JP7419097B2 - Curable composition, cured product, near-infrared absorption filter, method for producing cured product, method for producing near-infrared absorption filter, low-temperature storage method for curable composition, method for transporting curable composition, and method for producing curable composition How to provide - Google Patents

Description

The present invention provides a curable composition capable of producing a near-infrared absorption filter, a cured product, a near-infrared absorption filter, a method for producing a cured product, a method for producing a near-infrared absorption filter, a method for storing a curable composition at low temperature, The present invention relates to a method for transporting a curable composition and a method for providing a curable composition.

Optical filters (near-infrared absorption filters) that transmit visible light but cut near-infrared light are used for various purposes.
For example, solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal-oxide semiconductor) are used in imaging devices such as digital still cameras and video cameras. A near-infrared absorption filter is used to cut and correct visibility.

A near-infrared absorption filter is manufactured using, for example, a composition containing a near-infrared absorber and a solvent (see Patent Document 1).

Special table 2018-043185 publication

In recent years, there has been a demand for smaller devices. By increasing the content of the near-infrared absorbing agent in the composition for producing the near-infrared absorption filter, the near-infrared absorption filter can be made thinner, contributing to miniaturization of the device. For this reason, it is desired that the near-infrared absorbent has high solvent solubility in a composition for producing a near-infrared absorbing filter.

In addition, the composition for manufacturing the near-infrared absorption filter may be used after being stored at the composition manufacturing site or the near-infrared absorption filter manufacturing site, or the near-infrared absorption filter may be used from the composition manufacturing site. It is often transported to the production site. When the composition for producing a near-infrared absorption filter contains a thermosetting material, the near-infrared absorption filter can be produced by heating and curing the composition. The thermosetting material may react and deteriorate during storage or transportation. In order to prevent the reaction of thermosetting materials, it is possible to store and transport compositions containing thermosetting materials at low temperatures, but if storage and transport are performed at low temperatures, precipitates may form. There is a problem that there is. Therefore, it is also desired that a composition for producing a near-infrared absorption filter has excellent low-temperature stability, that is, it does not easily generate precipitates even when stored or transported at low temperatures.

The present invention was made in view of the above problems, and provides a curable composition with excellent solvent solubility and low-temperature stability of a near-infrared absorber, a cured product using the curable composition, and a near-infrared absorbent. An absorption filter, a method for producing the cured product, a method for producing the near-infrared absorption filter, a method for storing the above-mentioned curable composition at a low temperature, a method for transporting the above-mentioned curable composition, and a method for producing the above-mentioned curable composition. The purpose is to provide a method of providing information.

The present inventors have developed a method that includes a thermosetting material (A), a near-infrared absorbing dye (B), and a solvent (S), where the near-infrared absorbing dye (B) is a portion represented by >N ⁺ =. structure, the solvent (S) contains a solvent (S1) in which the polar term δp of the Hansen solubility parameter is 12 (MPa ^0.5 ) or more, and the solvent (S1) is based on the mass of the near-infrared absorbing dye (B). It has been discovered that the above problems can be solved by a composition in which the mass ratio of is 30 or more, and the present invention has been completed. More specifically, the present invention provides the following.

A first aspect of the present invention comprises a thermosetting material (A), a near-infrared absorbing dye (B), and a solvent (S), wherein the near-infrared absorbing dye (B) is expressed by >N ⁺ = The solvent (S) has ^a partial structure of A curable composition in which the mass ratio of (S1) is 30 or more.

The second aspect of the present invention is a cured product of the curable composition according to the first aspect.

A third aspect of the present invention is a near-infrared absorption filter comprising a cured product of the curable composition according to the first aspect.

A fourth aspect of the present invention is a method for producing a cured product, which includes curing the curable composition according to the first aspect.

A fifth aspect of the present invention is a method for producing a near-infrared absorption filter, which includes curing the curable composition according to the first aspect.

A sixth aspect of the present invention is a low-temperature storage method for a curable composition, in which the curable composition according to the first aspect is stored at 10° C. or lower.

A seventh aspect of the present invention is a method for transporting a curable composition, in which the curable composition according to the first aspect is transported by a transporter at a temperature of 10° C. or lower.

An eighth aspect of the present invention provides a process line that executes the method for manufacturing a cured product according to the fourth aspect or a process line that executes the method for manufacturing a near-infrared absorption filter according to the fifth aspect. This is a method for providing a curable composition, which provides a curable composition stored by the method for storing a curable composition at low temperature according to the sixth aspect.

According to the present invention, there is provided a curable composition with excellent solvent solubility and low-temperature stability of a near-infrared absorber, which can produce a near-infrared absorbing filter, and a cured product using the curable composition and a near-infrared absorbing filter. An infrared absorption filter, a method for producing the cured product, a method for producing the near-infrared absorption filter, a method for storing the curable composition at a low temperature, a method for transporting the curable composition, and the curable composition. and the provision method.

≪Curable composition≫
The curable composition includes a thermosetting material (A), a near-infrared absorbing dye (B), and a solvent (S). The near-infrared absorbing dye (B) has a partial structure represented by >N ⁺ =, and the solvent (S) is a solvent (S1) in which the polar term δp of the Hansen solubility parameter is 12 (MPa ^0.5 ) or more. )including. The ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is 30 or more.

This curable composition has a near-infrared absorber (B) with a specific structure and a specific solvent (S1) in a specific mass ratio, so it has excellent solubility of the near-infrared absorber (B) in the solvent (S1). . Therefore, the concentration of the near-infrared absorber (B) in the curable composition can be increased. Therefore, a cured product such as a near-infrared absorption filter formed using a curable composition can be made thin while having desired near-infrared absorption characteristics, and an element including the cured product such as a near-infrared absorption filter can be made thin. can be downsized.
Further, this curable composition has excellent low temperature stability, that is, it does not easily generate precipitates even when stored or transferred at low temperatures. For example, even if the curable composition is stored or transported at 10° C. or lower, no precipitate is generated.
The essential or optional components of the curable composition and the manufacturing method will be explained.

<Thermosetting material (A)>
The thermosetting material (A) is a component that becomes a base material of a cured product such as a near-infrared absorbing filter formed using the curable composition.
The thermosetting material (A) is not particularly limited as long as it is a component that can be cured by heating, and may be, for example, a low molecular compound or a high molecular compound such as a resin. When the thermosetting material (A) is a thermosetting resin, the mass average molecular weight is preferably 10,000 or more and 300,000 or less, more preferably 20,000 or more and 200,000 or less.
It is preferable that the cured product of the thermosetting material (A) transmits visible light. Visible light is, for example, light with a wavelength of 380 nm or more and less than 780 nm.

