CN113337170B

CN113337170B - Curable composition, cured product, near infrared absorbing filter, and method for producing same

Info

Publication number: CN113337170B
Application number: CN202110054998.3A
Authority: CN
Inventors: 濑下武广; 井上朋之
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2020-02-18
Filing date: 2021-01-15
Publication date: 2024-04-05
Anticipated expiration: 2041-01-15
Also published as: TW202132379A; JP2021130734A; KR20210105284A; CN113337170A; JP7419097B2

Abstract

The present invention aims to provide a curable composition excellent in solvent solubility and low-temperature stability of a near-infrared ray absorber, a cured product and a near-infrared ray absorption filter using the curable composition, a method for producing the cured product and a method for producing the near-infrared ray absorption filter, a method for storing the curable composition at a low temperature, a method for transporting the curable composition, and a method for providing the curable composition. The solution of the present invention is a curable composition comprising a thermosetting material (A), a near infrared absorbing dye (B) having a structure of > N, and a solvent (S) ⁺ Partial structure expressed by =solvent (S) having a polarity term δp of 12 (MPa) including hansen solubility parameter ^0.5 ) The above solvent (S1), the ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) is 30 or more.

Description

Curable composition, cured product, near infrared absorbing filter, and method for producing same

Technical Field

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

Background

Optical filters (near infrared absorbing filters) that transmit visible light but block near infrared light have been used for various purposes.

For example, imaging devices such as digital cameras and video cameras use solid-state imaging devices such as CCDs (charge coupled devices) and CMOS (complementary metal oxide semiconductors); in these solid-state imaging devices, a near-infrared absorbing filter for blocking near-infrared rays and performing visibility correction is used.

The near infrared absorbing filter can be manufactured using a composition containing a near infrared absorbing agent and a solvent, for example (see patent document 1).

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2018-043185

Disclosure of Invention

Problems to be solved by the invention

In recent years, miniaturization of elements is demanded. By increasing the content of the near infrared ray absorber in the composition for manufacturing the near infrared ray absorption filter, the near infrared ray absorption filter can be thinned, and the miniaturization of the element can be contributed. Therefore, for a composition for manufacturing a near infrared ray absorption filter, it is desirable that the solvent solubility of the near infrared ray absorber is high.

In addition, the composition for producing the near-infrared absorbing filter is often used after being stored at the production site of the composition, the production site of the near-infrared absorbing filter, or the like, or is transferred from the production site of the composition to the production site of the near-infrared absorbing filter. When the composition for producing a near infrared absorbing filter contains a thermosetting material, the composition may be cured by heating, but the thermosetting material may be modified by reaction during storage and transfer of the composition containing the thermosetting material. In order to prevent the reaction of the thermosetting material, it is considered to store and transfer the composition containing the thermosetting material at a low temperature, but there is a problem that a precipitate may be generated when storing and transferring the composition at a low temperature. Therefore, a composition for producing a near infrared absorbing filter is also required to have excellent low-temperature stability, that is, to be less likely to cause precipitation even when stored or transferred at low temperatures.

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a curable composition excellent in solvent solubility and low-temperature stability of a near-infrared ray absorber, a cured product and a near-infrared ray absorption filter using the curable composition, a method for producing the cured product and a method for producing the near-infrared ray absorption filter, a method for storing the curable composition at a low temperature, a method for transporting the curable composition, and a method for providing the curable composition.

Means for solving the problems

The inventors of the present application found that the above-mentioned problems can be solved by a composition comprising a thermosetting material (A), a near infrared absorbing dye (B) having a molecular weight of > N, and a solvent (S) ⁺ Partial structure expressed by =solvent (S) having a polarity term δp of 12 (MPa) including hansen solubility parameter ^0.5 ) The above solvent (S1), the ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) is 30 or more. More specifically, the present invention provides the following.

The invention according to item 1 is a curable composition comprising a thermosetting material (A), a near infrared absorbing dye (B) having a structure of > N, and a solvent (S) ⁺ Partial structure expressed by =solvent (S) having a polarity term δp of 12 (MPa) including hansen solubility parameter ^0.5 ) The above solvent (S1), the ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) is 30 or more.

In accordance with claim 2 of the present invention, there is provided a cured product of the curable composition according to claim 1.

In accordance with claim 3 of the present invention, there is provided a near infrared absorbing filter comprising a cured product of the curable composition according to claim 1.

A 4 th aspect of the present invention is a method for producing a cured product, comprising curing the curable composition according to the 1 st aspect.

A 5 th aspect of the present invention is a method for producing a near infrared absorbing filter, comprising curing the curable composition according to the 1 st aspect.

In accordance with claim 6 of the present invention, there is provided a method for storing a curable composition at a low temperature, wherein the curable composition according to claim 1 is stored at 10 ℃.

In accordance with claim 7 of the present invention, there is provided a method for transporting a curable composition, wherein the curable composition according to claim 1 is transported by a transport machine at a temperature of 10 ℃.

An 8 th aspect of the present invention is a method for providing a curable composition, wherein the method for producing a cured product according to the 4 th aspect or the method for producing a near infrared absorbing filter according to the 5 th aspect provides a curable composition stored by a low-temperature storage method for a curable composition according to the 6 th aspect.

ADVANTAGEOUS EFFECTS OF INVENTION

By the present invention, it is possible to provide: a curable composition which can produce a near infrared absorbing filter and has excellent solvent solubility and low-temperature stability of a near infrared absorbent; a cured product using the curable composition, and a near infrared absorbing filter; a method for producing the cured product and a method for producing the near infrared absorption filter; a method for storing the curable composition at a low temperature and a method for transporting the curable composition; and a method for providing the curable composition.

Detailed Description

Curable composition

The curable composition contains a thermosetting material (A), a near infrared absorbing dye (B), and a solvent (S). The near infrared absorbing dye (B) has a molecular structure of > N ⁺ Partial structure expressed by =solvent (S) having a polarity term δp of 12 (MPa) including hansen solubility parameter ^0.5 ) The above solvent (S1). The ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) is 30 or more.

