CN113337170A

CN113337170A - Curable composition, cured product, near-infrared absorption filter, and method for producing same

Info

Publication number: CN113337170A
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: 2021-09-03
Anticipated expiration: 2041-01-15
Also published as: CN113337170B; TW202132379A; JP2021130734A; JP7419097B2; KR20210105284A

Abstract

The present invention addresses the problem of providing a curable composition having excellent solvent solubility and low-temperature stability of a near-infrared absorber, a cured product and a near-infrared absorption filter using the curable composition, a method for producing the cured product and a method for producing the near-infrared absorption filter, and the curable compositionA method for storing a substance at a low temperature, a method for transporting a curable composition, and a method for providing a curable composition. The solution of the present invention is a curable composition comprising a thermosetting material (A), a near-infrared absorbing dye (B) and a solvent (S), wherein the near-infrared absorbing dye (B) has > N⁺The solvent (S) contains a polar term δ p of hansen solubility parameter of 12 (MPa)^0.5) The solvent (S1) is contained in an amount such that 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 absorption filter, and method for producing same

Technical Field

The present invention relates to a curable composition capable of producing a near-infrared absorption filter (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, a method for conveying a curable composition, and a method for providing a curable composition.

Background

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

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

The near-infrared absorption filter can be produced using a composition containing a near-infrared absorber and a solvent, for example (see patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese Kohyo publication No. 2018-043185

Disclosure of Invention

Problems to be solved by the invention

In recent years, miniaturization of elements is being demanded. By increasing the content of the near-infrared absorbent in the composition for producing the near-infrared absorption filter, the near-infrared absorption filter can be made thin, which contributes to the miniaturization of the device. Therefore, the composition for producing a near-infrared absorption filter is desired to have high solubility in a solvent of the near-infrared absorber.

In addition, the composition used for producing the near-infrared absorption filter is often used after storage in a place where the composition is produced, a place where the near-infrared absorption filter is produced, or the like, or is transferred from the place where the composition is produced to the place where the near-infrared absorption filter is produced. When the composition for producing the near-infrared absorption filter contains a thermosetting material, the composition can be cured by heating to produce the near-infrared absorption filter, but the composition containing the thermosetting material may be modified by reaction of the thermosetting material during storage or transfer. In order to prevent the reaction of the thermosetting material, it is conceivable to store or transfer the composition containing the thermosetting material at a low temperature, but there is a problem that precipitates are generated in some cases when the composition is stored or transferred at a low temperature. Therefore, it is also desired that the composition for producing a near-infrared absorption filter be excellent in low-temperature stability, i.e., that precipitates are not easily generated even when stored or transferred at low temperatures.

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

Means for solving the problems

The present inventors have found that the above-mentioned problems can be solved by a composition comprising a thermosetting material (a), a near-infrared ray absorbing dye (B) having > N, and a solvent (S), and have completed the present invention⁺The solvent (S) contains a polar term δ p of hansen solubility parameter of 12 (MPa)^0.5) The solvent (S1) is contained in an amount such that 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 of claim 1 is a curable composition, which comprises a thermosetting material (A), a near infrared ray absorption dye (B) and a solvent (S), the near infrared ray absorption dye (B) having > N⁺The solvent (S) contains a polar term δ p of hansen solubility parameter of 12 (MPa)^0.5) The solvent (S1) is contained in an amount such that the ratio of the mass of the solvent (S1) to the mass of the near-infrared absorbing dye (B) is 30 or more.

The 2 nd embodiment of the present invention is a cured product of the curable composition according to the 1 st embodiment.

The 3 rd aspect of the present invention is a near-infrared absorption filter formed from a cured product of the curable composition according to the 1 st aspect.

The present invention according to claim 4 is a method for producing a cured product, which comprises curing the curable composition according to claim 1.

The 5 th aspect of the present invention is a method for producing a near-infrared absorption filter, which comprises curing the curable composition according to the 1 st aspect.

The 6 th aspect of the present invention is a method for storing a curable composition at a low temperature, wherein the curable composition of the 1 st aspect is stored at 10 ℃ or lower.