Examples of the thermosetting material (A) include compounds having thermosetting groups such as epoxy groups, isocyanate groups, and blocked isocyanate groups. Specific examples include isocyanate compounds having an isocyanate group or blocked isocyanate group, and epoxy compounds having an epoxy group. From the viewpoint of visible light transmission (transparency), (meth)acrylic resins having thermosetting groups such as epoxy groups, isocyanate groups, and blocked isocyanate groups are preferred. In addition, in this specification, "(meth)acrylic" means both "acrylic" and "methacrylic."
These can be used alone or in combination of two or more.

（式（ａ１）、（ａ２）、及び（ａ３）中、Ｒ^１は、それぞれ独立に水素原子、又はメチル基であり、Ｒ^２は、単結合、又は炭素原子数１以上５以下のアルキレン基であり、Ｒ^３は、ブロックイソシアネート基であり、Ｒ^４は、２価の炭化水素基であり、Ｒ^５は、単結合、又は２価の連結基であり、Ｒ^６は、２以上のベンゼン環を含む炭化水素基である。） Since it is easy to obtain a curable composition that simultaneously satisfies good thermosetting properties, stability at low temperatures, and good visible light transmittance of the cured product, thermosetting materials having blocked isocyanate groups (meth ) Acrylic resin is preferable, and (meth)acrylic resin includes a structural unit represented by the following formula (a1), a structural unit represented by the following formula (a2), and a structural unit represented by the following formula (a3). (hereinafter also referred to as resin A) is more preferred.

(In formulas (a1), (a2), and (a3), R ¹ is each independently a hydrogen atom or a methyl group, and R ² is a single bond or an alkylene group having 1 to 5 carbon atoms. , R ³ is a blocked isocyanate group, R ⁴ is a divalent hydrocarbon group, R ⁵ is a single bond or a divalent linking group, and R ⁶ is two or more benzene groups. It is a hydrocarbon group containing a ring.)

Hereinafter, the structural unit represented by formula (a1) will also be referred to as "structural unit A1", the structural unit represented by formula (a2) will also be referred to as "structural unit A2", and the structural unit represented by formula (a3) It is also written as "structural unit A3".

The structural unit A1 represented by the above formula (a1) has a blocked isocyanate group as ^R3 . A blocked isocyanate group means a group in which an isocyanate group is blocked with a thermally dissociable protecting group.
Therefore, when the above-mentioned resin having the structural unit A1 is heated, the protective group in the blocked isocyanate group is removed and an active isocyanate group is generated.

Isocyanate groups generated by heating easily react with functional groups having active hydrogen. Here, the structural unit A2 represented by the above formula (a2) has a hydroxyl group which is a functional group having an active hydrogen group. Therefore, when the above resin is heated, active isocyanate groups are generated in the structural unit A1. By reacting this isocyanate group (-NCO) with the hydroxyl group in structural unit A2, crosslinking by the urethane bond (-NH-CO-O-) progresses and a cured product is formed.

Furthermore, the structural unit represented by the above formula (a3) has a hydrocarbon group containing two or more benzene rings as R ⁶ . Here, the hydrocarbon group containing two or more benzene rings contributes to the transparency, good mechanical properties, and heat resistance of the cured product.
Therefore, when the above-mentioned resin is heated, curing of the resin progresses well.

The essential or optional structural units contained in the resin, the method for producing the resin, etc. will be described below.

<Structural unit A1>
As described above, resin A includes a structural unit A1 having a blocked isocyanate group. Resin A may contain a combination of two or more types of structural units A1.

Structural unit A1 is a structural unit represented by the above-mentioned formula (a1). In formula (a1), R ¹ is a hydrogen atom or a methyl group.

In formula (a1), R ² is a single bond or an alkylene group having 1 or more and 5 or less carbon atoms. The alkylene group may be linear or branched, preferably linear. Specific examples of the alkylene group as ^R2 include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group. , butane-1,4-diyl group, and pentane-1,5-diyl group.
Among these groups, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group are preferred; ethane-1,2-diyl group, and propane-1,3-diyl group are more preferred, and ethane-1,2-diyl group is particularly preferred.

In formula (a1), R ³ is a blocked isocyanate group. As mentioned above, the blocked isocyanate group means a group in which the isocyanate group is blocked with a thermally dissociable protecting group.
Such a thermally dissociable protecting group is formed by reacting an isocyanate group with a blocking agent that provides a protecting group.

Examples of such blocking agents include alcohol compounds, phenol compounds, hydroxyl group-containing compounds other than alcohol compounds and phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, and carbamic acid compounds. , urea-based compounds, acid amide-based (lactam-based) compounds, acid imide-based compounds, triazole-based compounds, pyrazole-based compounds, pyrrole-based compounds, mercaptan-based compounds, and bisulfites.

Examples of alcohol compounds include methanol, ethanol, isopropanol, n-butanol, sec-butanol, 2-ethylhexyl alcohol, 1-octanol, 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2,2,2- Trifluoroethanol, 2,2,2-trichloroethanol, 2-(hydroxymethyl)furan, 2-methoxyethanol, methoxypropanol, 2-2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-(2 -ethoxyethoxy)ethanol, 2-(4-ethoxybutoxy)ethanol, 2-(2-butoxyethoxy)ethanol, N,N-dibutyl-2-hydroxyacetamide, N-morpholineethanol, 2,2-dimethyl-1, Examples include 3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12-hydroxystearic acid, and 2-hydroxyethyl methacrylate.

