalytic reduction using a palladium catalyst is preferred, with zinc reduction being more preferred. The reaction temperature is not particularly limited, but is preferably 20°C to 40°C, and more preferably 30°C to 40°C, for example. The reaction time is not particularly limited, but is preferably 1 to 6 hours, and more preferably 1 to 2 hours. The compound represented by formula (1) can be suitably produced by the method described in the Examples below.

[0085] The photosensitive composition according to the present disclosure may contain only one type of specific colorant precursor, or may contain two or more types.

[0086] The content of the specific colorant precursor in the photosensitive composition according to the present disclosure is not particularly limited, but from the viewpoint of achieving better effects of the present disclosure, for example, the content is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and even more preferably 3% by mass to 10% by mass, relative to the total solid content of the photosensitive composition.

[0087] <Components other than specific colorant precursor> The photosensitive composition according to the present disclosure may further contain an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator in addition to the specific colorant precursor. The photosensitive composition according to the present disclosure may also contain additives such as a heterocyclic compound, an aliphatic thiol compound, a thermally crosslinkable compound, a surfactant, a polymerization inhibitor, a hydrogen donor compound, and a solvent. These components will be described in detail below.

[0088] (alkali-soluble resin) The photosensitive composition according to the present disclosure may contain an alkali-soluble resin. Examples of alkali-soluble resins include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by reacting an epoxy resin with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reacting an epoxy acrylate resin with an acid anhydride.

[0089] A preferred embodiment of the alkali-soluble resin is a (meth)acrylic resin, from the viewpoint of excellent alkali developability and film formability. In the present disclosure, a (meth)acrylic resin refers to a resin containing structural units derived from a (meth)acrylic compound. The content of structural units derived from (meth)acrylic compounds is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on all structural units of the (meth)acrylic resin. The (meth)acrylic resin may be composed solely of structural units derived from (meth)acrylic compounds, or may contain structural units derived from polymerizable monomers other than (meth)acrylic compounds. That is, the upper limit of the content of structural units derived from (meth)acrylic compounds is 100% by mass or less of all structural units of the (meth)acrylic resin.

[0090] Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, and (meth)acrylonitrile. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, (meth)acrylic acid glycidyl esters, (meth)acrylic acid benzyl esters, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and (meth)acrylic acid alkyl esters are preferred. Examples of (meth)acrylamides include acrylamides such as diacetone acrylamide.

[0091] The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched. Specific examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate. The (meth)acrylic acid alkyl ester is preferably a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and more preferably methyl (meth)acrylate or ethyl (meth)acrylate.

[0092] The (meth)acrylic resin may contain structural units other than structural units derived from a (meth)acrylic compound. The polymerizable monomer that forms a structural unit other than a structural unit derived from a (meth)acrylic compound is not particularly limited as long as it is a compound other than a (meth)acrylic compound that is copolymerizable with a (meth)acrylic compound. Examples of compounds copolymerizable with the (meth)acrylic compound other than the (meth)acrylic compound include styrene compounds which may have a substituent at the α-position or on the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene; vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. The (meth)acrylic resin may contain only one type of structural unit derived from these polymerizable monomers, or may contain two or more types.

[0093] In addition, from the viewpoint of improving alkaline developability, the (meth)acrylic resin preferably contains a structural unit having an acid group, such as a carboxy group, a sulfo group, a phosphate group, or a phosphonate group. The (meth)acrylic resin more preferably contains a structural unit having a carboxy group, and even more preferably contains a structural unit derived from the above-mentioned (meth)acrylic acid.

[0094] When the (meth)acrylic resin contains a structural unit having an acid group in the (meth)acrylic resin (preferably a structural unit derived from (meth)acrylic acid; the same applies hereinafter), the content of the structural unit having an acid group in the (meth)acrylic resin is preferably 10% by mass or more relative to the structural units of the (meth)acrylic resin, from the viewpoint of excellent developability. The upper limit of the content of the structural unit having an acid group in the (meth)acrylic resin is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total structural units of the (meth)acrylic resin, from the viewpoint of excellent alkali resistance.

[0095] The (meth)acrylic resin more preferably contains a structural unit derived from the above-mentioned alkyl (meth)acrylate ester. When the (meth)acrylic resin contains structural units derived from a (meth)acrylic acid alkyl ester, the content of the structural units derived from a (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 1% by mass to 90% by mass, more preferably 1% by mass to 50% by mass, and even more preferably 1% by mass to 30% by mass, relative to all structural units of the (meth)acrylic resin.

[0096] As the (meth)acrylic resin, a resin containing both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferred, and a resin formed only from a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is more preferred. The (meth)acrylic resin may also be an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate.

[0097] From the viewpoint of achieving better effects of the present disclosure, the (meth)acrylic resin preferably contains at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester, and preferably contains both structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester. From the viewpoint of achieving superior effects of the present disclosure, the total content of the structural units derived from methacrylic acid and the structural units derived from an alkyl methacrylate ester in the (meth)acrylic resin is preferably 40% by mass or more, and more preferably 60% by mass or more, relative to all structural units of the (meth)acrylic resin. The upper limit of the total content of the structural units derived from methacrylic acid and the structural units derived from an alkyl methacrylate ester in the (meth)acrylic resin may be, for example, 100% by mass or less, and preferably 80% by mass or less, relative to all structural units of the (meth)acrylic resin.

[0098] From the viewpoint of achieving even better effects of the present disclosure, the (meth)acrylic resin may contain at least one structural unit selected from the group consisting of structural units derived from methacrylic acid and structural units derived from a methacrylic acid alkyl ester, and at least one structural unit selected from the group consisting of structural units derived from acrylic acid and structural units derived from an acrylic acid alkyl ester.

[0099] The (meth)acrylic resin preferably has an ester group at its terminal, from the viewpoint that a photosensitive composition layer formed using the photosensitive composition has excellent developability. The terminals of the (meth)acrylic resin are composed of moieties derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at its terminal can be synthesized by using a radical polymerization initiator having an ester group.

[0100] From the viewpoint of developability, the alkali-soluble resin is preferably a resin having an acid value of 60 mgKOH / g or more. Furthermore, from the viewpoint that the alkali-soluble resin is easily thermally crosslinked with the crosslinking component by heating to form a strong film, it is more preferable that the alkali-soluble resin is a resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin), and it is particularly preferable that the alkali-soluble resin is a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH / g or more (so-called carboxy group-containing (meth)acrylic resin). When the alkali-soluble resin has a carboxy group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound to thermally crosslink the resin. Furthermore, when the carboxy group of the resin is dehydrated and made hydrophobic, the wet heat resistance can be improved.

[0101] The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as it satisfies the above-mentioned acid value requirement, and can be appropriately selected from known (meth)acrylic resins. Examples of the carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH / g or more that can be preferably used include, for example, carboxyl group-containing (meth)acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph

[0025] of JP-A No. 2011-95716, and carboxyl group-containing (meth)acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs

[0033] to

[0052] of JP-A No. 2010-237589.

[0102] Another preferred embodiment of the alkali-soluble resin is a styrene-acrylic copolymer. In the present disclosure, a styrene-acrylic copolymer refers to a resin containing structural units derived from a styrene compound and structural units derived from a (meth)acrylic compound. The total content of the structural units derived from styrene compounds and the structural units derived from (meth)acrylic compounds in the styrene-acrylic copolymer is, for example, preferably 30% by mass or more, and more preferably 50% by mass or more, relative to all structural units of the styrene-acrylic copolymer. Furthermore, the content of structural units derived from styrene compounds in the styrene-acrylic copolymer is, for example, preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5% by mass to 80% by mass, relative to all structural units of the styrene-acrylic copolymer. Furthermore, the content of structural units derived from (meth)acrylic compounds in the styrene-acrylic copolymer is, for example, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass to 95% by mass, relative to all structural units of the styrene-acrylic copolymer.

[0103] From the viewpoint of achieving better effects of the present disclosure, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure. Examples of monomers that form structural units having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). As the monomer that forms the structural unit having an aromatic ring structure, a monomer having an aralkyl group or styrene is preferred. Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group and a substituted or unsubstituted benzyl group, with a substituted or unsubstituted benzyl group being preferred. An example of a monomer having a phenylalkyl group is phenylethyl (meth)acrylate. Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group [e.g., benzyl (meth)acrylate and chlorobenzyl (meth)acrylate] and vinyl monomers having a benzyl group [e.g., vinylbenzyl chloride and vinylbenzyl alcohol], with benzyl (meth)acrylate being preferred.

[0104] From the viewpoint of achieving better effects of the present disclosure, the alkali-soluble resin more preferably contains a structural unit represented by the following formula (S) (that is, a structural unit derived from styrene).

[0105] [ka]

[0106] When the alkali-soluble resin contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and even more preferably 20% by mass to 60% by mass, relative to all structural units of the alkali-soluble resin, from the viewpoint of achieving better effects of the present disclosure.

[0107] From the viewpoint of achieving superior effects of the present disclosure, the content of structural units having an aromatic ring structure in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 60 mol %, relative to all structural units of the alkali-soluble resin.

[0108] From the viewpoint of achieving superior effects of the present disclosure, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, even more preferably 20 mol % to 60 mol %, and particularly preferably 20 mol % to 50 mol %, relative to all structural units of the alkali-soluble resin.

[0109] In the present disclosure, when the content of a "structural unit" is specified as a molar ratio, the "structural unit" is synonymous with a "monomer unit." In addition, in the present disclosure, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0110] From the viewpoint of achieving superior effects of the present disclosure, the alkali-soluble resin preferably contains a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be monocyclic or polycyclic. The alkali-soluble resin may contain a structural unit having a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

[0111] Examples of the aliphatic hydrocarbon ring include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring. Examples of monomers that form structural units having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0112] Furthermore, from the viewpoint of achieving better effects of the present disclosure, the alkali-soluble resin more preferably contains a constitutional unit represented by the following formula (Cy), and even more preferably contains a constitutional unit represented by the above formula (S) and a constitutional unit represented by the following formula (Cy).

[0113] [ka]

[0114] In the formula (Cy), RM represents a hydrogen atom or a methyl group, and R Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0115] R in formula (Cy) M is preferably a methyl group.

[0116] R in formula (Cy) Cy From the viewpoint of achieving better effects of the present disclosure, is preferably a monovalent group having an aliphatic hydrocarbon ring structure with 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 6 to 16 carbon atoms, and even more preferably a monovalent group having an aliphatic hydrocarbon ring structure with 8 to 14 carbon atoms.

[0117] R in formula (Cy) Cy From the viewpoint of achieving better effects of the present disclosure, the aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and even more preferably a tetrahydrodicyclopentadiene ring structure.

[0118] Also, R in formula (Cy) Cy In terms of achieving better effects of the present disclosure, the aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are fused, and more preferably a ring in which two to four aliphatic hydrocarbon rings are fused.

[0119] Also, R in formula (Cy) Cy From the viewpoint of achieving better effects of the present disclosure, is preferably a group in which the oxygen atom of —C(═O)O— in formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, i.e., an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentanyl group, and even more preferably a dicyclopentanyl group.

[0120] The alkali-soluble resin may contain only one type of structural unit having an aliphatic hydrocarbon ring structure, or may contain two or more types.

[0121] When the alkali-soluble resin contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and even more preferably 20% by mass to 70% by mass, relative to all structural units of the alkali-soluble resin, from the viewpoint of achieving better effects of the present disclosure.

[0122] Furthermore, from the viewpoint of achieving superior effects of the present disclosure, the content of structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, relative to all structural units of the alkali-soluble resin.

[0123] From the viewpoint of achieving superior effects of the present disclosure, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, relative to all structural units of the alkali-soluble resin.

[0124] When the alkali-soluble resin contains structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is, from the viewpoint of achieving better effects of the present disclosure, preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 40% by mass to 75% by mass, based on all structural units of the alkali-soluble resin.

[0125] From the viewpoint of achieving superior effects of the present disclosure, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 mol % to 80 mol %, more preferably 20 mol % to 70 mol %, and even more preferably 40 mol % to 60 mol %, relative to all structural units of the alkali-soluble resin.

[0126] From the viewpoint of achieving superior effects of the present disclosure, the total content of the structural units represented by the formula (S) and the structural units represented by the formula (Cy) in the alkali-soluble resin is preferably 10 mol % to 80 mol %, more preferably 20 mol % to 70 mol %, and even more preferably 40 mol % to 60 mol %, relative to all structural units of the alkali-soluble resin.

[0127] From the viewpoint of achieving better effects of the present disclosure, the molar amount nS of the constitutional unit represented by the above formula (S) and the molar amount nCy of the constitutional unit represented by the above formula (Cy) in the alkali-soluble resin preferably satisfy the relationship shown in the following formula (SCy), more preferably satisfy the relationship shown in the following formula (SCy-1), and even more preferably satisfy the relationship shown in the following formula (SCy-2). 0.20≦nS / (nS+nCy)≦0.80...Formula (SCy) 0.30≦nS / (nS+nCy)≦0.75...Formula (SCy-1) 0.40≦nS / (nS+nCy)≦0.70...Formula (SCy-2)

[0128] From the viewpoint of achieving superior effects of the present disclosure, the alkali-soluble resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and the carboxy group is preferred. As the structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferred, and a structural unit derived from methacrylic acid is more preferred.

[0129] [ka]

[0130] When the alkali-soluble resin contains a structural unit having an acid group, it may contain only one type of structural unit having an acid group, or may contain two or more types of structural units having an acid group.

[0131] When the alkali-soluble resin contains a structural unit having an acid group, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 30% by mass, relative to all structural units of the alkali-soluble resin, from the viewpoint of achieving better effects of the present disclosure.

[0132] From the viewpoint of achieving better effects of the present disclosure, the content of structural units having an acid group in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 50 mol %, and even more preferably 20 mol % to 40 mol %, relative to all structural units of the alkali-soluble resin.

[0133] From the viewpoint of achieving superior effects of the present disclosure, the content of the (meth)acrylic acid-derived structural units in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 50 mol %, and even more preferably 20 mol % to 40 mol %, relative to all structural units of the alkali-soluble resin.

[0134] From the viewpoint of achieving better effects of the present disclosure, the alkali-soluble resin preferably has a reactive group, and more preferably contains a structural unit having a reactive group. The reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group. When the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably contains a structural unit having an ethylenically unsaturated group in a side chain. In the present disclosure, the term "main chain" refers to the relatively longest bond chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to an atomic group branching off from the main chain. The ethylenically unsaturated group is more preferably an allyl group or a (meth)acryloxy group. Examples of structural units having a reactive group include, but are not limited to, those shown below.

[0135] [ka]

[0136] The alkali-soluble resin may contain only one type of structural unit having a reactive group, or may contain two or more types.