The curable composition has a specific mass ratio of the near infrared ray absorber (B) having a specific structure to the specific solvent (S1), and therefore the solvent (S1) of the near infrared ray absorber (B) is excellent in solubility. Therefore, the concentration of the near infrared ray absorber (B) in the curable composition can be increased. Therefore, the cured product such as the near infrared ray absorption filter formed from the curable composition can be thinned while having desired near infrared ray absorption characteristics, and the device including the cured product such as the near infrared ray absorption filter can be miniaturized.

In addition, the curable composition is excellent in low-temperature stability, that is, is less likely to cause precipitation even when stored and transferred at low temperatures. For example, even when the curable composition is stored and transferred at 10 ℃ or lower, no precipitate is generated.

The essential or optional components of the curable composition and the method of manufacture are described.

Thermosetting material (A) >, and

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 curable 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.

The thermosetting material (a) is preferably a cured product thereof that transmits visible light. The visible light is, for example, light having a wavelength of 380nm 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 thereof include isocyanate compounds having an isocyanate group or a blocked isocyanate group, and epoxy compounds having an epoxy group. From the viewpoint of visible light transmittance (transparency), a (meth) acrylic resin having a thermosetting group such as an epoxy group, an isocyanate group, or a blocked isocyanate group is preferable. In the present specification, the term "(meth) propylene-" refers to both "propylene-" and "meth-propylene-".

They may be used alone or in combination of 1 or more than 2.

The thermosetting material is preferably a (meth) acrylic resin having a blocked isocyanate group, more preferably a (meth) acrylic resin (hereinafter also referred to as a resin a) containing a structural unit represented by the following formula (a 1), a structural unit represented by the following formula (a 2), and a structural unit represented by the following formula (a 3), from the viewpoint of easy availability of a curable composition satisfying both good thermosetting properties, stability at low temperatures, and good visible light transmittance of a cured product.

[ chemical formula 1]

(in the formulae (a 1), (a 2) and (a 3), R ¹ Each independently is a hydrogen atom, or a methyl group, R ² Is a single bond or an alkylene group having 1 to 5 carbon atoms, R ³ R is a blocked isocyanate group ⁴ Is a hydrocarbon group of 2 valency, R ⁵ Is a single bond, or a 2-valent linking group, R ⁶ Is a hydrocarbon group containing 2 or more benzene rings. )

Hereinafter, the structural unit represented by the formula (A1) is also referred to as "structural unit A1", the structural unit represented by the formula (A2) is also referred to as "structural unit A2", and the structural unit represented by the formula (A3) is also referred to as "structural unit A3".

The structural unit A1 represented by the above formula (A1) has a blocked isocyanate group as R ³ . The blocked isocyanate group means a group obtained by blocking an isocyanate group with a thermally dissociable protecting group.

Therefore, when the resin having the structural unit A1 is heated, the protecting group in the blocked isocyanate group is released, and an active isocyanate group is formed.

The isocyanate group formed by heating is easily reacted with a functional group having active hydrogen. Here, the structural unit A2 represented by the above formula (A2) has a hydroxyl group as a functional group having an active hydrogen group. Therefore, when the resin is heated, an active isocyanate group is formed in the structural unit A1. The isocyanate group (-NCO) reacts with the hydroxyl group in the structural unit A2, and thereby crosslinking by a urethane bond (-NH-CO-O-) is performed, whereby a cured product can be formed.

In addition, the above formula (a 3) tableThe structural unit shown has a hydrocarbon group containing more than 2 benzene rings as R ⁶ . Here, the hydrocarbon group containing 2 or more benzene rings contributes to transparency, good mechanical properties and heat resistance of the cured product.

Therefore, when the resin is heated, the curing of the resin proceeds well.

Hereinafter, the essential or optional structural units contained in the resin, the method of producing the resin, and the like will be described.

< structural Unit A1 >)

As described above, the resin a contains the structural unit A1 having a blocked isocyanate group. The resin a may also contain 2 or more structural units A1 in combination.

The structural unit A1 is a structural unit represented by the aforementioned formula (A1). In the formula (a 1), R ¹ Is a hydrogen atom or a methyl group.

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

Among these groups, methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, and pentane-1, 5-diyl are preferable, methylene, ethane-1, 2-diyl, and propane-1, 3-diyl are more preferable, and ethane-1, 2-diyl is particularly preferable.

In the formula (a 1), R ³ Is a blocked isocyanate group. As described above, the blocked isocyanate group means a group obtained by blocking an isocyanate group with a thermally dissociable protecting group.

The thermally dissociable protecting group may be formed by reacting an isocyanate group with a blocking agent that provides the protecting group.

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

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

Examples of the phenol-based compound include phenol, o-cresol, m-cresol, p-cresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-n-propylphenol, 3-n-propylphenol, 4-n-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-n-butylphenol, 3-n-butylphenol, 4-n-butylphenol, 2-sec-butylphenol, 3-sec-butylphenol, 4-sec-butylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 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-nonylphenol, 2, 3-n-nonylphenol, 2, 3-dimethylphenol, 2, 4-dimethylphenol, 5-dimethylphenol, 2, 6-dimethylphenol, 3-di-n-dimethylphenol, 3-di-n-propylphenol, 3-diethylphenol, 3, 5-diisopropylphenol, 2, 3-n-dimethylphenol, 3-di-n-propylphenol, 2, 3-dimethylphenol, 3-n-propylphenol, 2, 3-di-n-dimethylphenol, 3-propyl-2, 3-n-dimethylphenol, 2, 5-dimethylphenol, 2-di-n-propylphenol, 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, 3-di-n-butylphenol, and 2, 6-di-n-butylphenol, 3, 4-di-n-butylphenol, 3, 5-di-n-butylphenol, 2, 3-di-sec-butylphenol, 2, 4-di-sec-butylphenol, 2, 5-di-sec-butylphenol, 2, 6-di-sec-butylphenol, 3, 4-di-sec-butylphenol, 3, 5-di-sec-butylphenol, 2, 3-di-t-butylphenol, 2, 5-di-t-butylphenol, 2, 6-di-t-butylphenol, 3, 4-di-t-butylphenol, 3, 5-di-t-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-ethylhexyl phenol, 2, 4-di-2-ethylhexyl phenol, 2, 5-di-2-ethylhexyl phenol, 2, 6-di-2-ethylhexyl phenol, 3, 4-di-2-ethylhexyl phenol, 3, 5-di-2-ethylhexyl phenol, 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-nitrophenol, 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 trisubstituted for phenol based on alpha-methylbenzyl), 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, 2-chloro-3-pyridinol, and the like.