Examples of phenolic compounds include phenol, o-cresol, m-cresol, p-cresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-n-propylphenol, 3-n-propylphenol. , 4-n-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-n-butylphenol, 3-n-butylphenol, 4-n-butylphenol, 2-sec-butylphenol, 3-sec -butylphenol, 4-sec-butylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-n-hexylphenol, 3-n-hexylphenol, 4-n-hexylphenol, 2- (2-ethylhexyl)phenol, 3-(2-ethylhexyl)phenol, 4-(2-ethylhexyl)phenol, 2-n-octylphenol, 3-n-octylphenol, 4-n-octylphenol, 2-n-nonylphenol, 3 -n-nonylphenol, 4-n-nonylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5- Dimethylphenol, 2,3-di-n-propylphenol, 2,4-di-n-propylphenol, 2,5-di-n-propylphenol, 2,6-di-n-propylphenol, 3,4-di-n- Propylphenol, 3,5-di-n-propylphenol, 2,3-diisopropylphenol, 2,4-diisopropylphenol, 2,5-diisopropylphenol, 2,6-diisopropylphenol, 3,4-diisopropylphenol, 3, 5-diisopropylphenol, 3-isopropyl-2-methylphenol, 4-isopropyl-2-methylphenol, 5-isopropyl-2-methylphenol, 6-isopropyl-2-methylphenol, 2-isopropyl-3-methylphenol, 4-isopropyl-3-methylphenol, 5-isopropyl-3-methylphenol, 6-isopropyl-3-methylphenol, 2-isopropyl-4-methylphenol, 3-isopropyl-4-methylphenol, 5-isopropyl-4 -Methylphenol, 6-isopropyl-4-methylphenol, 2,3-di-n-butylphenol, 2,4-di-n-butylphenol, 2,5-di-n-butylphenol, 2,6-di-n-butylphenol, 3 , 4-di-n-butylphenol, 3,5-di-n-butylphenol, 2,3-disec-butylphenol, 2,4-disec-butylphenol, 2,5-disec-butylphenol, 2,6-disec -butylphenol, 3,4-disec-butylphenol, 3,5-disec-butylphenol, 2,3-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 3,4-di-tert-butylphenol, 3,5-di-tert-butylphenol, 2,3-di-n-octylphenol, 2,4-di-n-octylphenol, 2,5-di-n-octylphenol , 2,6-di-n-octylphenol, 3,4-di-n-octylphenol, 3,5-di-n-octylphenol, 2,3-di-2-ethylhexylphenol, 2,4-di-2-ethylhexylphenol, 2, 5-di2-ethylhexylphenol, 2,6-di2-ethylhexylphenol, 3,4-di2-ethylhexylphenol, 3,5-di2-ethylhexylphenol, 2,3-di-n-nonylphenol, 2,4 -Di-n-nonylphenol, 2,5-di-n-nonylphenol, 2,6-di-n-nonylphenol, 3,4-di-n-nonylphenol, 3,5-di-n-nonylphenol, 2-nitrophenol, 3-nitro Phenol, 4-nitrophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol , styrenated phenol (mono-, di-, or tri-substitution of phenol by α-methylbenzyl group), methyl salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl 4-hydroxybenzoate, 4 -[(dimethylamino)methyl]phenol, 4-[(dimethylamino)methyl]nonylphenol, bis(4-hydroxyphenyl)acetic acid, 2-hydroxypyridine, 2-hydroxyquinoline, 8-hydroxyquinoline, and 2-chloro- Examples include 3-pyridinol.

Examples of hydroxyl group-containing compounds other than alcohol compounds and phenol compounds include N-hydroxysuccinimide and triphenylsilanol.

Examples of active methylene compounds include Meldrum's acid, dialkyl malonate (e.g., dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-tert-butyl malonate, di-2-ethylhexyl malonate, methyl malonate). n-butyl, ethyl n-butyl malonate, methyl sec-butyl malonate, ethyl sec-butyl malonate, methyl tert-butyl malonate, ethyl tert-butyl malonate, diethyl methylmalonate, dibenzyl malonate, malonic acid diphenyl, benzylmethyl malonate, ethylphenyl malonate, tert-butylphenyl malonate, isopropylidene malonate, etc.), alkyl acetoacetate (e.g., methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate) , n-butyl acetoacetate, tert-butyl acetoacetate, benzyl acetoacetate, phenyl acetoacetate, etc.), 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate.

Examples of amine compounds include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis(2,2,6,6-tetramethylpiperidinyl)amine, di-n-propylamine, diisopropylamine, isopropyl Ethylamine, 2,2,4-trimethylhexamethyleneamine, 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis(3,5,5-trimethylcyclohexyl)amine, piperidine, 2, 6-dimethylpiperidine, tert-butylmethylamine, tert-butylethylamine, tert-butyl n-propylamine, tert-butyl n-butylamine, tert-butylbenzylamine, tert-butylphenylamine, 2,2,6-trimethyl Piperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino)-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6-methyl- Examples include 2-piperidine and 6-aminocaproic acid.

Examples of imine compounds include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, and guanidine.

Examples of oxime compounds include formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, cyclohexanoneoxime, diacetylmonoxime, benzophenoneoxime, 2,2,6,6-tetramethylcyclohexanoneoxime, diisopropylketoneoxime, methyl tert-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethyl heptyl ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone oxime, Examples include 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4'-dimethoxybenzophenone oxime, and 2-heptanone oxime.

Examples of carbamic acid compounds include phenyl N-phenylcarbamate.

Examples of urea-based compounds include urea, thiourea, and ethyleneurea.

Examples of acid amide (lactam) compounds include acetanilide, N-methylacetamide, acetamide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, and laurolactam. Can be mentioned.

Examples of acid imide compounds include succinimide, maleimide, and phthalimide.

Examples of triazole compounds include 1,2,4-triazole and benzotriazole.

Examples of pyrazole compounds include pyrazole, 3,5-dimethylpyrazole, 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-di-tert-butylpyrazole, 3-methylpyrazole, 4-benzyl- Examples include 3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole.

Examples of pyrrole compounds include pyrrole, 2-methylpyrrole, 3-methylpyrrole, 2,4-dimethylpyrrole, and the like.

Examples of mercaptan compounds include n-butylmercaptan, n-dodecylmercaptan, n-hexylmercaptan, thiophenol, and pyridine-2-thiol.

Examples of bisulfites include sodium bisulfite.

（式（ａ１－１）、式（ａ１－２）及び式（ａ１－３）中、Ｒ^１、及びＲ^２は、前記式（ａ１）と同様であり、Ｒ^７は、それぞれ独立に炭素原子数１以上１２以下の有機基であり、Ｒ^８は、それぞれ独立にハロゲン原子又は炭素原子数１以上６以下の有機基であり、Ｒ^９は、それぞれ独立に炭素原子数１以上６以下の有機基であり、ａは、０以上３以下の整数である。） Among the structural units A1 represented by the formula (a1) explained above, the following formulas (a1-1) and (a1- 2) or a structural unit represented by formula (a1-3) is preferable.

(In formula (a1-1), formula (a1-2) and formula (a1-3), R ¹ and R ² are the same as in formula (a1) above, and R ⁷ is each independently a carbon atom. R ⁸ is each independently a halogen atom or an organic group having 1 to 6 carbon atoms; R ⁹ is each independently an organic group having 1 to 6 carbon atoms; group, and a is an integer from 0 to 3.)

In formula (a1-1), the organic group as R ⁷ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an alkoxyalkyl group having 2 to 12 carbon atoms. group, a phenyl group, a phenylalkyl group having 7 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, and the like. Among these groups, an alkyl group is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, an alkyl group having 1 to 3 carbon atoms is even more preferred, and a methyl group or an ethyl group is particularly preferred.
The alkyl group may be linear or branched.
In formula (a1-1), two R ⁷ 's may be the same or different.

In formula (a1-2), R ⁸ is a substituent on the pyrazolyl group, and each independently represents a halogen atom or an organic group having 1 or more and 6 or less carbon atoms.
Suitable examples of ^R8 include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 carbon atoms. Examples include aliphatic acyl groups of 6 or less.
^R8 is preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. An alkyl group of 1 or more and 3 or less is more preferable, and a methyl group is particularly preferable.
In formula (a1-2), a is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less.

In formula (a1-3), the organic group as R ⁹ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an alkoxyalkyl group having 2 to 12 carbon atoms. group, a phenyl group, a phenylalkyl group having 7 or more and 12 or less carbon atoms, and the like.
In formula (a1-3), two R ⁹ 's may be the same or different.