[0137] When the alkali-soluble resin contains a structural unit having a reactive group, the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass, relative to all structural units of the alkali-soluble resin, from the viewpoint of achieving better effects of the present disclosure.

[0138] From the viewpoint of achieving superior effects of the present disclosure, the content of structural units having a reactive group in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and even more preferably 20 mol % to 50 mol %, relative to all structural units of the alkali-soluble resin.

[0139] Examples of a method for introducing a reactive group into an alkali-soluble resin include a method of reacting a functional group such as a hydroxy group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group with a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic acid anhydride.

[0140] A preferred example of a method for introducing a reactive group into an alkali-soluble resin is to synthesize a polymer having a carboxy group by polymerization, and then react some of the carboxy groups of the resulting polymer with glycidyl (meth)acrylate by a polymer reaction to introduce a (meth)acryloxy group into the polymer. By this method, an alkali-soluble resin having a (meth)acryloxy group in its side chain can be obtained. The polymerization reaction is preferably carried out at a temperature of 70 to 100°C, more preferably at a temperature of 80 to 90°C. The polymerization initiator used in the polymerization reaction is preferably an azo-based initiator, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferred. The polymer reaction is preferably carried out at a temperature of 80°C to 110°C. In the polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

[0141] As the alkali-soluble resin, the following polymers are preferred from the viewpoint of achieving better effects of the present disclosure. Note that the content ratios (a to d) of the following structural units, the weight average molecular weight Mw, and the like can be changed appropriately depending on the purpose.

[0142] [ka]

[0143] The preferred values ​​for the content ratio of the above structural units are shown below. a: 20% by mass ~ 60% by mass b: 10% by mass ~ 50% by mass c: 5% by mass to 25% by mass d: 10% by mass to 50% by mass

[0144] [ka]

[0145] The preferred values ​​for the content ratio of the above structural units are shown below. a: 20% by mass ~ 60% by mass b: 10% by mass ~ 50% by mass c: 5% by mass to 25% by mass d: 10% by mass to 50% by mass

[0146] [ka]

[0147] The preferred values ​​for the content ratio of the above structural units are shown below. a: 30% by mass ~ 65% by mass b: 1% by mass to 20% by mass c: 5% by mass to 25% by mass d: 10% by mass to 50% by mass

[0148] [ka]

[0149] The preferred values ​​for the content ratio of the above structural units are shown below. a: 1% by mass ~ 20% by mass b: 20% by mass ~ 60% by mass c: 5% by mass to 25% by mass d: 10% by mass to 50% by mass

[0150] The alkali-soluble resin may contain a polymer containing a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X"). The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure. The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0151] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing, in its main chain, a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1, or a structural unit in which a monovalent group obtained by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0152] [ka]

[0153] In formula P-1, R A1a represents a substituent, n 1a R A1a may be the same or different, and Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, and n 1a represents an integer greater than or equal to 0.

[0154] R A1a Examples of the substituent represented by the formula include an alkyl group.

[0155] Z 1a As the alkylene group, an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is even more preferable.

[0156] n 1a represents an integer greater than or equal to 0. 1a When represents an alkylene group having 2 to 4 carbon atoms, n 1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

[0157] n 1a If represents an integer of 2 or more, there are multiple R A1a may be the same or different. A1a may be bonded to each other to form a ring, but preferably do not bond to each other to form a ring.

[0158] As a structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is even more preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0159] Specific examples of structural units having a carboxylic acid anhydride structure are listed below, but the structural units having a carboxylic acid anhydride structure are not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group, or a CF3 group, and Me represents a methyl group.

[0160] [ka]

[0161] [ka]

[0162] The polymer X may contain only one type of structural unit having a carboxylic acid anhydride structure, or may contain two or more types.

[0163] The total content of structural units having a carboxylic acid anhydride structure in polymer X is preferably 0 mol % to 60 mol %, more preferably 5 mol % to 40 mol %, and even more preferably 10 mol % to 35 mol %, based on all structural units of polymer X.

[0164] When the photosensitive composition contains a polymer X, it may contain only one type of polymer X, or may contain two or more types of polymer X.

[0165] When the photosensitive composition contains polymer X, the content of polymer X in the photosensitive composition is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, even more preferably 0.5% by mass to 20% by mass, and still more preferably 1% by mass to 20% by mass, relative to the total solid content of the photosensitive composition, from the viewpoint of achieving better effects of the present disclosure.

[0166] From the viewpoint of achieving better effects of the present disclosure, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 15,000 to 30,000.

[0167] The acid value of the alkali-soluble resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, further preferably 60 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 130 mgKOH / g. The acid value of the alkali-soluble resin is a value measured according to the method described in JIS K 0070:1992.

[0168] From the viewpoint of developability, the dispersity of the alkali-soluble resin is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, even more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 3.0.

[0169] When the photosensitive composition according to the present disclosure contains an alkali-soluble resin, it may contain only one type of alkali-soluble resin, or may contain two or more types of alkali-soluble resin.

[0170] When the photosensitive composition according to the present disclosure contains an alkali-soluble resin, the content of the alkali-soluble resin in the photosensitive composition is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 30% by mass to 70% by mass, relative to the total solid content of the photosensitive composition, from the viewpoint of achieving better effects of the present disclosure.

[0171] (polymerizable monomer) The photosensitive composition according to the present disclosure may include a polymerizable monomer. The polymerizable monomer is a monomer having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, with the radically polymerizable group being preferred.

[0172] The polymerizable monomer preferably includes a radical polymerizable monomer having an ethylenically unsaturated group. The ethylenically unsaturated group is preferably a (meth)acryloxy group.

[0173] One preferred embodiment of the polymerizable monomer is a compound represented by the following formula (M) (also simply referred to as "compound M"). Q 2 -R 1 -Q 1 ...Formula (M) In formula (M), Q 1 and Q 2 each independently represents a (meth)acryloyloxy group, R 1 represents a divalent linking group having a chain structure.

[0174] Q in formula (M) 1 and Q 2 are preferably the same group from the viewpoint of ease of synthesis. Also, Q in formula (M) 1 and Q 2 is preferably an acryloyloxy group from the viewpoint of reactivity.

[0175] R in formula (M) 1From the viewpoint of achieving a more excellent effect of the present disclosure, the alkylene group, the alkyleneoxyalkylene group (-L 1 -OL 1 -), or a polyalkyleneoxyalkylene group (-(L 1 -O) p -L 1 -) is preferred, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferred, an alkylene group having 4 to 20 carbon atoms is further preferred, and a linear alkylene group having 6 to 18 carbon atoms is particularly preferred. The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited and may be, for example, a branched, cyclic, or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof. An alkylene group or a group combining two or more alkylene groups and one or more arylene groups is preferred, an alkylene group is more preferred, and a linear alkylene group is even more preferred. L 1 each independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.

[0176] Q in formula (M) 1 and Q 2 From the viewpoint of achieving better effects of the present disclosure, the number of atoms in the shortest linking chain connecting In this disclosure, "Q 1 and Q 2 The number of atoms in the shortest chain connecting the two is Q 1 Connect to R 1 Q from atoms in 2 Connect to R 1 is the shortest number of atoms that connects to the atom in

[0177] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture. From the viewpoint of achieving better effects of the present disclosure, compound M is preferably at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate, more preferably at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate, and even more preferably at least one compound selected from 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

[0178] One preferred embodiment of the polymerizable monomer is a di- or higher functional ethylenically unsaturated compound. In the present disclosure, the term "difunctional or higher functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule. The ethylenically unsaturated group in the ethylenically unsaturated compound is preferably a (meth)acryloyl group. As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0179] The difunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of the difunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, and 1,4-cyclohexanediol di(meth)acrylate.

[0180] Commercially available bifunctional ethylenically unsaturated compounds include, for example, tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and dioxane glycol diacrylate (trade name: KAYARAD (registered trademark) R-604, manufactured by Nippon Kayaku Co., Ltd.).

[0181] The tri- or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds. Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

[0182] In the present disclosure, the term "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and the term "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0183] Examples of polymerizable monomers include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation, etc.), and ethoxylated glycerin triacrylate (NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.).

[0184] The polymerizable monomer also includes a urethane (meth)acrylate compound. Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. The urethane (meth)acrylate may also be a trifunctional or higher functional urethane (meth)acrylate. The lower limit of the number of functional groups is preferably 6 or more, and more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of tri- or higher functional urethane (meth)acrylates include 8UX-015A (trade name) manufactured by Taisei Fine Chemical Co., Ltd., UA-32P (trade name), U-15HA (trade name), and UA-1100H (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd., AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H (trade name), UA-306T (trade name), UA-306I (trade name), UA-510H (trade name), and UX-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0185] One preferred embodiment of the polymerizable monomer is an ethylenically unsaturated compound having an acid group. Acid groups include phosphate groups, sulfo groups, and carboxy groups. The acid group is preferably a carboxy group.

[0186] Examples of the ethylenically unsaturated compound having an acid group include a tri- or tetrafunctional ethylenically unsaturated compound having an acid group [a compound obtained by introducing a carboxy group into a pentaerythritol tri- or tetraacrylate (PETA) skeleton (acid value: 80 mg KOH / g to 120 mg KOH / g)], a penta- or hexafunctional ethylenically unsaturated compound having an acid group [a compound obtained by introducing a carboxy group into a dipentaerythritol penta- or hexaacrylate (DPHA) skeleton (acid value: 25 mg KOH / g to 70 mg KOH / g)], and the like. The tri- or higher functional ethylenically unsaturated compound having an acid group may be used in combination with a difunctional ethylenically unsaturated compound having an acid group, if necessary.

[0187] The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof. When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of di- or higher functional ethylenically unsaturated compounds having a carboxy group and carboxylic acid anhydrides thereof, the developability and film strength are further improved. The di- or higher functional ethylenically unsaturated compound having a carboxy group is not particularly limited and can be appropriately selected from known compounds. Examples of the difunctional or higher ethylenically unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

[0188] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 is preferred, and the contents of this publication are incorporated herein by reference.

[0189] Examples of the polymerizable monomer include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, urethane monomers such as (meth)acrylate compounds having a urethane bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters. These may be used alone or in combination of two or more.

[0190] Examples of compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid include bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups; tri(meth)acrylate; Examples of the acrylate include methylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. The compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid is preferably an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure, and more preferably tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate.

[0191] Examples of the polymerizable monomer include caprolactone-modified ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified ethylenically unsaturated compounds (e.g., KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135 manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0192] As the polymerizable monomer (particularly, an ethylenically unsaturated compound), a polymerizable monomer containing an ester bond is also preferred from the viewpoint of excellent developability of a photosensitive composition layer formed using the photosensitive composition. The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule. However, from the viewpoint of achieving excellent effects of the present disclosure, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.

[0193] From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure. Examples of ethylenically unsaturated compounds having an aliphatic structure with 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0194] One suitable embodiment of the polymerizable monomer is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound). As the polymerizable monomer, a polymerizable compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferred, a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are fused is more preferred, and tricyclodecane dimethanol di(meth)acrylate is even more preferred. As the aliphatic hydrocarbon ring structure, from the viewpoint of achieving superior effects of the present disclosure, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isoborone structure is preferred.

[0195] The molecular weight of the polymerizable monomer is not particularly limited, but is preferably from 200 to 3,000, more preferably from 250 to 2,600, even more preferably from 280 to 2,200, and particularly preferably from 300 to 2,200.

[0196] Among the polymerizable monomers contained in the photosensitive composition, the content ratio of polymerizable monomers having a molecular weight of 300 or less is preferably 30 mass % or less, more preferably 25 mass % or less, and even more preferably 20 mass % or less, based on the content of all polymerizable monomers contained in the photosensitive composition.

[0197] As one preferred embodiment of the photosensitive composition, the photosensitive composition preferably contains a difunctional or higher ethylenically unsaturated compound as a polymerizable monomer, more preferably a trifunctional or higher ethylenically unsaturated compound, and even more preferably a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0198] In addition, as one suitable embodiment of the photosensitive composition, the photosensitive composition preferably contains, as the polymerizable monomer, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and, as the alkali-soluble resin, a resin having a structural unit having an aliphatic hydrocarbon ring.

[0199] In addition, as one suitable embodiment of the photosensitive composition, the photosensitive composition preferably contains, as polymerizable monomers, compound M and an ethylenically unsaturated compound having an acid group, more preferably contains, as polymerizable monomers, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably contains, as polymerizable monomers, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a succinic acid-modified product of dipentaerythritol pentaacrylate.

[0200] In addition, as one suitable embodiment of the photosensitive composition, the photosensitive composition preferably contains, as polymerizable monomers, a compound M and an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described below, and more preferably contains, as polymerizable monomers, a compound M and an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described below.

[0201] In addition, as one of the preferred embodiments of the photosensitive composition, from the viewpoints of suppressing development residues and rust prevention, the photosensitive composition preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher functional (meth)acrylate compound).

[0202] The mass ratio of the content of the difunctional ethylenically unsaturated compound to the content of the tri- or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, and more preferably 30:70 to 70:30.

[0203] The proportion of the content of the bifunctional ethylenically unsaturated compound relative to the total content of all ethylenically unsaturated compounds is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass.

[0204] The content of the difunctional ethylenically unsaturated compound in the photosensitive composition is preferably 10% by mass to 60% by mass, and more preferably 15% by mass to 40% by mass, based on the total solid content of the photosensitive composition.

[0205] In addition, as one of the preferred embodiments of the photosensitive composition, the photosensitive composition preferably contains a compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, from the viewpoint of rust prevention.

[0206] In addition, as one preferred embodiment of the photosensitive composition, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive composition preferably contains compound M and an ethylenically unsaturated compound having an acid group, more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, still more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a tri- or higher functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound.

[0207] Furthermore, as one suitable embodiment of the photosensitive composition, from the viewpoints of substrate adhesion, suppression of development residues, and rust prevention, the photosensitive composition preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, still more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

[0208] The photosensitive composition may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0209] The content of the difunctional or higher functional ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive composition.

[0210] When the photosensitive composition according to the present disclosure contains a polymerizable monomer, it may contain only one type of polymerizable monomer (particularly, an ethylenically unsaturated compound), or may contain two or more types.

[0211] When the photosensitive composition according to the present disclosure contains a polymerizable monomer, the content of the polymerizable monomer (particularly, an ethylenically unsaturated compound) in the photosensitive composition is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, even more preferably 5% by mass to 60% by mass, and particularly preferably 5% by mass to 50% by mass, relative to the total solid content of the photosensitive composition.

[0212] (Photopolymerization initiator) The photosensitive composition according to the present disclosure may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. The photopolymerization initiator may be a photoradical polymerization initiator.