The invention of claim 7 is a method for conveying a curable composition, wherein the curable composition of claim 1 is conveyed by a conveyor at 10 ℃ or lower.

An 8 th aspect of the present invention is a method for providing a curable composition, wherein a curable composition stored by the method for storing a curable composition according to the 6 th aspect at a low temperature is provided for a process route for carrying out the method for producing a cured product according to the 4 th aspect or a process route for carrying out the method for producing a near-infrared absorption filter according to the 5 th aspect.

ADVANTAGEOUS EFFECTS OF INVENTION

By the present invention, there can be provided: a curable composition which enables the production of a near-infrared absorption filter and is excellent in the solubility in a solvent of a near-infrared absorber and the stability at low temperatures; a cured product and a near-infrared absorption filter using the curable composition; 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) and near-infrared radiationA line-absorbing dye (B), and a solvent (S). The near infrared ray absorbing dye (B) has > N⁺The solvent (S) contains a polar term δ p of hansen solubility parameter of 12 (MPa)^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 near-infrared ray absorber (B) has excellent solubility 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 from the curable composition can be made thin while having desired near-infrared absorption characteristics, and an element provided with a cured product such as a near-infrared absorption filter can be miniaturized.

The curable composition is excellent in low-temperature stability, i.e., is less likely to form precipitates even when stored or 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 production method will be described.

< thermosetting Material (A) >)

The thermosetting material (a) is a component which becomes a base material of a cured product such as a near infrared absorption 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, and more preferably 20,000 or more and 200,000 or less.

The thermosetting material (a) is preferably a material that transmits visible light when cured. The visible light is, for example, light having a wavelength in the range of 380nm or more and less than 780 nm.

Examples of the thermosetting material (a) include compounds having a thermosetting group such as an epoxy group, an isocyanate group, and a blocked isocyanate group. Specific examples thereof include isocyanate compounds having an isocyanate group or a blocked isocyanate group, epoxy compounds having an epoxy group, and the like. 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, "(meth) acryl-" refers to both "acryl-" and "methacryl-".

These can be used alone in 1 kind, also can be combined with more than 2 kinds.

The thermosetting material is preferably a (meth) acrylic resin having a blocked isocyanate group, and more preferably a (meth) acrylic resin (hereinafter, also referred to as resin a) containing 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), in view of easily obtaining a curable composition satisfying both good thermosetting properties, stability at low temperature, and good visible light transmittance of a cured product.

[ chemical formula 1]

(in the formulae (a1), (a2) and (a3), R¹Each independently being a hydrogen atom, or a methyl group, R²Is a single bond or an alkylene group having 1 to 5 carbon atoms, R³To block the isocyanate group, R⁴Is a 2-valent hydrocarbon radical, R⁵Is a single bond, or a 2-valent linking group, R⁶Is a hydrocarbon group containing 2 or more benzene rings. )

Hereinafter, the structural unit represented by formula (a1) is also referred to as "structural unit a 1", the structural unit represented by formula (a2) is also referred to as "structural unit a 2", and the structural unit represented by formula (A3) is also referred to as "structural unit A3".

The structural unit A1 represented by the formula (a1) has a blocked isocyanate group as R³. The blocked isocyanate group means an isocyanate group-blocked compoundA thermally dissociative protecting group, and a group obtained by blocking the protecting group.

Therefore, when the above-mentioned resin having the structural unit a1 is heated, the protecting group in the blocked isocyanate group is released to generate an active isocyanate group.

The isocyanate group generated by heating easily reacts with a functional group having an 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 generated in the structural unit a 1. The isocyanate group (-NCO) reacts with the hydroxyl group (-OH) in the structural unit A2 to crosslink the isocyanate group (-NCO) with a urethane bond (-NH-CO-O-), thereby forming a cured product.

Further, the structural unit represented by the above formula (a3) has a hydrocarbon group containing 2 or more benzene rings as R⁶. 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 resin is cured satisfactorily.

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

< structural Unit A1 >

As described above, resin a contains structural unit a1 having a blocked isocyanate group. Resin A may also contain more than 2 structural units A1 in combination.