The structural unit A1 is incorporated into the resin by copolymerizing a (meth)acrylic acid ester represented by the following formula (a-I) with a monomer that provides another structural unit.
Among the (meth)acrylic acid esters represented by formula (a-I), those represented by the following formula (a-I-1), formula (a-I-2), or formula (a-I-3) are The (meth)acrylic ester represented by the following formula (a-I-1a), formula (a-I-2a), or formula (a-I-3a) is preferable. More preferred.
The structural unit A1 may be present in a block shape or randomly in the resin. The structural units A1 are preferably present randomly in the resin because the isocyanate groups generated in the structural units A1 by heating are likely to react well with the hydroxyl groups.

Preferred specific examples of the (meth)acrylic acid ester that provides the structural unit A1 include the following compounds.

Among these, the following (meth)acrylic esters are preferred because they are easy to manufacture and easy to obtain resins with good curability.

The amount of structural unit A1 in resin A is not particularly limited as long as it does not impede the object of the present invention. From the viewpoint of curability, the content of the structural unit A1 in the resin A is preferably 15 mol% or more, more preferably 15 mol% or more and 45 mol% or less, based on the total structural units of the resin A. From the viewpoint of good curability, the content of structural unit A1 in resin A is preferably 20 mol% or more and 40 mol% or less, and 25 mol% or more and 35 mol% or less, based on the total structural units of resin A. is more preferable.

<Structural unit A2>
Structural unit A2 is a structural unit represented by the above-mentioned formula (a2). In formula (a2), R ¹ is a hydrogen atom or a methyl group.

In formula (a2), R ⁴ is a divalent hydrocarbon group. The hydrocarbon group as R ⁴ may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group having an aliphatic portion and an aromatic portion. From the viewpoint of curability of the resin, R ⁴ is preferably a divalent aliphatic hydrocarbon group. When R ⁴ is a divalent aliphatic hydrocarbon group, the structure of the aliphatic hydrocarbon group may be linear, branched, or cyclic, or a combination of these. It may have any structure, preferably linear.

The number of carbon atoms in the hydrocarbon group as R ⁴ is not particularly limited. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 2 or more and 10 or less, particularly preferably 2 or more and 6 or less. When the hydrocarbon group is an aromatic group or a hydrocarbon group having an aliphatic portion and an aromatic portion, the number of carbon atoms is preferably 6 or more and 20 or less, more preferably 6 or more and 12 or less.

Specific examples of divalent aliphatic hydrocarbon groups include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, and propane-1,2-diyl group. Diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, and icosane- A 1,20-diyl group is mentioned.
Among these, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, Diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane- 1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, and icosane-1,20-diyl group are preferred, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group Diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group and decane-1,10-diyl group are more preferred, and ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1 ,5-diyl group, and hexane-1,6-diyl group are more preferred.

Specific examples of the divalent aromatic hydrocarbon group include p-phenylene group, m-phenylene group, o-phenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, and naphthalene- Examples include 2,7-diyl group, p-phenylene group and m-phenylene group are preferred, and p-phenylene group is more preferred.

（式（ａ－ＩＩ）中、Ｒ^１及びＲ^４は、式（ａ２）と同様である。） The structural unit A2 is incorporated into the resin by copolymerizing a (meth)acrylic acid ester represented by the following formula (a-II) with a monomer that provides another structural unit.
The structural unit A2 may be present in a block shape or randomly in the resin. The structural units A2 are preferably present randomly in the resin because the isocyanate groups generated in the structural units A1 by heating and the hydroxyl groups tend to react well.

(In formula (a-II), R ¹ and R ⁴ are the same as in formula (a2).)

Preferred specific examples of (meth)acrylic esters providing structural unit A2 include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, -hydroxybutyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl acrylate, and 3-hydroxyphenyl methacrylate.
Among these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.

The amount of structural unit A2 in resin A is not particularly limited as long as it does not impede the object of the present invention.
The amount of structural unit A2 in resin A is preferably 15 mol% or more, more preferably 15 mol% or more and 45 mol% or less, based on the total structural units of resin A. From the viewpoint of good curability, the content of structural unit A2 in resin A is preferably 20 mol% or more and 40 mol% or less, and 25 mol% or more and 35 mol% or less, based on the total structural units of resin A. is more preferable.
In addition, the number of moles of structural unit A1 and the number of moles of structural unit A2 in resin A are preferably 80/100 or more and 100/80 or less, as the number of moles of structural unit A1/the number of moles of structural unit A2. /100 or more and 100/90 or less are more preferable, and 95/100 or more and 100/95 or less are particularly preferable. It is most preferable that the number of moles of the structural unit A1 and the number of moles of the structural unit A2 in the resin A are equal moles.

<Structural unit A3>
Structural unit A3 is a structural unit represented by the above-mentioned formula (a3). In formula (a3), R ¹ is a hydrogen atom or a methyl group.

In formula (a3), R ⁶ is an organic group containing two or more benzene rings. By including the structural unit A3 having an organic group containing two or more benzene rings as R ⁶ , a cured product exhibiting good transparency can be formed.
Two or more benzene rings contained in R ⁶ may be fused with each other, or may be bonded by a single bond or a linking group.
The number of carbon atoms in R ⁶ is not particularly limited as long as it does not impede the purpose of the present invention. The number of carbon atoms in R ⁶ is preferably 10 or more and 50 or less, more preferably 10 or more and 30 or less.

The organic group containing two or more benzene rings as R ⁶ is a group obtained by removing one hydrogen atom from the following polycyclic compound or a compound in which a substituent is introduced into the following polycyclic compound. Can be mentioned. In the following formula, X is -O-, -S-, -CO-, -SO ₂ -, -CO-NH-, -CO-NH-CO-, -NH-CO-NH-, -CO-O- , -CO-O-CO-, -O-CO-O-, -SO ₂ , -NH-, -S-S-, -CH ₂ -, -CH(CH ₃ )-, or -C(CH ₃ ) ₂ -.

Substituents that can be introduced into the above polycyclic compound include halogen atoms, alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. group, an aliphatic acyl group having 2 to 6 carbon atoms, a nitro group, and a cyano group.
When substituents are introduced into the above polycyclic compound, the number of substituents is not particularly limited, but is preferably 4 or less, and preferably 1 or 2.

As R ⁶ explained above, a group represented by the following formula is preferable.
In the following formula, R ¹⁰ , R ¹¹ , and R ¹³ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 1 to 6 carbon atoms. A group selected from the group consisting of an alkoxy group having 6 or less, an aliphatic acyl group having 2 to 6 carbon atoms, a nitro group, and a cyano group, and R ¹² is a hydrogen atom or a group having 1 to 6 carbon atoms. is an alkyl group, b and c are each independently an integer of 0 to 4, and d is an integer of 0 to 7.