[0213] Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter also referred to as an "α-aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as an "N-phenylglycine-based photopolymerization initiator").

[0214] The photopolymerization initiator preferably contains at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylphenone-based polymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably contains at least one selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

[0215] Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP 2011-95716 A and paragraphs

[0064] to

[0081] of JP 2015-014783 A may be used.

[0216] Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE® OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE® OXE-02, manufactured by BASF], IRGACURE® OXE03 (manufactured by BASF), IRGACURE® OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad® 379EG, manufactured by IGM Resins], and the like. BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad® 907, IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad® 127, IGM Resins BV], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad® 369, IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad® 1173, IGM Resins BV], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad® 184, IGM Resins BV] BV)], 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad (registered trademark) 651, IGM Resins B.oxime esters [trade name: Lunar (registered trademark) 6, manufactured by DKSH Japan Co., Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG- 326, Changzhou Strong Electronic New Materials Co., Ltd.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.), and 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (trade name: APi-307, Shenzhen UV-ChemTech Ltd.).

[0217] When the photosensitive composition according to the present disclosure contains a photopolymerization initiator, it may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When the photosensitive composition according to the present disclosure contains two or more types of photopolymerization initiators, it preferably contains an oxime-based photopolymerization initiator and at least one selected from the group consisting of an α-aminoalkylphenone-based photopolymerization initiator and an α-hydroxyalkylphenone-based polymerization initiator.

[0218] When the photosensitive composition according to the present disclosure contains a photopolymerization initiator, the content of the photopolymerization initiator in the photosensitive composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the photosensitive composition. The upper limit of the content of the photopolymerization initiator in the photosensitive composition according to the present disclosure is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the photosensitive composition.

[0219] (acid generator) When the photosensitive composition according to the present disclosure contains a colorant precursor that develops a black color in the presence of an acid, it may also contain an acid generator. The acid generator may be a photoacid generator or a thermal acid generator, but is preferably a photoacid generator.

[0220] A photoacid generator is a compound that can generate an acid when irradiated with radiation such as ultraviolet light, far ultraviolet light, X-rays, or charged particle beams. The photoacid generator is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid. In addition, even if the photoacid generator is not directly sensitive to actinic rays with a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer, as long as it responds to actinic rays with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.

[0221] The photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and even more preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of the pKa is not particularly limited, but is preferably, for example, −10 or more.

[0222] Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators. Examples of the ionic photoacid generator include onium salt compounds, quaternary ammonium salt compounds, etc. Examples of the onium salt compounds include diaryliodonium salt compounds, triarylsulfonium salt compounds, etc. The ionic photoacid generator is preferably an onium salt compound, and more preferably at least one selected from the group consisting of diaryliodonium salt compounds and triarylsulfonium salt compounds.

[0223] As the ionic photoacid generator, for example, the ionic photoacid generators described in paragraphs

[0114] to

[0133] of JP-A-2014-85643 can also be preferably used.

[0224] Examples of the nonionic photoacid generator include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Specific examples of the trichloromethyl-s-triazine compound, the diazomethane compound, and the imide sulfonate compound include the compounds described in paragraphs

[0083] to

[0088] of JP-A No. 2011-221494. Specific examples of the oxime sulfonate compound include the compounds described in paragraphs

[0084] to

[0088] of WO 2018 / 179640.

[0225] From the viewpoint of sensitivity, the photoacid generator is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably an oxime sulfonate compound.

[0226] When the photosensitive composition according to the present disclosure contains an acid generator, it may contain only one type of acid generator or may contain two or more types of acid generators.

[0227] When the photosensitive composition according to the present disclosure contains an acid generator, the content of the acid generator is preferably 0.2% by mass to 5.0% by mass, and more preferably 0.5% by mass to 3.0% by mass, relative to the total solid content of the photosensitive composition, from the viewpoint of, for example, the color-developing properties of the colorant precursor that develops a black color in the presence of an acid.

[0228] (sensitizer) The photosensitive composition according to the present disclosure may also include a sensitizer. The sensitizer has the effect of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.

[0229] Sensitizers include, for example, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, N-phenylglycine, tributyltin acetate, and trithiane.

[0230] When the photosensitive composition according to the present disclosure contains a sensitizer, it may contain only one type of sensitizer, or may contain two or more types of sensitizers.

[0231] When the photosensitive composition according to the present disclosure contains a sensitizer, the content of the sensitizer in the photosensitive composition is preferably 0.01% by mass to 1% by mass, and more preferably 0.02% by mass to 0.5% by mass, relative to the total solid content of the photosensitive composition.

[0232] (heterocyclic compounds) The photosensitive composition according to the present disclosure may contain a heterocyclic compound. The heterocyclic ring contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring. Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

[0233] Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. The heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds.

[0234] Preferred specific examples of the heterocyclic compound are shown below. Examples of triazole compounds and benzotriazole compounds include the following compounds.

[0235] [ka]

[0236] [ka]

[0237] Examples of the tetrazole compound include the following compounds.

[0238] [ka]

[0239] [ka]

[0240] Examples of the thiadiazole compound include the following compounds:

[0241] [ka]

[0242] Examples of the triazine compound include the following compounds:

[0243] [ka]

[0244] Examples of rhodanine compounds include the following compounds:

[0245] [ka]

[0246] Examples of the thiazole compound include the following compounds:

[0247] [ka]

[0248] Examples of the benzothiazole compound include the following compounds:

[0249] [ka]

[0250] Examples of the benzimidazole compound include the following compounds:

[0251] [ka]

[0252] [ka]

[0253] Examples of the benzoxazole compound include the following compounds:

[0254] [ka]

[0255] When the photosensitive composition according to the present disclosure contains a heterocyclic compound, it may contain only one type of heterocyclic compound or may contain two or more types of heterocyclic compounds.

[0256] When the photosensitive composition according to the present disclosure contains a heterocyclic compound, the content of the heterocyclic compound in the photosensitive composition is preferably 0.01% by mass to 20.0% by mass, more preferably 0.10% by mass to 10.0% by mass, even more preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass, relative to the total solid content of the photosensitive composition.

[0257] (Aliphatic thiol compounds) The photosensitive composition according to the present disclosure may include an aliphatic thiol compound. When the photosensitive composition contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with the radical polymerizable compound having an ethylenically unsaturated group, thereby suppressing the cure shrinkage of the resulting film and alleviating the stress of the film.

[0258] The aliphatic thiol compound is preferably a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher functional aliphatic thiol compound).

[0259] As the aliphatic thiol compound, from the viewpoint of the adhesion of the pattern to be formed (particularly the adhesion after exposure), a polyfunctional aliphatic thiol compound is preferred. In the present disclosure, the term "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also called "mercapto groups") in the molecule.

[0260] The polyfunctional aliphatic thiol compound is preferably a low molecular weight compound having a molecular weight of at least 100. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

[0261] The number of functional groups in the polyfunctional aliphatic thiol compound is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, from the viewpoint of adhesion of the pattern to be formed.

[0262] Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionyloxy)ethyl ester), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.

[0263] Among these, the polyfunctional aliphatic thiol compound is preferably at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0264] Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0265] When the photosensitive composition according to the present disclosure contains an aliphatic thiol compound, it may contain only one type of aliphatic thiol compound, or may contain two or more types of aliphatic thiol compounds.

[0266] When the photosensitive composition according to the present disclosure contains an aliphatic thiol compound, the content of the aliphatic thiol compound in the photosensitive composition is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, even more preferably 5% by mass to 30% by mass, and particularly preferably 8% by mass to 20% by mass, relative to the total solid content of the photosensitive composition.

[0267] (Thermal crosslinkable compound) The photosensitive composition according to the present disclosure preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. In the present disclosure, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered an ethylenically unsaturated compound but is considered a thermally crosslinkable compound.

[0268] Examples of the thermally crosslinkable compound include an epoxy compound, an oxetane compound, a methylol compound, and a blocked isocyanate compound. The thermally crosslinkable compound is preferably a blocked isocyanate compound from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.

[0269] Since blocked isocyanate compounds react with hydroxy groups and carboxy groups, for example, when at least one of an alkali-soluble resin and a radically polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease and its function as a protective film tends to be enhanced. Note that the term "blocked isocyanate compound" refers to "a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

[0270] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably from 90°C to 160°C, and more preferably from 100°C to 150°C, for example. The dissociation temperature of a blocked isocyanate means "the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter." As the differential scanning calorimeter, for example, a differential scanning calorimeter (model number: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

[0271] Examples of blocking agents having a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime). Among these, as the blocking agent having a dissociation temperature of 90° C. to 160° C., at least one compound selected from the group consisting of oxime compounds and pyrazole compounds is preferred from the viewpoint of storage stability, for example.

[0272] The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesive strength to the transfer target. A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by isocyanuration. Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure in which an oxime compound is used as a blocking agent are preferred because the dissociation temperature can be more easily adjusted to a preferred range and development residues can be reduced compared to compounds not having an oxime structure.

[0273] The blocked isocyanate compound may have a polymerizable group. The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radical polymerizable group being preferred. Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group. Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

[0274] As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, and Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko K.K.), and the blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) SBN-70D, and Duranate (registered trademark) WT32-B75P manufactured by Asahi Kasei Chemicals Corporation).

[0275] From the viewpoint of achieving better effects of the present disclosure, it is preferable that the photosensitive composition contains a blocked isocyanate compound having an NCO value of 4.5 mmol / g or more (hereinafter also referred to as a "first blocked isocyanate compound"). The NCO value of the first blocked isocyanate compound is preferably 5.0 mmol / g or more, more preferably 5.3 mmol / g or more. From the viewpoint of achieving superior effects of the present disclosure, the upper limit of the NCO value of the first blocked isocyanate compound is preferably 8.0 mmol / g or less, more preferably 6.0 mmol / g or less, even more preferably 5.8 mmol / g or less, and particularly preferably 5.7 mmol / g or less. In the present disclosure, the NCO value of a blocked isocyanate compound means the number of moles of isocyanate groups contained in 1 g of the blocked isocyanate compound, and is a value calculated from the structural formula of the blocked isocyanate compound.

[0276] From the viewpoint of achieving better effects of the present disclosure, the first blocked isocyanate compound preferably has a ring structure. Examples of the ring structure include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocycle. From the viewpoint of achieving better effects of the present disclosure, an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring are preferred, and an aliphatic hydrocarbon ring is more preferred.

[0277] Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, and among these, a cyclohexane ring is preferred.

[0278] Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, with a benzene ring being preferred.

[0279] A specific example of the heterocyclic ring is an isocyanurate ring.

[0280] When the first blocked isocyanate compound has a ring structure, the number of rings is preferably 1 to 2, and more preferably 1, from the viewpoint of achieving better effects of the present disclosure. When the first blocked isocyanate compound contains a fused ring, the number of rings constituting the fused ring is counted; for example, the number of rings in a naphthalene ring is counted as two.

[0281] The number of blocked isocyanate groups in the first blocked isocyanate compound is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2, from the viewpoint of excellent strength of the formed pattern and better effects of the present disclosure.

[0282] From the viewpoint of achieving better effects of the present disclosure, the first blocked isocyanate compound is preferably a blocked isocyanate compound represented by the following formula Q: B 1 -A 1 -L 1 -A 2 -B 2 ...Formula Q

[0283] In formula Q, B 1 and B 2 each independently represents a blocked isocyanate group. The blocked isocyanate group is not particularly limited, but from the viewpoint of achieving better effects of the present disclosure, a group in which an isocyanate group is blocked with an oxime compound is preferred, and a group in which an isocyanate group is blocked with methyl ethyl ketoxime (specifically, a group represented by *-NH-C(=O)-ON=C(CH3)-C2H5, * represents A 1 or A 2 represents the bonding position with.) is more preferred. B 1 and B 2 are preferably the same group.

[0284] In formula Q, A 1 and A 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, and preferably an alkylene group having 1 to 10 carbon atoms. The alkylene group may be linear, branched, or cyclic, and is preferably linear. The alkylene group has 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 carbon atom, from the viewpoint of achieving better effects of the present disclosure. A 1 and A 2 are preferably the same group.

[0285] In formula Q, L 1 represents a divalent linking group. Specific examples of the divalent linking group include divalent hydrocarbon groups. Specific examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by linking two or more of these groups. The divalent saturated hydrocarbon group may be linear, branched, or cyclic, and is preferably cyclic from the viewpoint of achieving better effects of the present disclosure. The number of carbon atoms in the divalent saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 10, and even more preferably 5 to 8, from the viewpoint of achieving better effects of the present disclosure. The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. The divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group). The divalent linking group is preferably a linear, branched, or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a group in which a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms is linked to a linear alkylene group having 1 to 3 carbon atoms, a divalent aromatic hydrocarbon group which may have a substituent, or a group in which a divalent aromatic hydrocarbon group is linked to a linear alkylene group having 1 to 3 carbon atoms, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms or a phenylene group which may have a substituent, still more preferably a cyclohexylene group or a phenylene group which may have a substituent, and particularly preferably a cyclohexylene group.

[0286] From the viewpoint of achieving better effects of the present disclosure, the blocked isocyanate compound represented by formula Q is particularly preferably a blocked isocyanate compound represented by the following formula QA. B 1a -A 1a -L 1a -A 2a -B 2a ···QA

[0287] During the Q&A, B 1a and B 2a each independently represents a blocked isocyanate group. B 1a and B 2a A preferred embodiment of the formula Q is B 1 and B2 is the same as:

[0288] During the Q&A, A 1a and A 2a each independently represents a divalent linking group. A 1a and A 2a A preferred embodiment of the divalent linking group in formula Q is 1 and A 2 is the same as:

[0289] During the Q&A, L 1a represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group. L 1a The cyclic divalent saturated hydrocarbon group in the formula (I) preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, further preferably 5 or 6 carbon atoms, and particularly preferably 6 carbon atoms. L 1a A preferred embodiment of the divalent aromatic hydrocarbon group in formula Q is 1 is the same as: L 1a is preferably a cyclic divalent saturated hydrocarbon group, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, even more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, particularly preferably a cyclic divalent saturated hydrocarbon group having 5 to 6 carbon atoms, and most preferably a cyclohexylene group. L 1a When is a cyclohexylene group, the blocked isocyanate compound represented by the formula QA may be an isomeric mixture of cis and trans isomers. The mass ratio of cis isomer to trans isomer is preferably cis / trans=10 / 90 to 90 / 10, more preferably cis / trans=40 / 60 to 60 / 40.

[0290] Specific examples of the first blocked isocyanate compound are shown below, but the first blocked isocyanate compound is not limited to these.

[0291] [ka]

[0292] When the photosensitive composition according to the present disclosure contains a thermally crosslinkable compound, it may contain only one type of thermally crosslinkable compound, or may contain two or more types of thermally crosslinkable compounds.