The structural unit A1 is a structural unit represented by the formula (a 1). In the formula (a1), R¹Is a hydrogen atom or a methyl group.

In the formula (a1), R²A single bond or an alkylene group having 1 to 5 carbon atoms. The alkylene group may be linear or branched, and is preferably linear. With respect to as R²Specific 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, pentane-1, 5-diyl, and the like.

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 (a1), R³Is a blocked isocyanate group. As described above, the blocked isocyanate group means a group obtained by blocking an isocyanate group with a thermally dissociative 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 compounds, phenol compounds, hydroxyl group-containing compounds other than the alcohol compounds and the phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, carbamate compounds, urea compounds, amide (lactam) compounds, imide compounds, triazole compounds, pyrazole compounds, pyrrole compounds, thiol compounds, and bisulfite.

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, 2,2, 2-trifluoroethanol, 2,2, 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-dibutyl-2-hydroxyacetamide, N-morpholinoethanol, 2, 2-dimethyl-1, 3-dioxolan-4-methanol, and mixtures thereof, 3-oxazolidineethanol, 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, 4-tert-butylphenol, 2-n-hexylphenol, 3-n-hexylphenol, 4-n-hexylphenol, 2- (2-ethylhexyl) phenol, 3- (2-ethylhexyl) phenol, p-cresol, 2-ethylphenol, 3-isopropylphenol, 4-n-butylphenol, 2-n-butylphenol, 3-n-butylphenol, 4-n-hexylphenol, 2-ethylhexyl) phenol, 3- (2-ethylhexyl) phenol, p-propylphenol, and the like, 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, 4-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, 3-isopropyl-2-methylphenol, 3-isopropyl-4-methylphenol, 3-isopropyl-methyl-2-methyl-phenol, 3-isopropyl-4-methyl-phenol, 3-methyl-2, 5-isopropyl-methyl-2-methyl-phenol, methyl-4-ethyl-methyl-2, methyl-ethyl-2, ethyl-methyl-2, ethyl-methyl-ethyl, 2, 3-di-n-butylphenol, 2, 4-di-n-butylphenol, 2, 5-di-n-butylphenol, 2, 6-di-n-butylphenol, 3, 4-di-n-butylphenol, 3, 5-di-n-butylphenol, 2, 3-di-sec-butylphenol, 2, 4-di-sec-butylphenol, 2, 5-di-sec-butylphenol, 3, 4-di-sec-butylphenol, 3, 5-di-sec-butylphenol, 2, 3-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 5-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 3, 4-di-tert-butylphenol, 3, 5-di-tert-butylphenol, 2, 3-di-n-octylphenol, 2, 4-di-n-octylphenol, 2, 5-di-n-octylphenol, 2, 6-di-n-octylphenol, 3, 4-di-n-octylphenol, 3, 5-di-n-octylphenol, 2, 3-di-2-ethylhexylphenol, 2, 4-di-2-ethylhexylphenol, 2, 5-di-2-ethylhexylphenol, 2, 6-di-2-ethylhexylphenol, 3, 4-di-2-ethylhexylphenol, 3, 5-di-2-ethylhexylphenol, 2, 3-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 tri-substituted α -methylbenzyl-based phenol), 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-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 triphenyl silanol.

Examples of the active methylene-based compound include Meldrum's acid, dialkyl malonates (e.g., 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, ethyl-sec-butyl malonate, methyl-tert-butyl malonate, ethyl-tert-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzyl methyl malonate, ethylphenyl malonate, tert-butylphenyl malonate, and isopropylidene malonate), alkyl acetoacetates (e.g., methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, tert-butyl acetoacetate, t-butyl acetoacetate, methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, and isopropyl malonate), alkyl acetoacetates (e.g., methyl acetoacetate, methyl acetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, and n-butyl acetoacetate), Benzyl acetoacetate, phenyl acetoacetate, etc.), 2-acetoacetoxyethyl methacrylate, acetylacetone, ethyl cyanoacetate, etc.