Among these groups, the groups represented by the following formula are preferred because they easily form a highly transparent cured product and are easy to introduce into the resin, and in the following formula, two b are A biphenylyl group in which both groups are 0 is more preferred.

The group R ⁶ explained above is bonded to the main chain of the resin via R ⁵ . R ⁵ is a single bond or a divalent linking group.
The divalent linking group is not particularly limited as long as it does not impede the purpose of the present invention. Suitable examples of the divalent linking group include alkylene groups having 1 to 6 carbon atoms, -O-, -S-, -CO-, -SO ₂ -, -CO-NH-, -CO-NH -CO-, -NH-CO-NH-, -CO-O-, -CO-O-CO-, -O-CO-O-, -SO ₂ , -NH-, and -S-S- Examples include a divalent group selected from the group and a group combining two or more divalent groups selected from the above-mentioned group.
Among R ⁶ , a single bond, an alkylene group having 1 to 6 carbon atoms, and -CO-O- are preferable, a single bond and -CO-O- are more preferable, and -CO-O-* (* is , which represents the terminal end of the bond bonding to R ⁶ in formula (a3)) is particularly preferred. In addition, when R ⁶ is an alkylene group, the alkylene group may be linear or branched.

From the above, the structural unit A3 is preferably a structural unit represented by the following formula (a3-1). In formula (a3-1), R ¹ , R ¹⁰ and b are each as described above.

The structural unit A3 is incorporated into the resin by copolymerizing an unsaturated compound represented by the following formula (a-III) with a monomer providing another structural unit.
The structural unit A3 may be present in a block shape or randomly in the resin. Since it is easy to uniformly distribute the structural units A1 and A2 in the resin, it is preferable that the structural units A3 exist randomly in the resin.

As the unsaturated compound represented by the formula (a-III), a (meth)acrylic acid ester represented by the following formula (a-III-1) is preferable, and the unsaturated compound represented by the following formula (a-III-1a) is preferable. More preferred are (meth)acrylic acid esters. In formula (a-III), formula (a-III-1), and formula (a-III-1a), R ¹ , R ⁵ , R ⁶ , R ¹⁰ , and b are each as described above.

Preferred specific examples of unsaturated compounds providing structural unit A3 include acrylic acid (1,1'-biphenyl-4-yl) ester, methacrylic acid (1,1'-biphenyl-4-yl) ester, and acrylic acid (1,1'-biphenyl-4-yl) ester. (1,1'-biphenyl-3-yl) ester, methacrylic acid (1,1'-biphenyl-3-yl) ester, 4-vinyl-1,1'-biphenyl, and 3-vinyl-1,1' -Biphenyl.
Among these, acrylic acid (1,1'-biphenyl-4-yl) ester and methacrylic acid (1,1'-biphenyl-4-yl) ester are preferred.

The amount of structural unit A3 in resin A is not particularly limited as long as it does not impede the object of the present invention. The amount of structural unit A3 in resin A is preferably 30 mol% or more and 50 mol% or less, and 35 mol% or more and 50 mol% or less, based on the total structural units of resin A, from the viewpoint of good curability and curability of the cured product. is more preferable, and particularly preferably 40 mol% or more and 50 mol% or less.

<Other structural units>
Resin A may contain other structural units in addition to the above-mentioned structural unit A1, structural unit A2, and structural unit A3 within a range that does not impede the object of the present invention.

Examples of other structural units include structural units derived from (meth)acrylic esters. Those containing structural units can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. The (meth)acrylic ester is represented by the following formula (a-IV), and is not particularly limited as long as it does not impede the purpose of the present invention.

In the above formula (a-IV), R ^a1 is a hydrogen atom or a methyl group. R ^a11 is an organic group that does not have an active hydrogen-containing group that can react with the isocyanate group generated from the blocked isocyanate group in structural unit A1.
Examples of groups containing active hydrogen include hydroxyl groups, mercapto groups, amino groups, and carboxy groups. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom. Further, this organic group may be linear, branched, or cyclic.

Substituents other than hydrocarbon groups in the organic group of R ^a11 are not particularly limited as long as the effects of the present invention are not impaired, and include halogen atoms, alkylthio groups, arylthio groups, cyano groups, silyl groups, alkoxy groups, alkoxy carbonyl group, nitro group, nitroso group, acyl group, acyloxy group, alkoxyalkyl group, alkylthioalkyl group, aryloxyalkyl group, arylthioalkyl group, N,N-disubstituted amino group (-NRR': R and R' each independently represents a hydrocarbon group). The hydrogen atom included in the above substituent may be substituted with a hydrocarbon group. Moreover, the hydrocarbon group contained in the above-mentioned substituent may be linear, branched, or cyclic.

R ^a11 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, an alkyl group, or a heterocyclic group. Further, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

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

When R ^a11 is an alicyclic group or a group containing an alicyclic group, suitable alicyclic groups include monocyclic alicyclic groups such as a cyclopentyl group and a cyclohexyl group, an adamantyl group, and a norbornyl group. Polycyclic alicyclic groups such as a group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group can be mentioned.

Examples of monomers other than the above-mentioned (meth)acrylic esters that provide other structural units include allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers can be used alone or in combination of two or more.

Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; etc. Can be mentioned.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, diethylene glycol vinyl ether, Alkyl vinyl ethers such as dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether , vinyl aryl ethers such as vinyl anthrani ether; and the like.

Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl phenyl. Examples include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy Alkyl styrenes such as methylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Halostyrenes such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and the like.

When resin A contains other structural units other than the above-mentioned structural units A1, structural units A2, and structural units A3, the total amount of structural units A1, structural units A2, and structural units A3 in resin A is It is preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 95 mol% or more based on the total structural units.
Resin A contains only structural units A1, A2, and A3 without any other structural units, since it is easy to form a highly transparent cured product and have good curability. It is preferable to consist of

The method for producing resin A described above is not particularly limited. In general, after mixing predetermined amounts of the monomers that provide the above-mentioned structural units A1, A2, and A3, and monomers that provide other structural units as necessary, The resin can be obtained by polymerizing in a suitable solvent in the presence of a polymerization initiator at a temperature range of, for example, 50° C. or higher and 120° C. or lower. The resin is often obtained as a solution in an organic solvent, but the resin obtained as a solution can be blended as it is into the curable composition described below, or used as it is as a curable composition.

The mass average molecular weight of the resin A obtained by the above method is preferably 30,000 or more, more preferably 35,000 or more and 100,000 or less, particularly preferably 40,000 or more and 80,000 or less. The mass average molecular weight is a polystyrene equivalent molecular weight measured by GPC. When the weight average molecular weight of the resin is high to a certain extent, it is easy to form a cured product having excellent solvent resistance and heat decomposition resistance.