[0293] When the photosensitive composition according to the present disclosure contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound in the photosensitive composition is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass, relative to the total solid content of the photosensitive composition.

[0294] (surfactant) The photosensitive composition according to the present disclosure may also contain a surfactant. Examples of surfactants include those described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of JP-A-2009-237362.

[0295] Examples of surfactants include hydrocarbon surfactants, fluorine-based surfactants, and silicone-based surfactants. From the viewpoint of improving environmental friendliness, it is preferable that the surfactant does not contain fluorine atoms. The surfactant is preferably a hydrocarbon surfactant or a silicone surfactant.

[0296] Commercially available fluorine-based surfactants include, for example, Megafac (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, E XP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation), Fluorad (registered trademark) FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC Inc.), PolyFox (registered trademark) PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA), Ftergent (registered trademark) Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS Corporation), and U-120E (manufactured by Unichem Corporation).

[0297] Also suitable for use as fluorosurfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac (registered trademark) DS-21.

[0298] As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

[0299] Furthermore, a block polymer can also be used as the fluorine-based surfactant.

[0300] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably, five or more) alkyleneoxy groups (preferably, ethyleneoxy groups or propyleneoxy groups) can also be preferably used.

[0301] In addition, fluorine-containing polymers having an ethylenically unsaturated bond-containing group in the side chain can also be used as fluorine-containing surfactants, such as Megafac (registered trademark) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0302] From the viewpoint of improving environmental friendliness, preferred fluorine-based surfactants are surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

[0303] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters.

[0304] Commercially available hydrocarbon surfactants include, for example, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic (registered trademark) 304, 701, 704, 901, 904, and 150R1, HYDROPALAT (registered trademark) WE 3323 (all manufactured by BASF), Solsperse (registered trademark) 20000 (all manufactured by The Lubrizol Chemical Company, Ltd.), NCW-101, NCW-1001, and NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Paionin (registered trademark) D-1105, D-6112, D-6112-W, and D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine (registered trademark) E1010, and Surfynol (registered trademark). 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).

[0305] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers having organic groups introduced into the side chains or terminals, and polymers having a structural unit having a hydrophilic group in the side chain and a structural unit having a siloxane bond-containing group in the side chain. Among these, preferred silicone surfactants are polymers having a structural unit having a hydrophilic group in the side chain and a structural unit having a siloxane bond-containing group in the side chain. The polymer may be a random copolymer or a block copolymer.

[0306] Examples of the structural unit having a hydrophilic group in the side chain include structural units derived from monomers represented by the following formula:

[0307] [ka]

[0308] In the formula, R 4 represents a hydrogen atom or a methyl group, and R 5 represents a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.

[0309] Examples of the structural unit having a siloxane bond-containing group in the side chain include structural units derived from monomers represented by the following formula:

[0310] [ka]

[0311] In the formula, each R independently represents an alkyl group having 1 to 3 carbon atoms, and R 1 represents a hydrogen atom or a methyl group, and L 1 represents a divalent organic group or a single bond.

[0312] Further, examples of the structural unit having a siloxane bond-containing group in the side chain include structural units derived from monomers represented by the following formula:

[0313] [ka]

[0314] In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 1 to 10 carbon atoms, R3 represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50.

[0315] Commercially available silicone surfactants include, for example, EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation), DOWSIL (registered trademark) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone. SH8400 (manufactured by Dow Corning Toray Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, KF- 6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-12 1, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, K Examples of suitable esters include P-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials), and BYK300, BYK306, BYK307, BYK310, BYK320, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0316] The surfactant is preferably a nonionic surfactant.

[0317] When the photosensitive composition according to the present disclosure contains a surfactant, it may contain only one type of surfactant, or may contain two or more types of surfactants.

[0318] When the photosensitive composition according to the present disclosure contains a surfactant, the content of the surfactant in the photosensitive composition is preferably 0.01% by mass to 3.0% by mass, more preferably 0.01% by mass to 1.0% by mass, and even more preferably 0.05% by mass to 0.80% by mass, relative to the total solid content of the photosensitive composition.

[0319] (polymerization inhibitor) The photosensitive composition according to the present disclosure may contain a polymerization inhibitor. The polymerization inhibitor means a compound that has the function of delaying or inhibiting the polymerization reaction. The polymerization inhibitor is not particularly limited, and for example, a known compound used as a polymerization inhibitor can be used.

[0320] Examples of polymerization inhibitors include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-te nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; and metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. Among these, from the viewpoint of achieving better effects of the present disclosure, the polymerization inhibitor is preferably at least one selected from the group consisting of a phenothiazine compound, a nitroso compound or a salt thereof, and a hindered phenol compound, and more preferably at least one selected from the group consisting of phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), p-methoxyphenol, and N-nitrosophenylhydroxylamine aluminum salt.

[0321] When the photosensitive composition according to the present disclosure contains a polymerization inhibitor, it may contain only one type of polymerization inhibitor, or may contain two or more types of polymerization inhibitors.

[0322] When the photosensitive composition according to the present disclosure contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.02% by mass to 2.0% by mass, relative to the total solid content of the photosensitive composition. Furthermore, when the photosensitive composition according to the present disclosure contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive composition is preferably 0.005% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.01% by mass to 1.0% by mass, relative to the total mass of the polymerizable monomers.

[0323] (Hydrogen donor compounds) The photosensitive composition according to the present disclosure may also include a hydrogen donor compound. The hydrogen donor compound has the effect of further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing the inhibition of polymerization of the polymerizable compound by oxygen.

[0324] Examples of hydrogen donor compounds include amines and amino acid compounds.

[0325] Examples of amines include compounds described in M.R. Sander et al., Journal of Polymer Society, Vol. 10, p. 3173 (1972), JP-B-44-020189, JP-A-51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure No. 33825. More specifically, examples of amines include 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline. In terms of achieving better effects of the present disclosure, the amines are preferably at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0326] Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. As the amino acid compound, N-phenylglycine is preferred in that the effects of the present disclosure are more excellent.

[0327] Further, examples of the hydrogen donor compound include organometallic compounds (e.g., tributyltin acetate) described in JP-B-48-042965, hydrogen donors described in JP-B-55-034414, and sulfur compounds (e.g., trithiane) described in JP-A-6-308727.

[0328] When the photosensitive composition according to the present disclosure contains a hydrogen donor compound, it may contain only one type of hydrogen donor compound or may contain two or more types of hydrogen donor compounds.

[0329] When the photosensitive composition according to the present disclosure contains a hydrogen-donor compound, the content of the hydrogen-donor compound in the photosensitive composition is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and even more preferably 0.03% by mass to 5.0% by mass, relative to the total solid content of the photosensitive composition, from the viewpoint of improving the curing rate through a balance between the polymerization propagation rate and chain transfer.

[0330] (solvent) The photosensitive composition according to the present disclosure may contain a solvent. The solvent may be water or an organic solvent, but an organic solvent is preferred. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0331] The solvent may be an organic solvent having a boiling point of 180° C. to 250° C. (a so-called high-boiling solvent).

[0332] When the photosensitive composition according to the present disclosure contains a solvent, it may contain only one type of solvent, or may contain two or more types of solvent.

[0333] When the photosensitive composition according to the present disclosure contains a solvent, the content of the solvent in the photosensitive composition is preferably 20% by mass to 95% by mass, more preferably 60% by mass to 95% by mass, and even more preferably 70% by mass to 95% by mass, relative to the total mass of the photosensitive composition.

[0334] (Other ingredients) The photosensitive composition according to the present disclosure may contain components other than those already described (also referred to as "other components"). Other ingredients include, for example, colorants (eg, pigments and dyes), antioxidants, and particles (eg, metal oxide particles). Other components include other additives described in paragraphs

[0058] to

[0071] of JP-A No. 2000-310706.

[0335] -Coloring agent- The photosensitive composition according to the present disclosure may contain a colorant (pigment, dye, etc.), but preferably does not substantially contain a colorant, for example, from the viewpoint of transparency. When the photosensitive composition according to the present disclosure contains a colorant, the content of the colorant in the photosensitive composition is preferably less than 1 mass %, and more preferably less than 0.1 mass %, relative to the total solid content of the photosensitive composition.

[0336] -Antioxidants- The photosensitive composition according to the present disclosure may also include an antioxidant. Examples of antioxidants include 3-pyrazolidones such as 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. Among these, as the antioxidant, 3-pyrazolidones are preferred, and 1-phenyl-3-pyrazolidone is more preferred, from the viewpoint of achieving better effects of the present disclosure.

[0337] When the photosensitive composition according to the present disclosure contains an antioxidant, the content of the antioxidant in the photosensitive composition is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, based on the total solid content of the photosensitive composition. The upper limit is not particularly limited, but is preferably, for example, 1% by mass or less.

[0338] -particle- The photosensitive composition according to the present disclosure may include particles. The particles are preferably metal oxide particles. The metals in the metal oxide particles also include metalloids such as B, Si, Ge, As, Sb, and Te. The average primary particle size of the particles is preferably from 1 nm to 200 nm, and more preferably from 3 nm to 80 nm, from the viewpoint of the transparency of the cured film, for example. The average primary particle size of particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and calculating the arithmetic mean of the measurement results. If the particle shape is not spherical, the particle size is taken to be the longest side.

[0339] When the photosensitive composition according to the present disclosure contains particles, it may contain only one type of particles or two or more types of particles differing in metal type, size, etc.

[0340] The photosensitive composition according to the present disclosure does not contain particles, or if the photosensitive composition according to the present disclosure contains particles, the particle content is preferably more than 0% by mass and not more than 35% by mass, relative to the total solid content of the photosensitive composition; more preferably, the photosensitive composition does not contain particles, or the particle content is more than 0% by mass and not more than 10% by mass, relative to the total solid content of the photosensitive composition; even more preferably, the photosensitive composition does not contain particles, or the particle content is more than 0% by mass and not more than 5% by mass, relative to the total solid content of the photosensitive composition; even more preferably, the photosensitive composition does not contain particles, or the particle content is more than 0% by mass and not more than 1% by mass, relative to the total solid content of the photosensitive composition; and particularly preferably, the photosensitive composition does not contain particles.

[0341] When a film having a thickness of 1 μm is formed using the photosensitive composition according to the present disclosure, the absorbance of the film at a wavelength of 365 nm (hereinafter also referred to as "absorbance A1") is preferably 0.1 or less, more preferably 0.08 or less, even more preferably 0.06 or less, and particularly preferably 0.04 or less, from the viewpoint of patterning properties. The lower limit is not particularly limited, and may be, for example, 0.001 or more. The absorbance of the film at a wavelength of 365 nm being 0.1 or less means that the film in a state in which the specific colorant precursor has not been made light-absorbent by stimulation has excellent transmittance to light at a wavelength of 365 nm. When the absorbance of the film at a wavelength of 365 nm is 0.1 or less, incident light gradually attenuates in the thickness direction of the film formed using the photosensitive composition (i.e., the photosensitive composition layer) during exposure, and for example, in the case of a negative type, a phenomenon such as insufficient polymerization and curing is less likely to occur, and a pattern with a good shape tends to be easily obtained.

[0342] When the photosensitive composition according to the present disclosure is used to impart light absorption to a specific colorant precursor by stimulation to form a light-absorbing film having a thickness of 1 μm, the absorbance of the film at a wavelength of 365 nm (hereinafter also referred to as "absorbance A2") is preferably 0.14 or more, more preferably 0.16 or more, even more preferably 0.18 or more, and particularly preferably 0.2 or more. There is no particular upper limit, and it can be, for example, 4.0 or less.

[0343] The ratio of absorbance A2 to absorbance A1 (absorbance A2 / absorbance A1) is preferably 5.0 or more, and more preferably 7.0 or more.

[0344] When the photosensitive composition according to the present disclosure is used to impart light absorption to a specific colorant precursor by stimulation to form a light-absorbing film having a thickness of 1 μm, the average absorbance of the film at wavelengths of 400 nm to 700 nm is preferably 0.14 or more, more preferably 0.16 or more, even more preferably 0.18 or more, and particularly preferably 0.2 or more. The upper limit is not particularly limited, and may be, for example, 4.0 or less. The fact that the absorbance of the film at a wavelength of 365 nm and the average absorbance at wavelengths of 400 nm to 700 nm are both 0.14 or more means that the film in which the specific colorant precursor has been given light absorption properties through stimulation has excellent light-blocking properties for light with wavelengths from the ultraviolet region to the visible region.

[0345] When the photosensitive composition according to the present disclosure is used to form a film having a thickness of 1 μm and exhibiting light absorption by imparting light absorption to a specific colorant precursor in response to a stimulus, the film may have absorption at wavelengths of 700 nm or more. For example, the film may have absorption in the near-infrared region of 700 to 950 nm. The absorption at wavelengths of 700 nm or more may be absorbed by the compound that imparts light absorption to the specific colorant precursor in response to a stimulus, or may be absorbed by another colorant.

[0346] In this disclosure, "absorbance" is a value measured using a spectrophotometer. The spectrophotometer may be, for example, an ultraviolet-visible spectrophotometer (model number: UV-1800) manufactured by Shimadzu Corporation, although the spectrophotometer is not limited to this.

[0347] A preferred embodiment of the photosensitive composition according to the present disclosure comprises a colorant precursor that exhibits light absorption in response to at least one stimulus selected from the group consisting of heat, light, an acid, a base, and a radical, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, and satisfies all of the following (1) to (3): (1) When a film having a thickness of 1 μm is formed using the photosensitive composition, the absorbance of the film at a wavelength of 365 nm is 0.1 or less. (2) When the photosensitive composition is used and the colorant precursor is made light-absorbent by the above stimulus to form a light-absorbing film having a thickness of 1 μm, the film has an absorbance of 0.2 or more at a wavelength of 365 nm. (3) When the photosensitive composition is used and the colorant precursor is made light-absorbent by the above stimulus to form a light-absorbing film having a thickness of 1 μm, the average absorbance of the film at wavelengths of 400 nm to 700 nm is 0.2 or more.

[0348] <<Viscosity of photosensitive composition>> The viscosity of the photosensitive composition according to the present disclosure at 25°C is, for example, preferably from 1 mPa·s to 50 mPa·s, more preferably from 2 mPa·s to 40 mPa·s, and even more preferably from 3 mPa·s to 30 mPa·s, from the viewpoint of coatability. The viscosity of the photosensitive composition according to the present disclosure is measured using a viscometer. As the viscometer, for example, a viscometer (trade name: VISCOMETER TV-22) manufactured by Toki Sangyo Co., Ltd. can be suitably used. However, the viscometer is not limited to the above-mentioned viscometer.