Examples of the amine compound include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2,2,6, 6-tetramethylpiperidyl) amine, di-N-propylamine, diisopropylamine, isopropylethylamine, 2, 4-trimethylhexamethyleneamine, 2, 5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis (3,5, 5-trimethylcyclohexyl) amine, piperidine, 2, 6-dimethylpiperidine, t-butylmethylamine, t-butylethylamine, t-butyl-N-propylamine, t-butyl-N-butylamine, t-butylbenzylamine, t-butylaniline, 2, 6-trimethylpiperidine, 2,6, 6-tetramethylpiperidine, (dimethylamino) -2,2,6, 6-tetramethylpiperidine, 2,2,6, 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, and guanidine.

Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, cyclohexanone oxime, diacetyl monoxime, benzophenone oxime, 2,6, 6-tetramethylcyclohexanone oxime, diisopropyl ketoxime, methyl tert-butyl ketoxime, diisobutyl ketoxime, methyl isobutyl ketoxime, methyl isopropyl ketoxime, methyl 2, 4-dimethylpentyl ketoxime, methyl 3-ethylheptyl ketoxime, methyl isoamyl ketoxime, n-amyl ketoxime, 2,4, 4-tetramethyl-1, 3-cyclobutane dione monoxime, 4, 4' -dimethoxydibenzo ketoxime, and 2-heptanone oxime.

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

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

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

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

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

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

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

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

Examples of the bisulfite include sodium bisulfite and the like.

Among the structural unit A1 represented by the above-described formula (a1), the structural unit represented by the following formula (a1-1), formula (a1-2) or formula (a1-3) is preferable in terms of ease of preparation of the resin, good curability and the like.

[ chemical formula 2]

(in the formulae (a1-1), (a1-2) and (a1-3), R¹And R²R is the same as the above formula (a1)⁷Each independently an organic group having 1 to 12 carbon atoms, R⁸Each independently represents a halogen atom or an organic group having 1 to 6 carbon atoms, R⁹Each independently represents an organic group having 1 to 6 carbon atoms, and a is an integer of 0 to 3. )

In the formula (a1-1), R is⁷Examples of the organic group(s) 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, and an acyl group having 2 to 12 carbon atoms. Among 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 further preferable, and a methyl group or an ethyl group is particularly preferable.

The alkyl group may be linear or branched.

In the formula (a1-1), two R⁷May be the same or different.

In the formula (a1-2), R⁸Each of the substituents on the pyrazolyl group is independently a halogen atom or an organic group having 1 to 6 carbon atoms.

As R⁸Preferable examples thereof 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 an aliphatic acyl group having 2 to 6 carbon atoms.

As R⁸The halogen atom, the alkyl group having 1 to 6 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms are preferable, the alkyl group having 1 to 6 carbon atoms is more preferable, the alkyl group having 1 to 3 carbon atoms is further preferable, and the methyl group is particularly preferable.

In the formula (a1-2), a is an integer of 0 to 3 inclusive, preferably 0 to 2 inclusive.

In the formula (a1-3), R is⁹Examples of the organic group(s) 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 (a1-3), two R⁹May be the same or different.

The structural unit a1 can be inserted into the resin by copolymerizing a (meth) acrylate represented by the following formula (a-I) with a monomer that provides other structural units.

Among the (meth) acrylates represented by the formula (a-I), the (meth) acrylates represented by the following formula (a-I-1), formula (a-I-2) or formula (a-I-3) are preferable, and the (meth) acrylates represented by the following formula (a-I-1a), formula (a-I-2a) or formula (a-I-3a) are more preferable.

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 randomly present in the resin, because the isocyanate group and the hydroxyl group generated in the structural unit a1 by heating easily react well.

[ chemical formula 3]

Preferred specific examples of the (meth) acrylate ester which provides the structural unit A1 include the following compounds.

[ chemical formula 4]

Among these, the following (meth) acrylates are preferable in terms 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 not interfering with 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, with respect to the total structural units of the resin a. From the viewpoint of good curability, the content of the structural unit a1 in the resin a is preferably 20 mol% or more and 40 mol% or less, and more preferably 25 mol% or more and 35 mol% or less, with respect to the total structural units of the resin a.