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

Examples of the active methylene-based compound include michaelis acid (Meldrum's acid), dialkyl malonates (for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-t-butyl malonate, di-2-ethylhexyl malonate, methyl-n-butyl malonate, ethyl-n-butyl malonate, methyl-sec-butyl malonate, methyl-t-butyl malonate, ethyl-t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzyl-methyl malonate, ethylphenyl malonate, t-butylphenyl malonate, isopropylidene malonate, and the like), alkyl acetoacetates (for example, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, t-butyl acetoacetate, benzyl acetoacetate, phenyl acetoacetate, and the like), 2-acetoacetoxyethyl methacrylate, acetylacetone, ethyl cyanoacetate, and the like.

As the amine-based compound, there is used, examples thereof include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2, 6-tetramethylpiperidinyl) amine, di-N-propylamine, diisopropylamine, isopropylethylamine, 2, 4-trimethylhexamethyleneamine, 2, 5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis (3, 5-trimethylcyclohexyl) amine, piperidine 2, 6-Dimethylpiperidine, t-butylmethylamine, t-butylethylamine, t-butyl-N-propylamine, t-butyl-N-butylamine, t-butylbenzylamine, t-butylphenylamine 2, 6-trimethylpiperidine, 2, 6-tetramethylpiperidine, (dimethylamino) -2, 6-tetramethylpiperidine, 2, 6-tetramethyl-4-piperidine, 6-methyl-2-piperidine, 6-aminocaproic acid, and the like.

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

Examples of the oxime-based compound include formaldehyde oxime, aldoxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, diacetyl monooxime, benzophenone oxime, 2, 6-tetramethyl cyclohexanone oxime, diisopropyl ketoxime, methyl tert-butyl ketoxime, diisobutyl ketoxime, methyl isobutyl ketoxime, methyl isopropyl ketoxime, methyl 2, 4-dimethyl amyl ketoxime, methyl 3-ethylheptyl ketoxime, methyl isoamyl ketoxime, n-amyl ketoxime, 2, 4-tetramethyl-1, 3-cyclobutanedioxime, 4' -dimethoxy benzophenone oxime, and 2-heptanone oxime.

Examples of the urethane compound include phenyl N-phenylcarbamate and the like.

Examples of the urea compound include urea, thiourea, and ethylene urea.

Examples of the amide-based (lactam-based) compound include acetanilide, N-methylacetamide, acetamide, epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam, pyrrolidone, 2, 5-piperazinedione, and laurolactam.

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

Examples of the triazole-based compound include 1,2, 4-triazole and benzotriazole.

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

Examples of the azole compound include pyrrole, 2-methylpyrrole, 3-methylpyrrole, and 2, 4-dimethylpyrrole.

Examples of the thiol compound include n-butylthiol, n-dodecylthiol, n-hexylthiol, thiophenol, and pyridine-2-thiol.

Examples of the bisulfite include sodium bisulfite and the like.

Among the structural units A1 represented by the above-described formula (A1), structural units represented by the following formulas (A1-1), (A1-2), or (A1-3) are preferable in terms of ease of production of the resin, good curability, and the like.

[ chemical formula 2]

(formula (a 1-1), formula (a 1-2) and formula (a 1-3), R ¹ And R is ² R is the same as in the above formula (a 1) ⁷ Each independently is an organic group having 1 to 12 carbon atoms, R ⁸ Each independently is a halogen atom or an organic group having 1 to 6 carbon atoms, R ⁹ Each independently represents an organic group having 1 to 6 carbon atoms, and a represents an integer of 0 to 3. )

In the formula (a 1-1), R is ⁷ Examples of the organic group include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, and the like. Of these groups, an alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

The alkyl group may be linear or branched.

In the formula (a 1-1), two R ⁷ May be the same or different.

In the formula (a 1-2), R ⁸ Each of which is a substituent on a pyrazolyl group and is independently a halogen atom or an organic group having 1 to 6 carbon atoms.

As R ⁸ Preferable examples of (a) 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, an aliphatic acyl group having 2 to 6 carbon atoms, and the like.

As R ⁸ Preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atomsThe lower alkyl group is particularly preferably methyl.

In the formula (a 1-2), a is an integer of 0 to 3, preferably an integer of 0 to 2.

In the formula (a 1-3), R is ⁹ Examples of the organic group include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, a phenyl group, and a phenylalkyl group having 7 to 12 carbon atoms.

In the formula (a 1-3), two R' s ⁹ May be the same or different.

The structural unit A1 may be inserted into the resin by copolymerizing a (meth) acrylate represented by the following formula (a-I) with a monomer providing other structural units.

Among the (meth) acrylic acid esters represented by the formula (a-I), preferred are (meth) acrylic acid esters represented by the following formula (a-I-1), formula (a-I-2), or formula (a-I-3), and more preferred are (meth) acrylic acid esters represented by the following formula (a-I-1 a), formula (a-I-2 a), or formula (a-I-3 a).