[0349] <<Surface tension of photosensitive composition>> The surface tension of the photosensitive composition according to the present disclosure at 25°C is, for example, preferably from the viewpoint of coatability, 5 mN / m to 100 mN / m, more preferably from 10 mN / m to 80 mN / m, and even more preferably from 15 mN / m to 40 mN / m. The surface tension of the photosensitive composition according to the present disclosure is measured using a surface tensiometer. As the surface tensiometer, for example, a surface tensiometer (product name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. can be suitably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0350] [Transfer film] The transfer film according to the present disclosure has a temporary support and a photosensitive composition layer containing the photosensitive composition according to the present disclosure described above. The transfer film according to the present disclosure may have a composition layer other than the photosensitive composition layer (so-called other composition layer). The transfer film according to the present disclosure may have, for example, a protective film on the photosensitive composition layer or another composition layer. The photosensitive composition layer, the other composition layer, and the protective film may each be a single layer or a multi-layer consisting of two or more layers. The transfer film according to the present disclosure preferably has a structure of temporary support / photosensitive composition layer / protective film.

[0351] In the transfer film according to the present disclosure, when the transfer film further has another composition layer on the side opposite the temporary support side of the photosensitive composition layer, the total thickness (total film thickness) of the other composition layers arranged on the side opposite the temporary support side of the photosensitive composition layer is preferably 0.1% to 30%, and more preferably 0.1% to 20%, of the thickness (film thickness) of the photosensitive composition layer.

[0352] The maximum waviness width of the transfer film according to the present disclosure is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 60 μm or less, from the viewpoint of preventing the generation of bubbles in the lamination step described below. The lower limit of the maximum waviness width is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more. The maximum width of the undulation of the transfer film is a value measured by the following procedure. First, the transfer film is cut perpendicular to the main surface to a size of 20 cm x 20 cm to prepare a test sample. If the transfer film has a protective film, the protective film is peeled off. Next, the test sample is placed on a flat, horizontal stage with the surface of the temporary support facing the stage. After the sample is placed, a 10 cm square area in the center of the test sample is scanned with a laser microscope (e.g., Keyence VK-9700SP) to obtain a three-dimensional surface image. The minimum concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. This procedure is performed on 10 test samples, and the arithmetic average value is taken as the "maximum waviness width of the transfer film."

[0353] The configuration of the transfer film according to the present disclosure will be described in detail below.

[0354] <Temporary support> The transfer film according to the present disclosure has a temporary support. The temporary support is a member that supports the photosensitive composition layer, and is ultimately removed by a peeling treatment.

[0355] The temporary support may have a single-layer structure or a multi-layer structure.

[0356] The temporary support is preferably a film, more preferably a resin film, which is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of such films include polyethylene terephthalate films (for example, biaxially oriented polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films. Among these, a polyethylene terephthalate film is preferred as the temporary support. Furthermore, it is preferable that the film used as the temporary support is free from deformations such as wrinkles and scratches.

[0357] From the viewpoint of enabling pattern exposure through the temporary support, it is preferable that the temporary support has high transparency, and the transmittance at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. Preferred values ​​of the transmittance include 87%, 92%, and 98%. The transmittance is calculated as the ratio of light emitted from the temporary support to the amount of incident light of each wavelength (=amount of emitted light / amount of incident light×100; %).

[0358] From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the temporary support contains as few fine particles, foreign matter and defects as possible. The total number of particles, foreign matter, and defects with a diameter of 1 μm or more contained in the temporary support is 50 / 10 mm 2 Preferably, it is 10 pieces / 10 mm or less. 2 It is more preferable that the number of pieces is 3 pieces / 10 mm or less. 2 More preferably, it is 0 pieces / 10 mm or less. 2It is particularly preferred that:

[0359] In order to improve the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that comes into contact with the photosensitive composition layer may be surface-modified by ultraviolet (UV) irradiation, corona discharge, plasma, or the like.

[0360] When the surface is modified by ultraviolet irradiation, the exposure dose of ultraviolet light is not particularly limited, but is, for example, 10 mJ / cm 2 ~2000mJ / cm 2 and preferably 50 mJ / cm 2 ~1000mJ / cm 2 It is more preferable that:

[0361] Examples of light sources for ultraviolet irradiation include light sources that emit light in the wavelength band of 150 nm to 450 nm, such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes (LEDs). The lamp output and illuminance are not particularly limited and can be set appropriately depending on, for example, the desired exposure dose.

[0362] In order to provide ease of handling, a layer containing fine particles (also called a "lubricant layer") may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer is not particularly limited, but is preferably, for example, 0.05 μm to 0.8 μm. The thickness of the lubricant layer is not particularly limited, but is preferably, for example, 0.05 μm to 1.0 μm.

[0363] The thickness of the temporary support is not particularly limited, but is preferably, for example, 5 μm to 200 μm, and from the viewpoint of ease of handling and versatility, is more preferably 5 μm to 150 μm, even more preferably 5 μm to 50 μm, and particularly preferably 5 μm to 25 μm. The thickness of the temporary support is calculated as the average value of measurements taken at any five points by cross-sectional observation using a scanning electron microscope (SEM).

[0364] As the temporary support, a commercially available product can be used. Examples of commercially available temporary supports include Lumirror (registered trademark) 16KS40, Lumirror (registered trademark) 16FB40, Lumirror (registered trademark) #38-U48, Lumirror (registered trademark) #75-U34, and Lumirror (registered trademark) #25T60 (all manufactured by Toray Industries, Inc.), and COSMOSHINE (registered trademark) A4100, COSMOSHINE (registered trademark) A4160, COSMOSHINE (registered trademark) A4300, COSMOSHINE (registered trademark) A4360, and COSMOSHINE (registered trademark) A8300 (all manufactured by Toyobo Co., Ltd.).

[0365] The temporary support may be a recycled product. Examples of recycled products include films made from chips obtained by cleaning used films, etc. Specific examples of recycled products include the Ecouse series manufactured by Toray Industries, Inc.

[0366] Examples of the temporary support include a 16 μm thick biaxially oriented polyethylene terephthalate film, a 12 μm thick biaxially oriented polyethylene terephthalate film, and a 9 μm thick biaxially oriented polyethylene terephthalate film.

[0367] Preferred forms of the temporary support are described, for example, in paragraphs

[0017] to

[0018] of JP 2014-085643 A, paragraphs

[0019] to

[0026] of JP 2016-027363 A, paragraphs

[0041] to

[0057] of WO 2012 / 081680 A, and paragraphs

[0029] to

[0040] of WO 2018 / 179370 A, the contents of which are incorporated herein by reference.

[0368] <Photosensitive composition layer> The transfer film according to the present disclosure has a photosensitive composition layer containing the photosensitive composition according to the present disclosure. With the transfer film according to the present disclosure, a pattern can be formed on the transfer target by transferring the photosensitive composition layer onto the transfer target, followed by exposure and development. The photosensitive composition layer may be any layer containing the photosensitive composition according to the present disclosure, but is preferably a layer consisting of the photosensitive composition according to the present disclosure or a layer consisting of the solid content of the photosensitive composition according to the present disclosure.

[0369] The photosensitive composition layer may be a positive-type photosensitive composition layer or a negative-type photosensitive composition layer, but is preferably a negative-type photosensitive composition layer. The negative photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in a developer decreases upon exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.

[0370] The photosensitive composition layer may contain a certain amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among these, halide ions (e.g., chloride ions, bromide ions, and iodide ions), sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following values.

[0371] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less, by mass, and may be 1 ppb or more, or 0.1 ppm or more, by mass. A specific example of the content of impurities in the photosensitive composition layer is an embodiment in which the total amount of the above impurities is 0.6 ppm by mass.

[0372] Methods for adjusting the impurity content in the photosensitive composition layer to the above range include, for example, selecting raw materials for the photosensitive composition that have a low impurity content, preventing impurities from being mixed in when the photosensitive composition layer is formed, and removing impurities by washing the photosensitive composition layer. By such methods, the impurity content in the photosensitive composition layer can be adjusted to the above range.

[0373] Impurities can be quantitatively determined by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0374] The photosensitive composition layer may contain residual monomers of the respective structural units of the alkali-soluble resin (hereinafter, simply referred to as "residual monomers"). From the viewpoints of patterning ability and reliability, the content of residual monomers in the photosensitive composition layer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but may be, for example, 1 ppm by mass or more, or 10 ppm by mass or more.

[0375] From the viewpoints of patterning ability and reliability, the content of residual monomers in the photosensitive composition layer is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and even more preferably 100 ppm by mass or less, relative to the total solid content of the photosensitive composition. The lower limit is not particularly limited, but may be, for example, 0.1 ppm by mass or more, or 1 ppm by mass or more.

[0376] The amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.

[0377] The amount of residual monomer in the photosensitive composition layer can be measured by a known method such as liquid chromatography or gas chromatography.

[0378] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably small. The content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, by mass. The lower limit can be 10 ppb or more, or 100 ppb or more, by mass. The content of these compounds can be reduced, for example, by selecting raw materials for the photosensitive composition that contain a small amount of these compounds, and by preventing the inclusion of these compounds when forming the photosensitive composition layer. The content of these compounds can be determined by known measurement methods.

[0379] The content of water in the photosensitive composition layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties.

[0380] <<Thickness of the photosensitive composition layer>> The thickness of the photosensitive composition layer (also referred to as "film thickness") is not particularly limited. The film thickness of the photosensitive composition layer is preferably, for example, 5 μm or more, and more preferably 10 μm or more, from the viewpoint of further suppressing the guiding of light to an adjacent light detection sensor when used, for example, as a light guiding member of a light detection device for fingerprint authentication. The thickness of the photosensitive composition layer is preferably 200 μm or less, and more preferably 100 μm or less, from the viewpoint of ease of handling.

[0381] The film thickness of the photosensitive composition layer is calculated as the average value of measurements taken at any five points by cross-sectional observation using a scanning electron microscope (SEM).

[0382] <<Refractive Index of Photosensitive Composition Layer>> The refractive index of the photosensitive composition layer is not particularly limited, but is preferably from 1.41 to 1.59, and more preferably from 1.47 to 1.56. The refractive index of the photosensitive composition layer is a value measured at a wavelength of 550 nm in an environment at an atmospheric temperature of 25°C using an ellipsometer.

[0383] <<Color of the photosensitive composition layer>> The photosensitive composition layer is preferably achromatic. Specifically, total reflection (incident angle: 8°, light source: D-65 (2° field of view)) corresponds to L in the CIE1976 (L*, a*, b*) color space. * The value is preferably 10 to 90, and a * The value is preferably -1.0 to 1.0, and b * The value is preferably between −1.0 and 1.0.

[0384] <<Dissolution rate of the photosensitive composition layer>> The dissolution rate of the photosensitive composition layer in a 1.0 mass % aqueous sodium carbonate solution is preferably 0.01 μm / sec or more, more preferably 0.10 μm / sec or more, and even more preferably 0.20 μm / sec or more, from the viewpoint of suppressing residues during development. Furthermore, from the viewpoint of the edge shape of the pattern, the dissolution rate of the photosensitive composition layer in a 1.0 mass % aqueous sodium carbonate solution is preferably 5.0 μm / sec or less, more preferably 4.0 μm / sec or less, and even more preferably 3.0 μm / sec or less. Specific preferred values ​​include 1.8 μm / sec, 1.0 μm / sec, and 0.7 μm / sec.

[0385] The dissolution rate per unit time of the photosensitive composition layer in a 1.0 mass % aqueous sodium carbonate solution is measured as follows. A photosensitive composition layer (with a film thickness of 1.0 μm to 10 μm) formed on a glass substrate and from which the solvent had been thoroughly removed is subjected to shower development using a 1.0% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C until the photosensitive composition layer is completely dissolved (up to a maximum of 2 minutes). The film thickness of the photosensitive composition layer is determined by dividing it by the time required for the photosensitive composition layer to completely dissolve. If the photosensitive composition layer is not completely dissolved within 2 minutes, the thickness is similarly calculated from the amount of film thickness change up to that point. A shower nozzle (model number: 1 / 4MINJJX030PP) manufactured by Ikeuchi Co., Ltd. is used for development, and the shower spray pressure is 0.08 MPa. Under the above conditions, the shower flow rate per unit time is 1,800 mL / min.

[0386] <<Dissolution rate of the cured film of the photosensitive composition layer>> The dissolution rate of the cured film of the photosensitive composition layer (within the range of film thickness 1.0 μm to 10 μm) in a 1.0 mass % aqueous sodium carbonate solution is preferably 3.0 μm / sec or less, more preferably 2.0 μm / sec or less, even more preferably 1.0 μm / sec or less, and particularly preferably 0.2 μm / sec or less. The cured film of the photosensitive composition layer is obtained by exposing the photosensitive composition layer to i-rays (wavelength 365 nm) at an exposure dose of 300 mJ / cm. 2 The film is obtained by exposure to light. Specific preferred values ​​include 0.8 μm / sec, 0.2 μm / sec, and 0.001 μm / sec.

[0387] The dissolution rate of the cured film of the photosensitive composition layer (within the film thickness range of 1.0 μm to 10 μm) in a 1.0 mass % aqueous sodium carbonate solution is measured in the same manner as the dissolution rate per unit time of the photosensitive composition layer in a 1.0 mass % aqueous sodium carbonate solution described above.

[0388] <<Swelling ratio of photosensitive composition layer>> From the viewpoint of improving pattern formability, the swelling ratio of the photosensitive composition layer after exposure to a 1.0 mass % aqueous sodium carbonate solution is preferably 100% or less, more preferably 50% or less, and even more preferably 30% or less. The swelling ratio of the photosensitive composition layer after exposure to a 1.0% by mass aqueous solution of sodium carbonate is measured as follows. The photosensitive composition layer (thickness: 1.0 μm to 10 μm) formed on the glass substrate and from which the solvent had been thoroughly removed was exposed to i-line (wavelength: 365 nm) at a dose of 500 mJ / cm using an ultra-high pressure mercury lamp. 2 The glass substrate is immersed in a 1.0% by mass aqueous solution of sodium carbonate at a liquid temperature of 25°C, and the film thickness is measured after 30 seconds. The rate at which the film thickness after immersion has increased relative to the film thickness before immersion is then calculated. Specific preferred values ​​include 4%, 13%, and 25%.

[0389] <<Foreign matter in the photosensitive composition layer>> The number of foreign particles having a diameter of 1.0 μm or more in the photosensitive composition layer is limited to 10 particles / mm 2 It is preferable that the number of particles is less than 5 / mm 2 More preferably, it is: The number of foreign matters in the photosensitive composition layer is measured as follows. Five randomly selected areas (1 mm × 1 mm) on the surface of the photosensitive composition layer are visually observed using an optical microscope from the normal direction of the surface of the photosensitive composition layer. The number of foreign particles with a diameter of 1.0 μm or more in each area is counted, and the arithmetic average is calculated as the number of foreign particles. A specific preferred value is 0 pieces / mm 2 , 1 piece / mm 2 , 4 pieces / mm 2 , 8 pieces / mm 2 etc.