The solution of resin A obtained as described above may be mixed with a poor solvent such as hexane, diethyl ether, methanol, water, etc. to precipitate resin A, and the precipitated resin A may be recovered and used. The precipitated resin A is preferably washed after filtration and then dried under normal pressure or reduced pressure at a temperature that does not decompose the blocked isocyanate group in the structural unit A1. In this way, solid resin in powder form can be recovered. The powdered resin may be used as it is or may be blended into a curable composition.

The concentration of the thermosetting material (A) in the curable composition is preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 30% by mass or less.

<Near-infrared absorbing dye (B)>
The near-infrared absorbing dye (B) is a dye that absorbs in the near-infrared region (wavelength of 780 nm or more and 1200 nm or less), and has a partial structure represented by >N ⁺ =.
Specific examples of the near-infrared absorbing dye (B) include cyanine compounds, squarylium compounds, and diimonium compounds. Among these, cyanine compounds are preferred because they have good performance as a near-infrared absorbing dye (B) and good solubility in the curable composition.

（式（ｂ１－１）中、
Ｚ^１は下記式（ｂ１－２）又は（ｂ１－３）で表される基であり、
Ｚ^２は下記式（ｂ１－４）又は（ｂ１－５）で表される基であり、
Ｒ^２１～Ｒ^２４はそれぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよい炭素原子数１以上２０以下のアルキル基、又は、置換基を有していてもよい炭素原子数６以上２０以下のアリール基であり、
１又は複数のＲ^２１と、１又は複数のＲ^２２とからなる群より選択される任意の２つの基は、互いに結合して環を形成してもよく、
ｎ１は、１以上５以下の整数であり、
Ｘ１は、１価のアニオンである。）

（式（ｂ１－２）及び（ｂ１－３）中、
Ｒ^３１～Ｒ^３８はそれぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよい炭素原子数１以上２０以下のアルキル基、又は、置換基を有していてもよい炭素原子数６以上２０以下のアリール基であり、
Ｒ^４１～Ｒ^４６はそれぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよい炭素原子数１以上２０以下のアルキル基、又は、置換基を有していてもよい炭素原子数６以上２０以下のアリール基である。）

（式（ｂ１－４）及び（ｂ１－５）中、Ｒ^３１～Ｒ^３８及びＲ^４１～Ｒ^４６は、（ｂ１－２）及び（ｂ１－３）におけるＲ^３１～Ｒ^３８及びＲ^４１～Ｒ^４６と同じである。） Examples of cyanine compounds include compounds represented by the following formula (b1-1).

(In formula (b1-1),
Z ¹ is a group represented by the following formula (b1-2) or (b1-3),
Z ² is a group represented by the following formula (b1-4) or (b1-5),
R ²¹ to R ²⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom number which may have a substituent. an aryl group of 6 or more and 20 or less,
Any two groups selected from the group consisting of one or more R ²¹ and one or more R ²² may be bonded to each other to form a ring,
n1 is an integer from 1 to 5,
X1 is a monovalent anion. )

(In formulas (b1-2) and (b1-3),
R ³¹ to R ³⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom number which may have a substituent. an aryl group of 6 or more and 20 or less,
R ⁴¹ to R ⁴⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom number which may have a substituent. It is an aryl group of 6 or more and 20 or less. )

(In formulas (b1-4) and (b1-5), R ³¹ to R ³⁸ and R ⁴¹ to R ⁴⁶ are R ³¹ to R ³⁸ and R ⁴¹ to R in (b1-2) and (b1-3). (Same as ^46. )

In formula (b1-1), examples of the halogen atom as R ²¹ to R ²⁴ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
The alkyl group having 1 to 20 carbon atoms as R ²¹ to R ²⁴ may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n -butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group and the like.
Examples of the aryl group having 6 to 20 carbon atoms as R ²¹ to R ²⁴ include a phenyl group and a naphthyl group.
Examples of X1 include BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , I ⁻ and the like.
In formula (b1-1), when n1 is an integer from 2 to 5, the structures in the n1 parentheses may be the same or different.

In formula (b1-2) and formula (b1-3), as R ³¹ to R ³⁸ or R ⁴¹ to R ⁴⁶ , an alkyl having 1 to 20 carbon atoms that may have a halogen atom or a substituent; The aryl group having 6 or more and 20 or less carbon atoms which may have a group or a substituent is the same as R ²¹ to R ²⁴ in formula (b1-1).

The ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) ([mass of solvent (S1)]/[mass of near-infrared absorbing dye (B)]) is 30 or more, and 35 or more. The number is preferably 50 or more, and more preferably 50 or more. Further, the ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is preferably 300 or less.
Further, the near-infrared absorbing dye (B) is preferably 0.5 parts by mass or more and 10 parts by mass or less, and 1 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the thermosetting material (A). It is more preferable.
Further, the concentration of the near-infrared absorbing dye (B) in the curable composition is, for example, 0.1% by mass or more and 2% by mass or less, preferably 0.1% by mass or more and 0.5% by mass or less. .

<Solvent (S)>
The solvent (S) includes a solvent (S1) in which the polar term δp of the Hansen solubility parameter is 12 (MPa ^0.5 ) or more.

The polar term (term of energy due to dipole interaction) δp of the Hansen solubility parameter can be determined using software developed by Charles Hansen et al. (software name: Hansen Solubility Parameter in Practice (HSPiP)).
The polar term δp of the Hansen solubility parameter is preferably 13 (MPa ^0.5 ) or more, more preferably 16 (MPa ^0.5 ) or more. The upper limit of the polarity term δp of the Hansen solubility parameter is not particularly limited, but is, for example, 20 (MPa ^0.5 ) or less.
By forming a curable composition in which such a specific solvent (S1) is blended with a near-infrared absorber (B) having a specific structure in a specific mass ratio, the solvent (S1) for the near-infrared absorber (B) ) Excellent solubility and low temperature stability of the curable composition.
In addition, a curable composition containing a solvent (S1) whose polar term δp of the Hansen solubility parameter is 16 or more (MPa ^0.5 ) has excellent film formability by spin coating, so it is possible to reduce the film thickness etc. by spin coating. A uniform coating film can be formed, and a cured product with uniform film thickness etc. can be obtained.

The boiling point of the solvent (S1) is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. Note that the boiling point is the boiling point under atmospheric pressure. The upper limit of the boiling point of the solvent (S1) is not particularly limited, but is, for example, 250° C. or lower.

As the solvent (S1), a solvent having an ester structure, an amide structure, a sulfonic acid ester structure, or a sulfoxide structure in its chemical structure can be suitably used. By including such a structure in the chemical structure, it becomes easier to set δp to a desired value.
Moreover, the above-mentioned ester structure, amide structure, sulfonic acid ester structure, and sulfoxide structure may exist as part of the cyclic skeleton in the molecule.
Typical examples include solvents containing a lactone structure, a lactam structure, or a sultone structure in their chemical structure.
A solvent containing a lactone structure in its chemical structure is a solvent containing a lactone skeleton, which is a cyclic skeleton containing a -CO-O- bond.
A solvent containing a lactam structure in its chemical structure is a solvent containing a lactam skeleton, which is a cyclic skeleton containing a -CO-NH- bond.
A solvent containing a sultone structure in its chemical structure is a solvent containing a sultone skeleton, which is a cyclic skeleton containing an -O-SO ₂ - bond.