The structural unit A1 may be present in the resin in a block form or may be present in the resin in a random form. The structural unit A1 is preferably present in a random manner in the resin, from the viewpoint that the isocyanate group generated in the structural unit A1 by heating and the hydroxyl group easily react well.

[ chemical formula 3]

Preferable specific examples of the (meth) acrylic acid ester providing the structural unit A1 include the following compounds.

[ chemical formula 4]

Among these, (meth) acrylates are preferred from the viewpoints of ease of production of the resin, ease of obtaining a resin having good curability, and the like.

[ chemical formula 5]

The amount of the structural unit A1 in the resin a is not particularly limited within a range that does not hinder the object of the present invention. 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, with respect to the total structural units of the resin a, in view of curability. The content of the structural unit A1 in the resin a is preferably 20 mol% or more and 40 mol% or less, more preferably 25 mol% or more and 35 mol% or less, with respect to the total structural units of the resin a, from the viewpoint of good curability.

< structural Unit A2 >)

The structural unit A2 is a structural unit represented by the aforementioned formula (A2). In the formula (a 2), R ¹ Is a hydrogen atom or a methyl group.

In the formula (a 2), R ⁴ Is a 2-valent hydrocarbon group. As R ⁴ The hydrocarbon group of (2) may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group having an aliphatic moiety and an aromatic moiety. From the aspect of the curability of the resin, R ⁴ Aliphatic hydrocarbon groups of 2 valences are preferred. R is R ⁴ In the case of the aliphatic hydrocarbon group having a valence of 2, the structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof, and is preferably linear.

As R ⁴ The number of carbon atoms of the hydrocarbon group of (a) 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, and 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 the aliphatic hydrocarbon group having a valence of 2 include methylene, ethane-1, 2-diyl, ethane-1.1-diyl, propane-1, 3-diyl, propane-1, 2-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl, dodecane-1, 12-diyl, tridecane-1, 13-diyl, tetradecane-1, 14-diyl, pentadecane-1, 15-diyl, hexadecane-1, 16-diyl, heptadecane-1, 17-diyl, octadecane-1, 18-diyl, nonadecane-1, 19-diyl and eicosane-1, 20-diyl.

Of these, methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl, dodecane-1, 12-diyl, tridecane-1, 13-diyl, tetradecane-1, 14-diyl, pentadecane-1, 15-diyl, hexadecane-1, 16-diyl, heptadecane-1, 17-diyl, octadecane-1, 18-diyl, nonadecane-1, 19-diyl, and eicosane-1, 20-diyl, more preferably methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, pentadecane, 6-diyl, hexane-1, 16-diyl, decane, 1, 9-diyl, decane, 1, 2-diyl, 1, 5-diyl, 1, 9-diyl, 1, 2-decane, 1, 2-diyl, 1, 9-diyl, 1, 2-decane, 1, 9-diyl, 2-diyl, 1, 2-decane and 1, 2-diyl are preferable.

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

The structural unit A2 may be inserted into the resin by copolymerizing a (meth) acrylate represented by the following formula (a-II) with a monomer providing other structural units.

The structural unit A2 may be present in the resin in a block form or may be present in the resin in a random form. The structural unit A2 is preferably present in the resin in a random manner, from the viewpoint that the isocyanate group generated in the structural unit A1 by heating and the hydroxyl group easily react well.

[ chemical formula 6]

(in the formula (a-II), R ¹ R is R ⁴ The same applies to formula (a 2). )

As preferable specific examples of the (meth) acrylic acid ester providing the structural unit A2, there may be mentioned 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl acrylate, 3-hydroxyphenyl methacrylate and the like.

Among these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable.

The amount of the structural unit A2 in the resin a is not particularly limited within a range that does not hinder the object of the present invention.

The amount of the structural unit A2 in the resin a is preferably 15 mol% or more, more preferably 15 mol% or more and 45 mol% or less, with respect to the total structural units of the resin a. The content of the structural unit A2 in the resin a is preferably 20 mol% or more and 40 mol% or less, more preferably 25 mol% or more and 35 mol% or less, with respect to the total structural units of the resin a, from the viewpoint of good curability.

The number of moles of the structural unit A1 and the number of moles of the structural unit A2 in the resin a are preferably 80/100 or more and 100/80 or less, more preferably 90/100 or more and 100/90 or less, particularly preferably 95/100 or more and 100/95 or less, based on the number of moles of the structural unit A1/the number of moles of the structural unit A2. Most preferably, the number of moles of the structural unit A1 in the resin a is equal to the number of moles of the structural unit A2.

< structural Unit A3 >)

The structural unit A3 is a structural unit represented by the aforementioned formula (A3). In the formula (a 3), R ¹ Is a hydrogen atom or a methyl group.

In the formula (a 3)，R ⁶ Is an organic group containing more than 2 benzene rings. By containing, as R, an organic group having a benzene ring containing 2 or more ⁶ The structural unit A3 of (c) can form a cured product exhibiting good transparency.

R ⁶ More than 2 benzene rings contained in the aromatic hydrocarbon compound may be condensed with each other or may be bonded through a single bond or a linking group.

R ⁶ The number of carbon atoms of (2) is not particularly limited within a range that does not hinder the object of the present invention. R is R ⁶ The number of carbon atoms in (a) is preferably 10 to 50, more preferably 10 to 30.

Regarding R as ⁶ Examples of the organic group having 2 or more benzene rings include a group obtained by removing 1 hydrogen atom from the polycyclic compound described below or a compound obtained by introducing a substituent into the polycyclic compound described below. 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-。

[ chemical formula 7]

Examples of the substituent that can be introduced into the polycyclic compound 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, an aliphatic acyl group having 2 to 6 carbon atoms, a nitro group, and a cyano group.

In the case of introducing a substituent into the polycyclic compound described above, the number of substituents is not particularly limited, but is preferably 4 or less, and more preferably 1 or 2.

As R described hereinabove ⁶ Preferred are groups represented by the following formula.