[0390] <<Haze of the dissolved material in the photosensitive composition layer>> 1.0 cm in 1.0 L (liter) of 1.0 mass % sodium carbonate solution at a liquid temperature of 30°C 3The haze of the solution obtained by dissolving the photosensitive composition layer is preferably 60% or less, more preferably 30% or less, even more preferably 10% or less, and particularly preferably 1% or less, from the viewpoint of preventing the formation of aggregates during development.

[0391] The haze is measured as follows. First, a 1.0 mass % sodium carbonate aqueous solution is prepared, and the liquid temperature is adjusted to 30° C. Next, 1.0 cm 3 of the 1.0 mass % sodium carbonate aqueous solution at a liquid temperature of 30° C. is added. 3 The photosensitive composition layer is placed in the solution. The mixture is stirred at 30°C for 4 hours, taking care not to introduce air bubbles. After stirring, the haze of the solution in which the photosensitive composition layer has been dissolved is measured. The haze is measured using a haze meter as the measuring device, a liquid measurement unit, and a dedicated liquid measurement cell with an optical path length of 20 mm. As the haze meter, for example, a haze meter (model number: NDH4000) manufactured by Nippon Denshoku Industries Co., Ltd. can be suitably used. However, the haze meter is not limited to the above. Specific preferred values ​​include 0.4%, 1.0%, 9%, and 24%.

[0392] <Protective film> The transfer film according to the present disclosure may have a protective film. The protective film may be, for example, a resin film having heat resistance and solvent resistance. Examples of the protective film include polyolefin films such as polypropylene film and polyethylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, and polystyrene film. Furthermore, as the protective film, a resin film made of the same material as the temporary support may be used. The protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and even more preferably a polyethylene film.

[0393] The thickness of the protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, even more preferably from 5 μm to 40 μm, and particularly preferably from 15 μm to 30 μm. The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and is preferably 100 μm or less from the viewpoint of being relatively inexpensive.

[0394] The number of fisheyes in the protective film with a diameter of 80 μm or more is 5 per 1 m. 2 It is preferable that: "Fisheyes" are foreign matter, undissolved material, oxidized degradation products, etc. that are trapped in the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, or other methods are used to produce the film.

[0395] The number of particles with a diameter of 3 μm or more contained in the protective film is 30 / mm 2 It is preferable that the number of particles is less than 10 / mm 2 It is more preferable that the number of particles is 5 or less per mm. 2 It is more preferable that the following is satisfied: This makes it possible to suppress defects caused by unevenness due to particles contained in the protective film being transferred to the photosensitive composition layer.

[0396] In order to provide good winding properties, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. On the other hand, the arithmetic mean roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0397] From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the protective film surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more, while the surface roughness Ra of the protective film surface in contact with the photosensitive composition layer is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0398] The protective film may be a recycled product. Examples of recycled products include films made from chips made from used films that have been cleaned and turned into chips. Specific examples of recycled products include the Ecouse series manufactured by Toray Industries, Inc.

[0399] <<Relationship between temporary support, photosensitive composition layer, and protective film>> In the transfer film according to the present disclosure, it is preferred that the breaking elongation at 120°C of the cured film obtained by curing the photosensitive composition layer is 15% or more, the arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive composition layer is 50 nm or less, and the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive composition layer is 150 nm or less.

[0400] The transfer film according to the present disclosure preferably satisfies the following formula (T1). X×Y<1500...Formula (T1) In formula (T1), X represents the breaking elongation (%) of the cured film obtained by curing the photosensitive composition layer at 120°C, and Y represents the arithmetic mean roughness Ra (nm) of the surface of the temporary support on the photosensitive composition layer side. It is more preferable that X×Y is 750 or less. Specific values ​​of X include 18%, 25%, 30%, 35%, and the like. Specific values ​​of Y include 4 nm, 8 nm, 15 nm, and 30 nm. Specific values ​​of X×Y include 150, 200, 300, 360, 900, etc.

[0401] In the transfer film according to the present disclosure, it is preferable that the breaking elongation at 120°C of the cured film obtained by curing the photosensitive composition layer is at least twice as large as the breaking elongation at 23°C of the cured film obtained by curing the photosensitive composition layer.

[0402] The elongation at break was measured by exposing a 20 μm thick photosensitive composition layer to an exposure dose of 120 mJ / cm using an ultra-high pressure mercury lamp. 2 After curing by exposure to 400 mJ / cm using a high-pressure mercury lamp, 2 The cured film is then subjected to additional exposure at 145° C. for 30 minutes, and the cured film is used as a test sample, which is then measured by a tensile test.

[0403] The transfer film according to the present disclosure preferably satisfies the following formula (T2). Y≦Z...Formula (T2) In formula (T2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface of the temporary support on the side of the photosensitive composition layer, and Z represents the value (nm) of the arithmetic mean roughness Ra of the surface of the protective film on the side of the photosensitive composition layer.

[0404] <Transfer film manufacturing method> The method for producing the transfer film according to the present disclosure is not particularly limited, and known methods can be used. As a method for manufacturing a transfer film according to the present disclosure, for example, from the viewpoint of excellent productivity, a method including a step of applying a photosensitive composition to the surface of a temporary support to form a coating film, and a step of drying the formed coating film to form a photosensitive composition layer can be mentioned.

[0405] Examples of methods for applying the photosensitive composition include printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (that is, slit coating).

[0406] Examples of methods for drying the coating film include natural drying, heat drying, and reduced pressure drying, and these drying methods can be applied alone or in combination. The method for drying the coated film is preferably heat drying and / or reduced pressure drying. In this disclosure, "drying" means removing at least a portion of the solvent contained in the composition. The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher. The upper limit of the drying temperature is preferably 130° C. or lower, more preferably 120° C. or lower. Drying may be performed by continuously changing the temperature. The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. The upper limit of the drying time is not particularly limited, but is, for example, preferably 600 seconds or less, more preferably 300 seconds or less.

[0407] When the transfer film according to the present disclosure has a protective film on the side of the photosensitive composition layer opposite the temporary support, for example, the protective film can be pressed onto and bonded to the photosensitive composition layer formed above, thereby producing a transfer film having a temporary support / photosensitive composition layer / protective film configuration.

[0408] The method for laminating the protective film and the photosensitive composition layer is not particularly limited, and any known method can be used. For laminating the protective film and the photosensitive composition layer, a known laminator such as a vacuum laminator or an auto laminator can be used. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0409] The transfer film produced as described above may be wound up to prepare a transfer film in a roll form and stored. The transfer film in a roll form can be provided in its original form for a lamination step with a substrate in a roll-to-roll system.

[0410] [Method of manufacturing laminate] The method for producing a laminate according to the present disclosure (hereinafter also referred to simply as "the production method according to the present disclosure") is a method for producing a laminate having a light-shielding pattern, and includes, in this order, a step of forming a photosensitive composition layer containing the photosensitive composition according to the present disclosure described above on a substrate (hereinafter also referred to as "the formation step"), a step of patternwise exposing the photosensitive composition layer (hereinafter also referred to as "the exposure step"), and a step of developing the photosensitive composition layer (hereinafter also referred to as "the development step"), and includes, after the patternwise exposing step, a step of imparting light absorption properties to a specific colorant precursor (hereinafter also referred to as "the color development step"). The procedure of the above steps will be explained in detail below.

[0411] <Formation process> The forming step is a step of forming a photosensitive composition layer containing the photosensitive composition according to the present disclosure described above on a substrate. The formation step may be any step of forming a photosensitive composition layer containing the photosensitive composition according to the present disclosure on a substrate, and may be, for example, a step of forming a photosensitive composition layer by forming a coating film of the photosensitive composition according to the present disclosure on a substrate and drying the formed coating film, or may be a step of using the transfer film according to the present disclosure described above and contacting and laminating the surface of the photosensitive composition layer of the transfer film opposite the temporary support to the substrate, thereby forming a photosensitive composition layer on the substrate (hereinafter also referred to as a "lamination step"). However, a lamination step is preferred.

[0412] In the laminating step, the surface of the photosensitive composition layer of the transfer film according to the present disclosure opposite the temporary support is brought into contact with the substrate and laminated to form a photosensitive composition layer on the substrate. Note that, when the transfer film according to the present disclosure has a protective film on the surface of the photosensitive composition layer opposite the temporary support, the protective film is peeled off before the laminating step is carried out.

[0413] The method for laminating the photosensitive composition layer and the substrate is not particularly limited, and any known method can be used. For laminating the photosensitive composition layer and the substrate, a known laminator such as a vacuum laminator or an auto laminator can be used. The laminator is preferably equipped with any heatable roller such as a rubber roller and is capable of applying pressure and heat. The lamination temperature is preferably, for example, 70°C to 130°C.

[0414] The substrate is preferably a glass substrate or a resin substrate. The substrate is preferably a transparent substrate, more preferably a transparent resin substrate. The refractive index of the substrate is preferably 1.50 to 1.52. Examples of the glass substrate include tempered glass such as Gorilla Glass (registered trademark) manufactured by Corning Incorporated. The thickness of the glass substrate is preferably 0.01 mm to 1.1 mm, and more preferably 0.1 mm to 0.7 mm. Examples of resin substrates include substrates made of resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), triacetyl cellulose (TAC), polyimide (PI), polybenzoxazole (PBO), and cycloolefin polymer (COP). The thickness of the resin substrate is preferably 5 μm to 500 μm, and more preferably 10 μm to 100 μm. As the material of the substrate, for example, the materials described in JP-A Nos. 2010-86684, 2010-152809, and 2010-257492 are preferably used.

[0415] <Exposure process> The exposure step is a step of pattern-exposing the photosensitive composition layer. The term "pattern exposure" refers to a form of patterned exposure, i.e., an exposure form in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in the patterned exposure is not particularly limited and may be adjusted as appropriate. For example, when the photosensitive composition layer is negative type, the exposed portion of the photosensitive composition layer on the substrate in the pattern exposure is cured, and finally becomes a cured film.On the other hand, the non-exposed portion of the photosensitive composition layer on the substrate in the pattern exposure is not cured, and is dissolved and removed by the developer in the development step described below.The non-exposed portion can form an opening in the cured film after the development step.

[0416] The light source for pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range (e.g., 365 nm or 405 nm) that can cure the photosensitive composition layer. In particular, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. The dominant wavelength refers to the wavelength with the highest intensity.

[0417] Examples of light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure dose was 5 mJ / cm 2 ~200mJ / cm 2 and preferably 10 mJ / cm 2 ~200mJ / cm 2 It is more preferable that:

[0418] When a photosensitive composition layer is formed on a substrate using a transfer film, the temporary support may be peeled off before pattern exposure, or the temporary support may be peeled off before pattern exposure is performed via the temporary support, and then the temporary support may be peeled off. From the viewpoint of preventing contamination of the mask due to contact with the photosensitive composition layer and avoiding the influence of foreign matter adhering to the mask on the exposure, it is preferred to carry out pattern exposure without peeling off the temporary support. From the viewpoint of improving resolution by suppressing scattering of exposure light by the temporary support and by suppressing diffraction of light transmitted through the mask, it is preferable to perform pattern exposure after peeling off the temporary support.

[0419] The pattern exposure may be exposure through a mask or digital exposure using a laser or the like. When exposure is performed through a mask, examples of the mask substrate include a quartz mask, a soda lime glass mask, and a film mask. Among these, a quartz mask is preferred because it has excellent dimensional accuracy, and a film mask is preferred because it can be easily made into a large size. The substrate of the film mask is preferably a polyester film, more preferably a polyethylene terephthalate film. A specific example of the substrate of the film mask is XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.).

[0420] Preferred embodiments of the light source, exposure dose, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of WO 2018 / 155193, the contents of which are incorporated herein by reference.

[0421] <Developing process> The development step is a step of developing the photosensitive composition layer after pattern exposure. After the pattern exposure, the photosensitive composition layer is developed to form a pattern. The photosensitive composition layer after the pattern exposure can be developed using a developer. The developer is preferably an alkaline aqueous solution. Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). The pH of the alkaline aqueous solution at 25°C is preferably 8-13, more preferably 9-12, and even more preferably 10-12. The content of the alkaline compound in the alkaline aqueous solution is preferably 0.1% by mass to 5% by mass, and more preferably 0.1% by mass to 3% by mass, based on the total mass of the alkaline aqueous solution. In the present disclosure, examples of developers that can be suitably used include the developers described in paragraph

[0194] of WO 2015 / 093271.

[0422] Examples of the development method include puddle development, shower development, spin development, and dip development. In the present disclosure, examples of a development method that can be suitably used include the development method described in paragraph

[0195] of WO 2015 / 093271.

[0423] The development step may include a step of carrying out the development and a step of heat-treating (also referred to as "post-baking") the pattern obtained by the development. The post-baking temperature is preferably 80 to 260° C., more preferably 90 to 160° C. The post-baking time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.

[0424] <Coloring process> The manufacturing method according to the present disclosure includes a step of imparting light absorption properties to the specific color material precursor contained in the photosensitive composition layer (i.e., a color development step) after the step of patterned exposure (i.e., an exposure step). The color-developing step may be performed after the exposure step, for example, during or after the development step. Furthermore, "after the exposure step" means "after exposure for curing the photosensitive composition layer." In the color-developing step, a stimulus is applied to the photosensitive composition layer and / or the specific color material precursor contained in the photosensitive composition layer, thereby imparting light-absorbing properties to the specific color material precursor.

[0425] The method for imparting light-absorbing properties to the specific colorant precursor varies depending on the stimulus for imparting light-absorbing properties to the specific colorant precursor. For example, when the stimulus is heat, a method of heating the photosensitive composition layer after the exposure step can be mentioned. The method of heating the photosensitive composition layer after the exposure step is not particularly limited, and any known heating method can be used. Examples of the heating means include an oven, a hot plate, and a heat roll. The heating temperature is not particularly limited as long as it is a temperature at which the specific colorant precursor exhibits light absorption, and can be appropriately set depending on the color-developing temperature of the specific colorant precursor. For example, when the specific colorant precursor is a compound represented by formula (1), the heating temperature is preferably 80°C to 260°C. The heating time is not particularly limited and can be appropriately set depending on the degree of color development. When the photosensitive composition layer contains a thermoplastic resin, it is preferable to appropriately adjust the heating time, for example, to a shorter time, in consideration of maintaining the shape of the pattern.