Preferred specific examples of the solvent (S1) include γ-butyrolactone (δp: 16.6 MPa ^0.5 , boiling point: 204-205°C), N,N-dimethylformamide (δp: 13.7 MPa ^0.5 , boiling point : 153°C), dimethyl sulfoxide (δp: 16.4 MPa ^0.5 , boiling point: 189°C), N-methylpyrrolidone (δp: 12.3 MPa ^0.5 , boiling point: 202°C), and the like.

The solvent (S) may contain a solvent (S2) different from the solvent (S1).
As the solvent (S2), propylene glycol methyl ether acetate (PGMEA), cyclopentanone (CP), methyl ethyl ketone (MEK), cyclohexanone, cyclopentanone, ethyl lactate (EL), propylene glycol monomethyl ether (PGME), 3- Examples include methoxybutyl acetate, butyl acetate, 3-methoxy-1-butanol, and the like.
When containing a solvent (S2), the content of the solvent (S1) is preferably 15% by mass or more based on the total mass of the solvent (S1) and the mass of the solvent (S2), and the content of the solvent (S1) is preferably 15% by mass or more, and 20% by mass. % or more is more preferable. The content of the solvent (S1) is preferably 80% by mass or less, more preferably 60% by mass or less based on the total mass of the solvent (S1) and the mass of the solvent (S2).

The solid content concentration of the curable composition is not particularly limited as long as it does not impede the object of the present invention. The solid content concentration is, for example, preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less.

<Other additives>
In addition to the thermosetting material (A), the near-infrared absorbing dye (B), and the solvent (S), the curable composition may contain other ingredients as long as they do not impede the purpose of the present invention. . Examples of other compounding agents include surfactants and antioxidants.

The surfactant is used, for example, to improve antifoaming properties during the production of the curable composition, and to further improve the stability of the curable composition, the applicability of the curable composition, and the like.

As the surfactant, water-soluble surfactants can be preferably used. As the surfactant, any of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants can be used. The surfactant may be silicone-based.

<Method for manufacturing curable composition>
The curable composition can be manufactured by mixing the thermosetting material (A), the near-infrared absorbing dye (B), the solvent (S), and other additives added as necessary. I can do it.

≪Cured product, near-infrared absorption filter, and manufacturing method thereof≫
A cured product can be obtained by curing the curable composition.
The cured product may be a patterned cured product or a flat non-patterned cured product.

A cured product of such a curable composition can be used as a near-infrared absorption filter. A near-infrared absorption filter is an optical filter that transmits visible light but absorbs (cuts) near-infrared light, and the near-infrared light is absorbed by the near-infrared absorption dye (B) contained in the curable composition. Ru. The near-infrared absorption filter may transmit all light having wavelengths in the visible light region, or may transmit only light having a specific wavelength among the wavelengths in the visible light region.
The near-infrared absorption filter can be used as a member of various devices, such as solid-state imaging devices such as CCDs and CMOSs, and image display devices such as liquid crystal display devices and organic EL devices.

The cured product can be produced, for example, by forming a curable composition layer made of a curable composition on a support and curing the curable composition layer.

Examples of the support on which the curable composition layer is formed include transparent substrates such as glass, substrates in which a solid-state imaging device is provided on a semiconductor substrate, and the like.
Methods for forming the curable composition layer on the support include coating methods such as spin coating, slit coating, spraying, roll coating, dropping, inkjet, screen printing, and applicator methods, and nanoimprinting. Examples include a transfer method using a mold or the like.
The curable composition layer may be a single layer or a multilayer.

The curable composition layer is cured by heating. The heating conditions are not particularly limited as long as the curable composition can be cured, but for example, the heating temperature is 140°C or more and 220°C or less, and the heating time is 1 minute or more and 30 minutes or less.
Moreover, it is preferable to remove the solvent (S) by heating simultaneously with or separately from curing.

When obtaining a patterned cured product, for example, after curing the curable composition, a resist layer having a desired pattern shape is provided on the surface of the cured product, and the cured product is processed by etching or the like using the resist layer as a mask. Bye.

Since the above-mentioned curable composition has excellent solvent solubility of the near-infrared absorber, by increasing the concentration of the near-infrared absorber (B) in the curable composition, a thin near-infrared absorbent can be obtained while having the desired near-infrared absorption characteristics. Cured products such as infrared absorption filters can be manufactured. In addition, since the above-mentioned curable composition has excellent low-temperature stability, even when the curable composition is used after being stored or transported at low temperatures, cured products such as near-infrared absorbing filters with uniform film thickness, etc. can be obtained.

≪Low-temperature storage method for curable composition and method for transporting curable composition≫
In the low temperature storage method for a curable composition, the curable composition is stored at 10°C or lower.
In the method for transporting a curable composition, the curable composition is transported by a transporter at a temperature of 10° C. or lower.
Here, the transporter is not particularly limited as long as it can transport the curable composition at a desired temperature. Specific examples of transport aircraft include automobiles such as trucks, railway vehicles, ships, and aircraft.
The storage and transportation temperature can be 10°C or lower, and further can be 5°C or lower or -20°C or lower.
The lower limit of the temperature for storage and transportation is not particularly limited as long as the curable composition does not solidify or components in the curable composition precipitate. The storage and transportation temperature may be, for example, -22°C or higher, or -15°C or higher.
The above curable composition has excellent low temperature stability. Therefore, even if the curable composition is stored at a low temperature or transported by a transporter at a low temperature, the generation of precipitates in the curable composition is suppressed. Therefore, even after storage or transportation at low temperatures, the composition of the curable composition is unlikely to change from before storage or transportation, and the curable composition can be used to produce a cured product with desired properties. be able to.

<<Method for providing curable composition>>
In the method for providing a curable composition, the curable composition is stored at a low temperature in a process line that executes the above method for producing a cured product or a process line that executes the above method for producing a near-infrared absorbing filter. A curable composition stored by a method is provided. The temperature of the curable composition provided may be the temperature at which it was stored at a low temperature, and may be higher than 10°C, specifically, for example, about 15°C or higher and 25°C or lower.
The curable composition here may be a composition appropriately selected and prepared from the materials mentioned above, and the curable composition may be prepared depending on the size and operating speed of the process line. All you have to do is plan the timing of the provision.
Moreover, the temperature for storage and transportation may be appropriately set according to the curable composition.
Note that the business entity that executes the method for manufacturing the cured product or near-infrared absorption filter and the business entity that executes the present provision method are not necessarily the same.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

[Solvent solubility test]
The following cyanine compound B1 (product name: S01965, manufactured by Spectruminfo) was used as a near-infrared absorbing dye (B), stirred at 25° C. for 1 hour, and the maximum concentration dissolved in the solvent shown in Table 1 was measured. The results are shown in Table 1.