In the following formula, R ¹⁰ 、R ¹¹ And R is ¹³ Each independently is selected from halogenA group selected from the group consisting of a plain 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, an aliphatic acyl group having 2 to 6 carbon atoms, a nitro group, and a cyano group, R ¹² Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, b and c are each independently an integer of 0 to 4, and d is an integer of 0 to 7.

[ chemical formula 8]

Among these groups, groups represented by the following formula are preferable, and biphenyl groups in which 2 b are 0 are more preferable, in view of ease of forming a cured product having high transparency and ease of introducing into a resin.

[ chemical formula 9]

The radicals R specified above ⁶ Via R ⁵ Is bonded to the backbone of the resin. R is R ⁵ Is a single bond or a 2-valent linking group.

The 2-valent linking group is not particularly limited insofar as it does not interfere with the object of the present invention. As a preferred example of the 2-valent linking group, there may be mentioned a linking group selected from the group consisting of 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-, and a group obtained by combining 2 or more kinds of 2-valent groups selected from the group.

R ⁶ Of these, preferred are a single bond, an alkylene group having 1 to 6 carbon atoms, and-CO-O-, more preferably a single bond, and-CO-O-, particularly preferred is-CO-O- (-) R in the formula (a 3) ⁶ The end of the bonded chemical bond. ). R is as follows ⁶ In the case of alkylene, alkyleneThe compound may be linear or branched.

Based on the above, as the structural unit A3, a structural unit represented by the following formula (A3-1) is preferable. In the formula (a 3-1), R ¹ 、R ¹⁰ And b are each as described above.

[ chemical formula 10]

The structural unit A3 may be inserted into the resin by copolymerizing an unsaturated compound represented by the following formula (a-III) with a monomer providing other structural units.

The structural unit A3 may be present in the resin in a block form or may be present in the resin in a random form. The structural unit A3 is preferably present in the resin in a random manner from the viewpoint of easy uniform distribution of the structural units A1 and A2 in the resin.

As the unsaturated compound represented by the formula (a-III), preferred is a (meth) acrylate represented by the following formula (a-III-1), and more preferred is a (meth) acrylate represented by the following formula (a-III-1 a). In the formula (a-III), the formula (a-III-1), and the formula (a-III-1 a), R ¹ 、R ⁵ 、R ⁶ 、R ¹⁰ And b are each as described above.

[ chemical formula 11]

Preferable specific examples of the unsaturated compound providing the structural unit A3 include (1, 1 '-biphenyl-4-yl) acrylate, (1, 1' -biphenyl-4-yl) methacrylate, (1, 1 '-biphenyl-3-yl) acrylate, (1, 1' -biphenyl-3-yl) methacrylate, 4-vinyl-1, 1 '-biphenyl, and 3-vinyl-1, 1' -biphenyl.

Among these, (1, 1 '-biphenyl-4-yl) acrylate and (1, 1' -biphenyl-4-yl) methacrylate are preferable.

The amount of the structural unit A3 in the resin a is not particularly limited within a range that does not hinder the object of the present invention. The amount of the structural unit A3 in the resin a is preferably 30 mol% or more and 50 mol% or less, more preferably 35 mol% or more and 50 mol% or less, particularly preferably 40 mol% or more and 50 mol% or less, of all the structural units in the resin a, from the viewpoint of good curability and curability of the cured product.

< other structural units >)

The resin a may contain other structural units in addition to the aforementioned structural unit A1, structural unit A2, and structural unit A3 within a range that does not hinder the object of the present invention.

Examples of the other structural unit include structural units derived from (meth) acrylic esters. Compounds comprising structural units may be used. The (meth) acrylic acid is acrylic acid, or methacrylic acid. The (meth) acrylic acid ester is a compound represented by the following formulas (a-IV), and is not particularly limited as long as the object of the present invention is not impaired.

[ chemical formula 12]

In the above formula (a-IV), R ^a1 Is a hydrogen atom or a methyl group. R is R ^a11 Is an organic group which is reactive with an isocyanate group formed from a blocked isocyanate group in the structural unit A1 and does not have a group containing active hydrogen.

Examples of the active hydrogen-containing group include a hydroxyl group, a mercapto group, an amino group, and a carboxyl group. The organic group may contain a bond other than a hydrocarbon group such as a heteroatom, and a substituent. The organic group may be any of linear, branched, and cyclic.

As R ^a11 The substituent other than the hydrocarbon group in the organic group of (a) is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a halogen atom, an alkylthio group, an arylthio group, a cyano group, a silyl group, an alkoxy group, an alkoxycarbonyl group, a nitro group, a nitroso group, an acyl group, an acyloxy group Alkoxyalkyl, alkylthioalkyl, aryloxyalkyl, arylthioalkyl, N-disubstituted amino (-NRR ': R and R' each independently represent a hydrocarbon group), and the like. The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.

As R ^a11 Preferably, an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with a halogen atom, an alkyl group, or a heterocyclic group. In addition, in the case where 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 a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, particularly preferably 1 to 10. Examples of the preferable alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl.

R ^a11 When the alicyclic group is an alicyclic group or a group containing an alicyclic group, preferable alicyclic groups include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, and polycyclic alicyclic groups such as adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl and tetracyclododecyl.

Examples of the monomer other than the (meth) acrylic acid ester, which provides the other structural unit, include allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These monomers may be used singly or in combination of 2 or more.

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

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

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl benzoate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

As the styrenes, styrene may be mentioned; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, and the like; etc.

When the resin a contains other structural units in addition to the structural units A1, A2, and A3, the total amount of the structural units A1, A2, and A3 in the resin a is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more, with respect to the total of the structural units in the resin a.

From the viewpoint of easy realization of both the effect of easily forming a cured product having high transparency and good curability, the resin a preferably contains no other structural unit and is formed of only the structural unit A1, the structural unit A2, and the structural unit A3.