[0426] A preferred method for imparting light absorption to the specific colorant precursor by heat is to perform post-baking in the development step to cause the specific colorant precursor contained in the photosensitive composition layer to develop a black color. For example, when the specific colorant precursor is a compound represented by formula (1), the pattern containing the specific colorant precursor obtained by development is heated during post-baking to cause the compound represented by formula (1) to react with oxygen in the air and become an oxidized product, thereby imparting light absorption.

[0427] For example, when the stimulus is an acid, a method of generating an acid in the photosensitive composition layer after the exposure step using an acid generator or the like can be mentioned.

[0428] Examples of a method for generating an acid in the photosensitive composition layer after the exposure step using an acid generator or the like include a method that utilizes the difference in reaction rate between a curing reaction due to photoradical polymerization of a polymerizable monomer or the like and a color-developing reaction of a specific color material precursor due to an acid generated from the photoacid generator. For example, when the specific colorant precursor is a leuco dye, the curing reaction due to photoradical polymerization of a polymerizable monomer or the like precedes the color-developing reaction of the leuco dye due to the acid generated from the photoacid generator, and therefore the curing reaction is less likely to be affected by the color-developing reaction. Although there is no clear distinction between the curing step in which a curing reaction is carried out and the color-developing step in which a color-developing reaction is carried out, the color-developing step is not included in the exposure step in the production method according to the present disclosure, because the color-developing step is not a step in which the photosensitive composition is exposed to light for curing.

[0429] Furthermore, examples of a method for generating an acid in the photosensitive composition layer after the exposure step using an acid generator or the like include a method that utilizes the difference in absorption spectrum between the photoradical polymerization initiator and the photoacid generator. For example, when polymerizable monomers or the like are subjected to a curing reaction by photoradical polymerization, light having a wavelength that is absorbed by the photoradical polymerization initiator but not absorbed by the photoacid generator is irradiated, and when a specific color material precursor is caused to develop color, light having a wavelength that is not absorbed by the photoacid generator is irradiated, thereby making the curing reaction less susceptible to the influence of the color development reaction.

[0430] Further, for example, when the stimulus is an acid, a method of bringing the photosensitive composition layer after the exposure step into contact with an acidic solution can also be mentioned. Examples of methods for contacting the photosensitive composition layer after the exposure step with an acidic solution include immersion in the acidic solution, spraying the acidic solution, and coating the acidic solution. Examples of the acidic solution include an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid, and an aqueous solution of nitric acid. Among these, the acidic solution is preferably an aqueous hydrochloric acid solution. The concentration of the aqueous hydrochloric acid solution is preferably, for example, 5% by mass to 15% by mass.

[0431] Furthermore, examples of methods for imparting light absorption to the specific colorant precursor include, for example, when the stimulus for imparting light absorption to the specific colorant precursor is light, a method of irradiating the photosensitive composition layer after the exposure step with light, and, for example, when the stimulus is a base, a method of generating a base in the photosensitive composition layer after the exposure step using a base generator, etc., and, for example, when the stimulus is a radical, a method of generating a radical in the photosensitive composition layer after the exposure step using a radical generator, etc. It is preferable that either method be appropriately adjusted within a range that does not interfere with the exposure step.

[0432] The film thickness of the light-shielding pattern of the laminate produced by the production method according to the present disclosure is, for example, preferably 5 μm or more, more preferably 10 μm or more, and the upper limit is, for example, preferably 200 μm or less, more preferably 100 μm or less, from the viewpoint of handleability. If the exposed film has light absorption properties, the exposure light is absorbed, resulting in insufficient polymerization and curing, making it difficult to form a thick film pattern. In contrast, in the production method according to the present disclosure, by exposing a photosensitive composition layer before the specific colorant precursor exhibits light absorption properties, i.e., a photosensitive composition layer that does not exhibit light absorption properties, the exposure light is less likely to be absorbed and sufficient polymerization and curing occurs, making it possible to form a light-shielding pattern with a thickness of 5 μm or more.

[0433] [Embodiments of the Light Detection Device According to the Present Disclosure] The light detection device according to the present disclosure includes the laminate according to the present disclosure as a light guide member. The light-detecting device according to the present disclosure includes the laminate according to the present disclosure, i.e., a substrate, and a light-shielding pattern having a film thickness of 5 μm or more, an aspect ratio (ratio of film thickness to line width at the bottom) of 1.0 or more, and an average absorbance of 2.0 or more at wavelengths of 400 nm to 700 nm. The light-shielding pattern can function as a light guide.

[0434] (Configuration of the detection device) FIG. 1 is a schematic diagram illustrating a detection device according to an embodiment of the present disclosure. The detection device according to an embodiment of the present disclosure is a device that detects information by receiving light L. In this embodiment, the detection device detects biometric information of a user. As shown in FIG. 1, the detection device includes a sensor unit 10, a light guide 100, a light source unit S, and a cover glass G. In this embodiment, the sensor unit 10, the light guide 100, the light source unit S, and the cover glass G are stacked in this order.

[0435] The light source unit S has a light irradiation surface Sa for emitting light, and emits light L0 from the light irradiation surface Sa. The light source unit S may have, for example, a light emitting diode (LED) or an organic light emitting diode (OLED) as a light source. The light source unit S may also be a light source (e.g., an LED) that emits light directly from the light irradiation surface. The light source unit S may also be a so-called side light type light source that has a light guide plate and multiple light sources lined up at one end or both ends of the light guide plate. The light source unit S is not limited to the configuration of this embodiment, and may be provided to the side or below the sensor unit 10, or may emit light L0 from the side or above the user's finger Fg. If natural light is used as the light L, the light source unit S may not be provided.

[0436] The light source unit S can also serve as a display panel. The display panel may be, for example, an organic light emitting diode (OLED) display panel or an inorganic light emitting diode (μ-LED, Mini-LED). Alternatively, the display panel may be a liquid crystal display panel (LCD) that uses liquid crystal elements as display elements.

[0437] The sensor unit 10 is, for example, a light reflection type biometric information sensor, and can detect unevenness (e.g., fingerprints) on the surface of a user's finger Fg or palm by detecting light L, which is reflected light of light L0. The sensor unit 10 may also detect a vascular pattern or other biometric information by detecting light L reflected inside the finger Fg or palm. The wavelength of the light L from the light source unit S may be varied depending on the detection target. For example, in the case of fingerprint detection, visible light L0 may be emitted from the light source unit S, and in the case of vascular pattern detection, near-infrared light L0 may be emitted from the light source unit S. Visible light is light in a wavelength band in the visible light region, and near-infrared light is light in a wavelength band in the near-infrared region, for example, a wavelength band of 700 nm or more and 950 nm or less.

[0438] The sensor unit 10 includes a light receiving element PD, and a known optical sensor module can be used.

[0439] The light guide 100 is provided on the side of the sensor unit 10 facing the object to be detected (finger Fg), and is an optical element that guides light L to the sensor unit 10. The light guide 100 is composed of a light guide portion 101 and a light absorption portion 111. The laminate of the light-shielding pattern of the present disclosure can be used as the pattern of the light guide portion 101 and the light absorption portion 111 of the light guide 100.

[0440] The cover glass G is a member for protecting the sensor unit 10 and the light source unit S, and covers the light guide 100, the sensor unit 10, and the light source unit S. The cover glass G is, for example, a glass substrate. Note that the cover glass G is not limited to a glass substrate, and may be a resin substrate or the like. Furthermore, the cover glass G does not necessarily have to be provided.

[0441] [Laminate used as a light guide] 2 and 3 are schematic diagrams of a light guide according to the present disclosure. Fig. 2 is a cross-sectional view of the light guide 100, and Fig. 3 is a view of the light guide 100 as viewed from the side of the object to be detected (finger Fg). The light guide 100 uses a laminate in which a pattern layer 101 is formed on a substrate 102 by a manufacturing method according to the present disclosure. The light-shielding pattern layer has a light-guiding region 110 that transmits light and a light-absorbing region 111 that absorbs light.

[0442] The absorption region 111 is a region that does not transmit light L, and is a light-shielding pattern obtained by patterning a photosensitive composition containing a colorant precursor that exhibits light absorption in response to a stimulus according to the present disclosure. The light-guiding region 110 is a region that is removed during the patterning process of the light-shielding pattern, and may remain as a space or may be filled with a transparent resin. The transparent resin is not particularly limited as long as it transmits light L, and examples that can be used include acrylic resin, silicone resin, and epoxy resin.

[0443] In this embodiment, the light guide region 110 has a cylindrical shape. However, the shape of the light guide region does not have to be cylindrical, and may be a polygonal prism such as a quadrangular prism.

[0444] The thickness of the light-shielding pattern of the laminate according to the present disclosure is 5 μm or more, preferably 10 μm or more. The upper limit is not particularly limited, but is preferably 200 μm or less, more preferably 100 μm or less, for example.

[0445] The aspect ratio, which is the ratio of the film thickness to the width of the space portion to be removed in the light-shielding pattern of the laminate according to the present disclosure, is preferably 1.0 or more, more preferably 2.0 or more, and even more preferably 5.0 or more. The width of the space portion refers to the diameter of the cylinder in the case of a cylindrical shape, or the width of the shortest distance passing through the center of the polygonal prism in the case of a polygonal prism.

[0446] In the present disclosure, the aspect ratio is determined by observing the cross section of the light-shielding pattern using a scanning electron microscope (SEM), measuring the film thickness and bottom width of the light-shielding pattern, and using the following formula. "Aspect ratio" = "film thickness" / "width of bottom of space"

[0447] The light-shielding pattern of the laminate according to the present disclosure has an average absorbance at wavelengths of 400 nm to 700 nm of 2.0 or more, preferably 3.0 or more. There are no particular upper limits, and examples include 5.0 or less.

[0448] The light-shielding pattern of the laminate according to the present disclosure preferably has a ratio of the width of the top of the space portion to the width of the bottom of the space portion (top width / bottom width) of 0.8 to 1.2, more preferably 0.9 to 1.1. A ratio of the width of the top of the space portion to the width of the bottom of the space portion of 0.8 to 1.2 means that the light-shielding pattern has excellent rectangularity.

[0449] In the present disclosure, the ratio of the top width to the bottom width (top width / bottom width) is determined by observing the cross section of the light-shielding pattern using an SEM (scanning electron microscope) and measuring the bottom width and top width of the light-shielding pattern.

[0450] The light-shielding pattern of the laminate according to the present disclosure preferably contains a coloring material represented by the following formula (I). The colorant represented by formula (I) is an oxidized form of the compound represented by formula (1) described above, and is a compound formed when the compound represented by formula (1) reacts with oxygen in the air when stimulated by heat. When the compound represented by formula (I) has tautomers and / or geometric isomers, the existing tautomers and / or geometric isomers are included in the compound represented by formula (I).

[0451] [ka]

[0452] In formula (I), X1a , X 2a , X 3a , X 4a , Y 1a and Y 2a are each independently an oxygen atom, a sulfur atom, or NL 1a Represents L 1a represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, or an aminocarbonyl group. A', B', and C' each independently represent an aromatic ring.

[0453] X in formula (I) 1a , X 2a , X 3a , X 4a , Y 1a and Y 2a is the X in the above formula (1). 1 , X 2 , X 3 , X 4 , Y 1 and Y 2 Since the definition is the same as above and the preferred embodiments are also the same, the explanation will be omitted here. A', B' and C' in formula (I) have the same meanings as A, B and C in formula (1) above, and preferred embodiments are also the same, so explanation will be omitted here.

[0454] When the light-shielding pattern of the laminate according to the present disclosure contains a coloring material represented by formula (I), it may contain only one type of coloring material represented by formula (I), or may contain two or more types of coloring materials.

[0455] When the light-shielding pattern of the laminate according to the present disclosure contains a coloring material represented by formula (I), the content of the coloring material represented by formula (I) in the light-shielding pattern is not particularly limited, but is preferably 5% by mass to 25% by mass, and more preferably 10% by mass to 20% by mass, relative to the total mass of the light-shielding pattern. [Example]

[0456] The present disclosure will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure should not be interpreted as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are by mass. In the following examples, the weight average molecular weight of the resin is determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0457] [Synthesis of binder polymer P-1] A 1000 mL flask was charged with 82.4 g of propylene glycol monomethyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and then heated to 90° C. under a nitrogen stream. To the heated propylene glycol monomethyl ether, a solution prepared by dissolving 38.4 g of styrene (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 30.1 g of dicyclopentanyl methacrylate (trade name: FANCRIL® FA-513M, manufactured by Hitachi Chemical Co., Ltd.), and 34.0 g of methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) in 20 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 5.4 g of dimethyl 2,2′-azobis(2-methylpropionate) (trade name: V-601, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a polymerization initiator in 43.6 g of propylene glycol monomethyl ether acetate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were simultaneously added dropwise over 3 hours. After the dropwise addition, 0.75 g of the polymerization initiator (V-601) was added three times to the solution after the dropwise addition at one-hour intervals, and the solution after the addition was allowed to react for another 3 hours. The resulting solution was then diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. The diluted solution was then heated to 100° C. under a stream of air. Next, 0.53 g of tetraethylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.26 g of p-methoxyphenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the heated solution. Next, 25.5 g of glycidyl methacrylate (trade name: Blenmer (registered trademark) GH, manufactured by NOF Corporation) was added dropwise to the resulting solution over 20 minutes. The resulting solution was then reacted at 100° C. for 7 hours to obtain 350.6 g of a solution of binder polymer P-1.

[0458] The solid content of the resulting solution was 36.3% by mass. The obtained binder polymer P-1 contained the structural units shown in Table 1, and had a weight average molecular weight (Mw) of 17,000, a dispersity (Mw / Mn) of 2.4, and an acid value of 94.5 mgKOH / g.

[0459] The weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) using standard polystyrene standards. The same method was used for the binder polymer P-2 described below. The acid value was measured according to the method described in JIS K 0070: 1992. The acid value of binder polymer P-2 described below was also measured in the same manner. The amount of residual monomer measured by gas chromatography (GC) was less than 0.1% by mass relative to the solid content of binder polymer P-1 for all monomers. The term "solid content" refers to all components of the binder polymer P-1 solution excluding the solvent, and even if the components are in a liquid state, they are included in the solid content. The same applies to the binder polymer P-2 described below.