また、近赤外線吸収染料（Ｂ）として上記シアニン系化合物Ｂ１（製品名：Ｓ０１９６５、Ｓｐｅｃｔｒｕｍｉｎｆｏ社製）を用いた。
また、溶剤（Ｓ１）として、ガンマブチロラクトン（ＧＢＬ）、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）を用いた。
また、溶媒（Ｓ２）として、シクロペンタノン（ＣＰ）、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）を用いた。 [Examples 1 to 5 and Comparative Examples 1 to 4]
In Examples 1 to 5 and Comparative Examples 1 to 4, the following resin a was used as the thermosetting material (A). The number at the bottom right of the parentheses in each structural unit in the structural formula below represents the content (mol %) of the structural unit in the resin. The mass average molecular weight Mw of resin a is 50,000, and the degree of dispersion (mass average molecular weight Mw/number average molecular weight Mn) is 4.5.

Further, the above cyanine compound B1 (product name: S01965, manufactured by Spectruminfo) was used as the near-infrared absorbing dye (B).
Further, as the solvent (S1), gamma butyrolactone (GBL), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) were used.
Moreover, cyclopentanone (CP) and propylene glycol monomethyl ether acetate (PGMEA) were used as the solvent (S2).

(Manufacture of curable composition)
A mixed solvent of solvent (S1) and solvent (S2) of the type and mixing ratio (mass ratio) listed in Table 2, resin a, and cyanine compound B1 were placed in a container and heated at 25°C for 1 hour. By stirring, curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were obtained. Resin a was used in an amount such that the ratio of the mass of resin a to the total mass of the mixed solvent and resin a (mass of resin a/(mass of mixed solvent + mass of resin a)) was 0.20. Further, the cyanine compound B1 was used in an amount such that the mass ratio of the cyanine compound B1 to the resin a (mass of the cyanine compound B1/mass of the resin a) was 0.015.
The resulting curable compositions of Examples 1 to 5 and Comparative Examples 1 to 4 had resin a and cyanine compound B1 dissolved in a mixed solvent, and were uniform solutions.

[Low temperature stability]
After storing the curable compositions of Examples 1 to 5 and Comparative Examples 1 to 4 at 25°C, 5°C, or -20°C for 7 days, they were visually observed, and the cases where no precipitates were observed were marked as ○. The case where a precipitate was formed was evaluated as ×. The results are shown in Table 2.

Table 1 shows that gamma-butyrolactone (GBL), dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF) as the solvent (S1) have excellent solubility of the near-infrared absorbing dye (B). Therefore, it can be seen that the curable composition containing the solvent (S1) has excellent solvent solubility of the near-infrared absorbing dye (B).
From Table 2, the curable compositions of Examples 1 to 5 in which the mass ratio of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is 30 or more can be stored at 5°C or -20°C. , it can be seen that no precipitates were formed. Therefore, it can be seen that the curable compositions of Examples 1 to 5 have excellent low temperature stability.

Claims (11)

Including a thermosetting material (A), a near-infrared absorbing dye (B), and a solvent (S),
The near-infrared absorbing dye (B) has a partial structure represented by >N ⁺ =,
The solvent (S) includes a solvent (S1) whose polar term δp of the Hansen solubility parameter is 12 (MPa ^0.5 ) or more,
The ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is 30 or more,
The near-infrared absorbing dye (B) is at least one selected from cyanine compounds, squarylium compounds, and diimonium compounds,
A curable composition , wherein the thermosetting material (A) has at least one thermosetting group selected from an epoxy group, an isocyanate group, and a blocked isocyanate group . The curable composition according to claim 1, wherein the solvent (S1) is a solvent containing one or more structures selected from the group consisting of an ester structure, an amide structure, a sulfonic acid ester structure, and a sulfoxide structure in its chemical structure. . Contains a solvent (S2) different from the solvent (S1),
The curable composition according to claim 1 or 2, wherein the content of the solvent (S1) is 15% by mass or more based on the total mass of the solvent (S1) and the mass of the solvent (S2). . The curable composition according to any one of claims 1 to 3, wherein the ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is 300 or less. A cured product of the curable composition according to any one of claims 1 to 4 . A near-infrared absorbing filter comprising a cured product of the curable composition according to any one of claims 1 to 4 . A method for producing a cured product, comprising curing the curable composition according to any one of claims 1 to 4 . A method for producing a near-infrared absorption filter, comprising curing the curable composition according to any one of claims 1 to 4 . A method for storing a curable composition at a low temperature, the method comprising: storing the curable composition at a temperature of 10° C. or lower,
The curable composition includes a thermosetting material (A), a near-infrared absorbing dye (B), and a solvent (S),
The near-infrared absorbing dye (B) has a partial structure represented by >N ⁺ =,
The solvent (S) includes a solvent (S1) whose polar term δp of the Hansen solubility parameter is 12 (MPa ^0.5 ) or more,
The ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is 30 or more,
A method for storing a curable composition at a low temperature, wherein the thermosetting material (A) has at least one thermosetting group selected from an epoxy group, an isocyanate group, and a blocked isocyanate group . A method for transporting a curable composition, the method comprising: transporting the curable composition using a transporter at a temperature of 10°C or lower,
The curable composition includes a thermosetting material (A), a near-infrared absorbing dye (B), and a solvent (S),
The near-infrared absorbing dye (B) has a partial structure represented by >N ⁺ =,
The solvent (S) includes a solvent (S1) whose polar term δp of the Hansen solubility parameter is 12 (MPa ^0.5 ) or more,
The ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is 30 or more,
A method for transporting a curable composition, wherein the thermosetting material (A) has at least one thermosetting group selected from an epoxy group, an isocyanate group, and a blocked isocyanate group . For a process line that executes a method for producing a cured product, which includes curing a curable composition, or a process line that executes a method for producing a near-infrared absorption filter, which includes curing a curable composition ,
A method for providing a curable composition, which provides a curable composition stored by a low-temperature storage method for a curable composition, in which the curable composition is stored at 10 ° C. or lower ,
The curable composition includes a thermosetting material (A), a near-infrared absorbing dye (B), and a solvent (S),
The near-infrared absorbing dye (B) has a partial structure represented by >N ⁺ =,
The solvent (S) includes a solvent (S1) whose polar term δp of the Hansen solubility parameter is 12 (MPa ^0.5 ) or more,
The ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is 30 or more,
A method for providing a curable composition, wherein the thermosetting material (A) has at least one thermosetting group selected from an epoxy group, an isocyanate group, and a blocked isocyanate group .