The method for producing the resin a described above is not particularly limited. In general, the above-described monomers for providing the structural units A1, A2, and A3, and the other structural units as needed, are mixed in predetermined amounts, and then polymerized in an appropriate solvent in the presence of a polymerization initiator, for example, in a temperature range of 50 ℃ to 120 ℃ inclusive, to obtain a resin. The resin is usually obtained as a solution in an organic solvent, and the resin obtained as a solution may be directly blended into a curable composition described later, or may be directly used as a curable composition.

The mass average molecular weight of the resin a obtained by the above method is preferably 30000 or more, more preferably 35000 or more and 100000 or less, particularly preferably 40000 or more and 80000 or less. The mass average molecular weight is a molecular weight in terms of polystyrene measured by GPC. By increasing the mass average molecular weight of the resin to a certain extent, a cured product excellent in solvent resistance and thermal decomposition resistance can be easily formed.

The solution of the resin a obtained as described above may be mixed with a poor solvent such as hexane, diethyl ether, methanol, water, etc., to precipitate the resin a, and the precipitated resin a may be recovered and used. The precipitated resin a is preferably washed after filtration, and then dried at a temperature at which the blocked isocyanate groups in the structural unit A1 are not decomposed under normal pressure or reduced pressure. In this way, the resin in the form of a powdery solid can be recovered. The powdery resin may be used as it is or may be blended with 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 having absorption in the near infrared (wavelength 780nm to 1200 nm), and has a wavelength > N ⁺ Partial structure expressed by =.

Specific examples of the near infrared absorbing dye (B) include cyanine compounds, squarylium compounds, and diimmonium compounds. Among these, the cyanine compound is preferable in terms of its performance as the near infrared absorbing dye (B) and its good solubility in the curable composition.

The cyanine compound may be a compound represented by the following formula (b 1-1).

[ chemical formula 13]

(in the formula (b 1-1),

Z ¹ is a group represented by the following formula (b 1-2) or (b 1-3),

Z ² is a group represented by the following formula (b 1-4) or (b 1-5),

R ²¹ ～R ²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent,

selected from 1 or more R ²¹ And 1 or more R ²² Any 2 groups in the group may be bonded to each other to form a ring,

n1 is an integer of 1 to 5,

x1 is a 1-valent anion. )

[ chemical formula 14]

(in the formula (b 1-2) and (b 1-3),

R ³¹ ～R ³⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent,

R ⁴¹ ～R ⁴⁶ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. )

[ chemical formula 15]

(in the formulae (b 1-4) and (b 1-5), R ³¹ ～R ³⁸ R is R ⁴¹ ～R ⁴⁶ R in (b 1-2) and (b 1-3) ³¹ ～R ³⁸ R is R ⁴¹ ～R ⁴⁶ The same applies. )

In the formula (b 1-1), R is ²¹ ～R ²⁴ Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As R ²¹ ～R ²⁴ The alkyl group having 1 to 20 carbon atoms may be straight or branched, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and the like.

Regarding R as ²¹ ～R ²⁴ Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl and the like.

As X1, BF is exemplified ₄ ^- 、PF ₆ ^- 、ClO ₄ ^- 、I ^- Etc.

In the formula (b 1-1), when n1 is an integer of 2 or more and 5 or less, the structures in n1 brackets may be the same or different.

In the formula (b 1-2) and the formula (b 1-3), R is ³¹ ～R ³⁸ 、R ⁴¹ ～R ⁴⁶ A halogen atom of (C1-C20) or an alkyl group having 6-C20 which may have a substituent, and R in the formula (b 1-1) ²¹ ～R ²⁴ Likewise, the same is true.

The ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) ([ mass of the solvent (S1 ]/[ mass of the near infrared absorbing dye (B)) is 30 or more, preferably 35 or more, more preferably 50 or more. The ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) is preferably 300 or less.

The near infrared absorbing dye (B) is preferably 0.5 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 5 parts by mass or less, per 100 parts by mass of the thermosetting material (a).

The concentration of the near infrared absorbing dye (B) in the curable composition is, for example, 0.1 mass% or more and 2 mass% or less, and preferably 0.1 mass% or more and 0.5 mass% or less.

Solvent (S) >

The solvent (S) has a polarity term δp of 12 (MPa) containing hansen solubility parameters ^0.5 ) The above solvent (S1).

The polarity term δp of the hansen solubility parameter (term based on energy of dipole interaction) can be found using software developed by charles hansen et al (software name: hansen Solubility Parameter in Practice (hsPIP)).

The polarity term δp of the hansen solubility parameter is preferably 13 (MPa) ^0.5 ) The above is more preferably 16 (MPa) ^0.5 ) The above. The upper limit of the polarity term δp of the hansen solubility parameter is not particularly limited, and is, for example, 20 (MPa) ^0.5 ) The following is given.

The curable composition obtained by blending such a specific solvent (S1) and a near infrared ray absorber (B) having a specific structure at a specific mass ratio is excellent in the solubility of the solvent (S1) of the near infrared ray absorber (B) and in the low-temperature stability of the curable composition.

In addition, the polarity term δp including hansen solubility parameter is 16 or more (MPa) ^0.5 ) Since the curable composition of the solvent (S1) is excellent in film forming property by spin coating, a coating film having a uniform thickness and the like can be formed by spin coating, and a cured product having a uniform thickness and the like can be obtained.

The boiling point of the solvent (S1) is preferably 150℃or higher, more preferably 180℃or higher, and still more preferably 200℃or higher. The boiling point is the boiling point at atmospheric pressure. The upper limit of the boiling point of the solvent (S1) is not particularly limited, and is, for example, 250℃or lower.

As the solvent (S1), a solvent having an ester structure, an amide structure, a sulfonate structure, or a sulfoxide structure in the chemical structure can be preferably used. By providing such a structure in the chemical structure, δp will be easily brought to a desired value.