[0460] [Synthesis of binder polymer P-2] A 2000 mL flask was charged with 60 g of propylene glycol monomethyl ether acetate (trade name: PGM-Ac, manufactured by Sanwa Chemical Industry Co., Ltd.) and 240 g of propylene glycol monomethyl ether (trade name: PGM, manufactured by Sanwa Chemical Industry Co., Ltd.) Then, the liquid in the flask was heated to 90°C while stirring at a stirring speed of 250 rpm (revolutions per minute). Next, 107.1 g of methacrylic acid (trade name: ACRYESTER (registered trademark) M, manufactured by Mitsubishi Chemical Corporation), 5.46 g of methyl methacrylate (trade name: MMA, manufactured by Mitsubishi Gas Chemical Company, Inc.), and 231.42 g of cyclohexyl methacrylate (trade name: CHMA, manufactured by Mitsubishi Gas Chemical Company, Inc.) were mixed and then diluted with 60 g of propylene glycol monomethyl ether acetate to prepare a dropping solution (1). Next, 9.637 g of dimethyl 2,2'-azobis(2-methylpropionate) (trade name: V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) serving as a polymerization initiator was dissolved in 136.56 g of propylene glycol monomethyl ether acetate to prepare a dropping solution (2). The dripping liquid (1) and dripping liquid (2) prepared above were simultaneously added dropwise over a period of 3 hours to a 2000 mL flask containing the liquid heated to 90°C. Next, the container containing dripping liquid (1) was washed with 12 g of propylene glycol monomethyl ether acetate, and the resulting washings were added dropwise to the 2000 mL flask. Next, the container containing dripping liquid (2) was washed with 6 g of propylene glycol monomethyl ether acetate, and the resulting washings were added dropwise to the 2000 mL flask. During the dripping of these washings, the reaction liquid in the 2000 mL flask was maintained at a liquid temperature of 90°C and stirred at a stirring speed of 250 rpm. After the dripping, the reaction liquid in the flask was further stirred for 1 hour as a post-reaction, maintaining the liquid temperature at 90°C and stirring at a stirring speed of 250 rpm. Next, 2.401 g of V-601 was added to the reaction solution after the post-reaction as the first additional addition of polymerization initiator. Next, the container containing V-601 was washed with 6 g of propylene glycol monomethyl ether acetate, and the obtained washings were further added to the reaction solution, followed by stirring at 90°C for 1 hour. Next, 2.401 g of V-601 was added to the obtained reaction solution as the second additional addition of the polymerization initiator. Next, the container containing V-601 was washed with 6 g of propylene glycol monomethyl ether acetate, and the obtained washings were further added to the reaction solution, followed by stirring at 90°C for 1 hour. Next, 2.401 g of V-601 was added to the obtained reaction solution as the third additional addition of polymerization initiator. Next, the container containing V-601 was washed with 6 g of propylene glycol monomethyl ether acetate, and the obtained washings were further added to the reaction solution, followed by stirring at 90°C for 3 hours.

[0461] Next, 178.66 g of propylene glycol monomethyl ether acetate was added to the resulting reaction solution. Next, 1.8 g of tetraethylammonium bromide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 0.8 g of hydroquinone monomethyl ether (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to the resulting reaction solution. Next, the container containing the tetraethylammonium bromide and the container containing the hydroquinone monomethyl ether were each washed with 6 g of propylene glycol monomethyl ether acetate, and the resulting washings were further added to the reaction solution. Then, the temperature of the resulting reaction solution was raised to 100°C. Next, 76.03 g of glycidyl methacrylate (trade name: Blenmer (registered trademark) G, manufactured by NOF Corporation) was added dropwise to the reaction solution after heating over 1 hour. Next, the vessel containing Blenmer G was washed with 6 g of propylene glycol monomethyl ether acetate, and the resulting washings were added to the reaction solution, followed by stirring at 100°C for 6 hours to allow the addition reaction to occur. Next, the resulting reaction liquid was cooled and then filtered using a mesh filter (mesh size: 100 mesh) for removing dust, to obtain 1158 g of a solution of binder polymer P-2.

[0462] The solid content of the resulting solution was 36.3% by mass. The obtained binder polymer P-2 contained the structural units shown in Table 1, and had a weight average molecular weight (Mw) of 27,000, a dispersity (Mw / Mn) of 1.8, and an acid value of 95.0 mgKOH / g. The amount of residual monomer measured by gas chromatography (GC) was less than 0.1% by mass relative to the solid content of binder polymer P-2 for all monomers.

[0463] [Table 1]

[0464] In Table 1, the structural units other than the structural unit having a (meth)acryloyl group are shown by the abbreviation of the monomer that forms each structural unit. Structural units having a (meth)acryloyl group are shown in the form of an addition structure between monomers. For example, MAA-GMA means a structural unit in which glycidyl methacrylate (GMA) is added to a structural unit derived from methacrylic acid (MAA).

[0465] The following abbreviations represent the following monomers: "St": Styrene "MAA": methacrylic acid "GMA": Glycidyl methacrylate "DCPMA": dicyclopentanyl methacrylate

[0466] [Synthesis of colorant precursors that exhibit light absorption upon stimulation] The following compound (1) was synthesized based on the following scheme. In the scheme, NR represents Y in formula (1). 2 Corresponds to.

[0467] [ka]

[0468] [ka]

[0469] [Synthesis of compound (1)] A compound corresponding to the light-absorbing compound in the above scheme [compound (100)] was synthesized using isatin as the starting material, following the procedure described in J. Am. Chem. Soc. 2015, 137, 15947-15956. To a 300 mL three-neck flask, 150 mL of tetrahydrofuran (THF) [stabilizer-containing, Wako First Grade, Fujifilm Wako Pure Chemical Industries, Ltd.] was added, followed by 10.0 g of the synthesized compound (100) and 4.9 g of zinc powder [Wako Special Grade, Fujifilm Wako Pure Chemical Industries, Ltd.]. The three-neck flask was immersed in ice water to maintain the internal temperature below 5°C, and 15 mL of trifluoroacetic acid [Wako Special Grade, Fujifilm Wako Pure Chemical Industries, Ltd.] was added dropwise. After the addition was complete, the external equipment was removed and the mixture was allowed to react in a water bath for 2 hours, ensuring the internal temperature did not exceed 40°C. The reaction solution was filtered through Celite, and 10 mL of ultrapure water was added to the filtrate. The mixture was heated to 40°C and THF was distilled off under reduced pressure. The precipitated gray solid was filtered by suction and washed with 300 mL of ultrapure water. The solid was dried for 12 hours using a blower dryer set at 50°C to obtain 4.5 g of compound (1) (yield: 46%).

[0470] [ka]

[0471] [Preparation of Photosensitive Composition] [Examples 1 and 2, Comparative Example 1] The components were mixed to obtain the composition shown in Table 2. Zirconia beads (bead diameter: 0.1 mm) in an amount three times the mass of the mixture were added to the resulting mixture, and then the mixture was dispersed using an MSE (Multi-Stacked Elements) mixer at a peripheral speed of 9 m / sec for 90 minutes. After dispersion, the zirconia beads were separated using a filter with a nominal filtration particle size of 73 μm, and the photosensitive compositions of Examples 1 and 2 and Comparative Example 1 were obtained.

[0472] [Table 2]

[0473] [Creating transfer film] The photosensitive composition of Example 1 was applied onto a temporary support (trade name: Lumirror (registered trademark) 16KS40, biaxially oriented polyethylene terephthalate (PET) film, thickness: 16 μm, manufactured by Toray Industries, Inc.) using a slit nozzle in an amount sufficient to form a coating film with a dry thickness of 30 μm. The solvent in the coating film was then evaporated in a drying zone at 100°C to form a photosensitive composition layer. A protective film (trade name: Lumirror (registered trademark) 16KS40, biaxially oriented polyethylene terephthalate (PET) film, thickness: 16 μm, manufactured by Toray Industries, Inc.) was then pressure-bonded onto the photosensitive composition layer to produce the transfer film of Example 1. Transfer films for Example 2 and Comparative Example 1 were also prepared in the same manner, except that the respective photosensitive compositions were used.

[0474] [Laminate fabrication] After peeling the protective film from the transfer film of Example 1, the exposed surface of the photosensitive composition layer was laminated to a 50 μm-thick PET film (trade name: COSMOSHINE® A4360, manufactured by Toyobo Co., Ltd.) to obtain a laminate having a laminate structure of temporary support / photosensitive composition layer / PET film. The lamination conditions were a roll temperature of 110°C, a linear pressure of 0.6 MPa, and a linear speed (so-called lamination speed) of 2 m / min. Next, without peeling off the temporary support, the prepared laminate was exposed to i-line light (wavelength 365 nm) at an exposure dose of 150 mJ / cm2 using a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp and a photomask. The photomask had a circular pattern with diameters ranging from 1 μm to 100 μm, varying in 1 μm increments (the circular portions were light-shielded). After exposure, the temporary support was peeled off from the laminate. The laminate was then developed for 30 seconds using a 1% by mass potassium carbonate aqueous solution (liquid temperature: 30°C), rinsed with a shower of pure water, and then dried at 75°C for 13 seconds to develop and remove the photosensitive composition layer in the unexposed areas. The laminate was then exposed to i-rays (wavelength 365 nm) at an exposure dose of 1000 mJ / cm2 to harden the photosensitive composition layer. The laminate with the hardened photosensitive composition layer was then heat-treated for 5 minutes using a convection oven with the temperature set to 210°C, producing a laminate having the pattern of Example 1.

[0475] In the same manner as in Example 1, laminates having the patterns of Example 2 and Comparative Example 1 were produced using the transfer films of Example 2 and Comparative Example 1.

[0476] [Laminate evaluation] The laminates having the patterns of Examples 1 and 2 and Comparative Example 1 were subjected to the following evaluations. [Absorbance] The absorbance of the patterned portion of the patterned laminate was measured using a UV-visible spectrophotometer (model: UV-2600) manufactured by Shimadzu Corporation to determine the average absorbance at wavelengths of 400 nm to 600 nm and evaluate it according to the following evaluation criteria. The results are shown in Table 3. In the following evaluation criteria, "A" and "B" are practically acceptable levels, with "A" being the most preferable. (Evaluation criteria) A: Absorbance is 3.0 or more B: Absorbance is 2.0 or more and less than 3.0 C: Absorbance is 1.0 or more and less than 2.0 D: absorbance less than 1.0

[0477] Aspect Ratio The cross section of the patterned laminate was observed using a scanning electron microscope (SEM), and the film thickness and minimum resolved width of the pattern were measured. The "minimum resolved width" refers to the diameter of the bottom of the smallest circular space pattern among the circular space patterns in which no residue was found when the space portion was observed in cross section using an SEM. The aspect ratio was calculated from the measured film thickness and minimum resolved width of the pattern using the following formula, and evaluation was performed according to the following evaluation criteria. The results are shown in Table 3. In the following evaluation criteria, "A," "B," and "C" are practically acceptable levels, with "A" being the most preferable. "Aspect ratio" = "film thickness" / "minimum resolved width"

[0478] -Evaluation criteria- A: The minimum line width is 15 μm or less, and the aspect ratio is 5 or more. B: The minimum line width is 15 μm or less, and the aspect ratio is 2 or more and less than 5. C: The minimum line width is 15 μm or less, and the aspect ratio is 1 or more and less than 2. D: The minimum line width is greater than 15 μm and / or the aspect ratio is less than 1.

[0479] [Table 3]

[0480] [Fabrication of an optical detection device for fingerprint authentication] [Example 1] An optical detection device for fingerprint authentication of Example 1 was produced using the transfer film of Example 1. In the schematic diagram shown in Fig. 1, an OLED display device in which pixels were arranged at a pitch of 50 µm was used as the light source section, and a module in which photodiode elements were arranged at a pitch of 50 µm was used as the sensor section. As a light guide, a light-shielding pattern having circular spaces at a pitch of 50 µm was produced using the transfer film of Example 1 as follows.

[0481] (Production of light-shielding pattern) After peeling the protective film from the transfer film of Example 1, the exposed surface of the photosensitive composition layer was laminated to a 50 μm-thick PET film (trade name: COSMOSHINE (registered trademark) A4360, manufactured by Toyobo Co., Ltd.) to obtain a laminate having a laminate structure of temporary support / photosensitive composition layer / PET film. The lamination conditions were a roll temperature of 110°C, a linear pressure of 0.6 MPa, and a linear speed (so-called lamination speed) of 2 m / min. Next, without peeling off the temporary support, the prepared laminate was exposed to i-line light (wavelength 365 nm) at an exposure dose of 150 mJ / cm2 using a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp and a photomask. The photomask used had a circular pattern with a diameter of 5 μm (circular portions were light-shielded) arranged at a 50 μm pitch. After exposure, the temporary support of the laminate was peeled off. The laminate was then developed for 30 seconds using a 1% by mass potassium carbonate aqueous solution (liquid temperature: 30°C), rinsed with a shower of pure water, and dried at 75°C for 13 seconds to develop and remove the photosensitive composition layer in the unexposed areas. The laminate was then exposed to i-rays (wavelength 365 nm) at an exposure dose of 1000 mJ / cm2 to harden the photosensitive composition layer. The laminate with the hardened photosensitive composition layer was then heat-treated for 5 minutes using a convection oven with the temperature set to 210°C to produce a laminate having the pattern of Example 1.

[0482] The light source section made of the above-mentioned OLED display device, the sensor section, and the laminate having the pattern of Example 1 were combined to fabricate the photodetector for fingerprint authentication of Example 1.

[0483] In the same manner as in Example 1, the transfer films of Example 2 and Comparative Example 1 were used to fabricate detection devices for fingerprint authentication of Example 2 and Comparative Example 1.

[0484] It was confirmed that the detection devices for fingerprint authentication of Examples 1 and 2 functioned properly. The detection device for fingerprint authentication of Comparative Example 1 did not function.

[0485] These results confirm that the photosensitive composition according to the present disclosure can form a high-resolution, high-aspect-ratio light-shielding pattern and is applicable to a high-resolution fingerprint authentication detection device. [Explanation of symbols]

[0486] Fg finger G. Cover glass 10 Sensor section 100 Light guide 110 Light guiding area 111 Absorption region S Light source section Sa light irradiation surface PD photodetector

Claims

1. A photosensitive composition containing a colorant precursor that exhibits light absorption in response to a stimulus, the photosensitive composition being used in a light guide member of a light detection device.

2. 2. The photosensitive composition according to claim 1, wherein the stimulus is at least one selected from the group consisting of heat, light, an acid, a base, and a radical.

3. 2. The photosensitive composition according to claim 1, further comprising an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator.

4. 10. The photosensitive composition of claim 1, wherein the photodetector is a biometric device.

5. A temporary support; a photosensitive composition layer containing the photosensitive composition according to any one of claims 1 to 4; With transfer film.

6. A method for manufacturing a laminate having a light-shielding pattern, comprising: forming a photosensitive composition layer containing the photosensitive composition according to any one of claims 1 to 4 on a substrate; patternwise exposing the photosensitive composition layer; and developing the photosensitive composition layer, a step of causing the colorant precursor to exhibit light absorbing properties after the step of patterned exposure.

7. A laminate having a light-shielding pattern, the laminate being produced by the production method according to claim 6.

8. A photodetector comprising the laminate according to claim 7 .

9. A biometric authentication device comprising the laminate according to claim 7.

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