The ester structure, amide structure, sulfonate structure, and sulfoxide structure may be part of a cyclic skeleton in the molecule.

Typical examples include solvents having a lactone structure, a lactam structure, and a sultone structure in their chemical structures.

The solvent having a lactone structure in its chemical structure is a solvent having a lactone skeleton which is a cyclic skeleton having a-CO-O-bond.

The solvent having a chemical structure containing a lactam structure is a solvent containing a lactam skeleton which is a cyclic skeleton containing a-CO-NH-bond.

The solvent having a chemical structure containing a sultone structure is a solvent containing-O-SO ₂ -a solvent of the sultone (sultone) skeleton of the cyclic skeleton of the bond.

As a preferable specific example of the solvent (S1), gamma-butyrolactone (δp:16.6 MPa) may be mentioned ^0.5 Boiling point: 204-205 ℃), N-dimethylformamide (δp:13.7MPa ^0.5 Boiling point: 153 ℃), dimethyl sulfoxide (δp:16.4MPa ^0.5 Boiling point: 189 ℃), N-methylpyrrolidone (δp:12.3MPa ^0.5 Boiling point: 202 c), etc.

The solvent (S) may contain a solvent (S2) different from the solvent (S1).

Examples of the solvent (S2) include Propylene Glycol Methyl Ether Acetate (PGMEA), cyclopentanone (CP), methyl Ethyl Ketone (MEK), cyclohexanone, cyclopentanone, ethyl Lactate (EL), propylene Glycol Monomethyl Ether (PGME), 3-methoxybutyl acetate, butyl acetate, and 3-methoxy-1-butanol.

When the solvent (S2) is contained, the content of the solvent (S1) is preferably 15 mass% or more, more preferably 20 mass% or more, based on the total mass of the solvent (S1) and the solvent (S2). The content of the solvent (S1) is preferably 80 mass% or less, more preferably 60 mass% or less, based on the total of the mass of the solvent (S1) and the mass of the solvent (S2).

The solid content concentration of the curable composition is not particularly limited within a range that does not hinder 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 >)

The curable composition may contain other compounding agents in addition to the thermosetting material (a), the near infrared absorbing dye (B) and the solvent (S), as long as the object of the present invention is not impaired. Examples of the other compounding agents include surfactants and antioxidants.

The surfactant may be used, for example, to improve defoaming property at the time of producing the curable composition, to further improve stability of the curable composition, to improve coatability of the curable composition, and the like.

As the surfactant, a water-soluble surfactant 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 a silicone based.

Method for producing curable composition

The curable composition can be produced by mixing the thermosetting material (a), the near infrared absorbing dye (B), the solvent (S), and other additives added as needed.

Cured product, near infrared absorbing filter, and method for producing the same

By curing the curable composition, a cured product can be obtained.

The cured product may be a patterned cured product or an unpatterned flat cured product.

The cured product of such a curable composition can be used as a near infrared absorbing filter. The near infrared absorbing filter is an optical filter that transmits visible light but absorbs (blocks) near infrared light, and the near infrared light can be absorbed by the near infrared absorbing dye (B) contained in the curable composition. The near infrared absorbing filter may transmit all light having a wavelength in the visible light range, or may transmit only light having a specific wavelength among the wavelengths in the visible light range.

The near infrared absorbing filter is used as a member of various devices such as a solid-state imaging device such as a CCD or CMOS, a liquid crystal display device, and an image display device such as an organic EL.

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 for forming the curable composition layer include a transparent base material such as glass, a substrate having a solid-state imaging device provided on a semiconductor substrate, and the like.

Examples of the method for forming the curable composition layer on the support include spin coating, slit coating, spray coating, roll coating, drop coating, inkjet method, screen printing, coating methods such as an applicator method, nanoimprint method, and transfer method using a mold or the like.

The curable composition layer may be a single layer or a plurality of layers.

The curing of the curable composition layer is performed by heating. The heating condition is not particularly limited as long as the curable composition can be cured, and for example, the heating temperature is 140 ℃ or higher and 220 ℃ or lower, and the heating time is 1 minute or higher and 30 minutes or lower.

In addition, the solvent (S) is preferably removed by heating simultaneously with or separately from the curing.

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

Since the above curable composition has excellent solvent solubility of the near infrared ray absorber, a cured product such as a thin near infrared ray absorption filter having not only a desired near infrared ray absorption characteristic but also a desired near infrared ray absorption characteristic can be produced by increasing the concentration of the near infrared ray absorber (B) in the curable composition. Further, since the curable composition is excellent in low-temperature stability, even when a curable composition which has been stored and transferred at a low temperature is used, a cured product such as a near infrared absorption filter having a uniform film thickness can be obtained.

Low-temperature storage method for curable composition and method for transporting curable composition

In the method for storing the curable composition at a low temperature, the curable composition is stored at a temperature of 10 ℃ or lower.

In the method for transporting the curable composition, the curable composition is transported by a transport machine at a temperature of 10 ℃ or lower.

The transport machine is not particularly limited as long as the curable composition can be transported at a desired temperature. Specific examples of the transport machine include automobiles such as trucks, railway vehicles, ships, and aircraft.

The temperature for storage and transportation may be 10℃or lower, and further, may be 5℃or lower and-20℃or lower.

The lower limit of the temperature for storage and transportation is not particularly limited as long as the curable composition does not cure or components in the curable composition do not precipitate. The temperature for storage and transportation may be, for example, at-22℃or higher, or at-15℃or higher.

The curable composition is excellent in low-temperature stability. Therefore, even when the curable composition is stored at a low temperature or transported by a transport machine at a low temperature, the occurrence of a precipitate in the curable composition can be suppressed. Therefore, even after storage and transportation at low temperature, the composition of the curable composition is less likely to change from that before storage and transportation, and a cured product having desired properties can be produced using the curable composition.

Method for providing curable composition

In the method for providing a curable composition, a curable composition stored by the method for storing a curable composition at a low temperature is provided for a process route for carrying out the method for producing a cured product or a process route for carrying out the method for producing a near infrared absorbing filter. The temperature of the curable composition to be provided may be a temperature in a state of being stored at a low temperature or may be higher than 10 ℃, specifically, may be, for example, 15 ℃ or more and 25 ℃ or less.

The curable composition may be one appropriately selected from the above materials, and the preparation of the curable composition and the timing to be provided to the process route may be considered depending on the size and the operation speed of the process route.

The temperature for storage and transfer may be appropriately set according to the curable composition.

The entity for implementing the method for manufacturing the cured product and the near infrared absorption filter is not necessarily the same as the entity for implementing the method for providing the present invention.

Examples

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. The present invention is not limited in any way by the following examples.

[ solvent solubility test ]

As the near infrared absorbing dye (B), the following cyanine compound B1 (product name: S01965, manufactured by Spectrumfo) was used, and stirring was performed at 25℃for 1 hour, and the maximum concentration dissolved in the solvent shown in Table 1 was measured. The results are shown in Table 1.

[ chemical formula 16]

TABLE 1

[ 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 lower right hand digit of brackets in each structural unit in the following structural formula indicates the content (mol%) of the structural unit in the resin. The mass average molecular weight Mw of the resin a was 50000 and the dispersity (mass average molecular weight Mw/number average molecular weight Mn) was 4.5.

[ chemical formula 17]

Resin a

The above-mentioned cyanine compound B1 (product name: S01965, manufactured by Spectrum fo) was used as the near infrared absorbing dye (B).

As the solvent (S1), γ -butyrolactone (GBL), N-Dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) were used.

Further, as the solvent (S2), cyclopentanone (CP) and Propylene Glycol Monomethyl Ether Acetate (PGMEA) were used.

(production of curable composition)

The solvent (S1) and the solvent (S2) mixed in the types and mixing ratios (mass ratios) described in table 2, the resin a, and the cyanine compound B1 were placed in a container, and stirred at 25 ℃ for 1 hour to obtain curable compositions of examples 1 to 5 and comparative examples 1 to 3. For the resin a, an amount was used in which the ratio of the mass of the resin a to the total mass of the mixed solvent and the resin a (mass of the resin a/(mass of the mixed solvent+mass of the resin a)) was 0.20. In addition, the cyanine compound B1 was used in an amount such that the mass ratio of the cyanine compound B1 to the resin a (the mass of the cyanine compound B1/the mass of the resin a) was 0.015.

The curable compositions of examples 1 to 5 and comparative examples 1 to 4 obtained were homogeneous solutions in which the resin a and the cyanine compound B1 were dissolved in a mixed solvent.

[ Low temperature stability ]

The curable compositions of examples 1 to 5 and comparative examples 1 to 4 were stored at 25℃and 5℃or-20℃for 7 days, and then observed visually, and the case where no precipitate was generated was evaluated as "O", and the case where a precipitate was generated was evaluated as "X". The results are shown in Table 2.

TABLE 2

As is clear from table 1, the solubility of the near infrared absorbing dye (B) of γ -butyrolactone (GBL), dimethyl sulfoxide (DMSO), and N, N-Dimethylformamide (DMF) as the solvent (S1) was excellent. Therefore, it was found that the near infrared absorbing dye (B) in the curable composition containing the solvent (S1) was excellent in solvent solubility.

As is clear from Table 2, the curable compositions of examples 1 to 5, in which the ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) was 30 or more, did not generate precipitates even when stored at 5℃and-20 ℃. Therefore, it was found that the curable compositions of examples 1 to 5 were excellent in low-temperature stability.

Claims

1. A curable composition comprising a thermosetting material (A), a near infrared absorbing dye (B), and a solvent (S),

The near infrared absorbing dye (B) has a molecular structure of > N ⁺ The partial structure represented by =,

the solvent (S) has a polarity term δp of 13 (MPa) including a Hansen solubility parameter ^0.5 ) The above solvent (S1),

the ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) is 30 or more.

2. The curable composition according to claim 1, wherein the solvent (S1) is a solvent having one or more structures selected from the group consisting of an ester structure, an amide structure, a sulfonate structure, and a sulfoxide structure.

3. The curable composition according to claim 1 or 2, which contains a solvent (S2) different from the solvent (S1),

the content of the solvent (S1) is 15 mass% or more relative to the total of the mass of the solvent (S1) and the mass of the solvent (S2).

4. The curable composition according to claim 1 or 2, wherein a ratio of the mass of the solvent (S1) to the mass of the near infrared absorbing dye (B) is 300 or less.

5. The curable composition according to claim 1 or 2, wherein the near infrared absorbing dye (B) is at least one selected from the group consisting of cyanine compounds, squarylium compounds, and diimmonium compounds.

6. The curable composition according to claim 1 or 2, wherein the thermosetting material (a) has at least one thermosetting group selected from epoxy groups, isocyanate groups and blocked isocyanate groups.

7. A cured product of the curable composition according to any one of claims 1 to 6.

8. A near infrared absorbing filter comprising a cured product of the curable composition according to any one of claims 1 to 6.

9. A method for producing a cured product, which comprises curing the curable composition according to any one of claims 1 to 6.

10. A method for producing a near infrared absorbing filter, which comprises curing the curable composition according to any one of claims 1 to 6.

11. A method for storing a curable composition at a low temperature, wherein the curable composition according to any one of claims 1 to 6 is stored at 10 ℃.

12. A method for transporting a curable composition, wherein the curable composition according to any one of claims 1 to 6 is transported by a transport machine at a temperature of 10 ℃ or lower.

13. A method for providing a curable composition, wherein a curable composition stored by the method for storing a curable composition at a low temperature according to claim 11 is provided for a process route for carrying out the method for producing a cured product according to claim 9 or a process route for carrying out the method for producing a near infrared absorbing filter according to claim 10.