< structural Unit A2 >

The structural unit A2 is a structural unit represented by the formula (a 2). In the formula (a2), R¹Is a hydrogen atom or a methyl group.

In the formula (a2), R⁴Is a 2-valent hydrocarbon group. As R⁴The hydrocarbon group (b) may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group having an aliphatic portion and an aromatic portion. From curing of resinsIn view of sex, R⁴Aliphatic hydrocarbon groups having a valence of 2 are preferred. R⁴In the case of a 2-valent aliphatic hydrocarbon group, the structure of the aliphatic hydrocarbon group may be linear, branched, or cyclic, or a combination thereof, and is preferably linear.

As R⁴The number of carbon atoms of the hydrocarbon group (2) 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 moiety and an aromatic moiety, the number of carbon atoms is preferably 6 or more and 20 or less, and 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 and hexadecane-1, 16-diyl, heptadecane-1, 17-diyl, octadecane-1, 18-diyl, nonadecane-1, 19-diyl and eicosane-1, 20-diyl.

Of these, preferred are 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 eicosan-1, 20-diyl, more preferably 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 and decane-1, 10-diyl, more preferably ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl and hexane-1, 6-diyl.

Specific examples of the aromatic hydrocarbon group having a valence of 2 include p-phenylene, m-phenylene, o-phenylene, naphthalene-1, 4-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl and the like, with p-phenylene and m-phenylene being preferred, and p-phenylene being more preferred.

The structural unit a2 can be inserted into the resin by copolymerizing a (meth) acrylate represented by the following formula (a-II) with a monomer that provides 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 randomly present in the resin, because the isocyanate group and the hydroxyl group generated in the structural unit a1 by heating easily react well.

[ chemical formula 6]

(in the formula (a-II), R¹And R⁴The same as in formula (a 2). )

Preferable specific examples of the (meth) acrylic ester providing the structural unit A2 include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl acrylate, and 3-hydroxyphenyl methacrylate.

Of 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 not interfering with 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, based on the total structural units of the resin a. From the viewpoint of good curability, the content of the structural unit a2 in the resin a is preferably 20 mol% or more and 40 mol% or less, and more preferably 25 mol% or more and 35 mol% or less, with respect to the total structural units of the resin a.

The number of moles of the structural unit a1 and the number of moles of the structural unit a2 in the resin a is preferably 80/100 or more and 100/80 or less, more preferably 90/100 or more and 100/90 or less, and particularly preferably 95/100 or more and 100/95 or less, in terms of the number of moles of the structural unit a1 per mole of the structural unit a 2. Most preferably, the number of moles of the structural unit A1 in the resin A is equimolar to the number of moles of the structural unit A2.

< structural Unit A3 >

The structural unit A3 is a structural unit represented by the formula (a 3). In the formula (a3), R¹Is a hydrogen atom or a methyl group.

In the formula (a3), R⁶Is an organic group containing 2 or more benzene rings. By containing as R an organic group having 2 or more benzene rings⁶The structural unit A3 (A) can form a cured product having good transparency.

R⁶The 2 or more benzene rings contained in (a) may be condensed with each other, or may be bonded by a single bond or a linking group.

R⁶The number of carbon atoms of (b) is not particularly limited within a range not interfering with the object of the present invention. R⁶The number of carbon atoms of (b) is preferably 10 to 50, more preferably 10 to 30.

With respect to as R⁶Examples of the organic group containing 2 or more benzene rings include groups obtained by removing 1 hydrogen atom from the following polycyclic compound or a compound obtained by introducing a substituent into the following polycyclic compound. In the following formula, X is-O-, -S-, -CO-, -SO₂-、-CO-NH-、-CO-NH-CO-、-NH-CO-NH-、-CO-O-、-CO-O-CO-、-O-CO-O-、-SO₂、-NH-、-S-S-、-CH₂-、-CH(CH₃) -, 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.

When a substituent is introduced into the polycyclic compound, the number of the substituent is not particularly limited, but is preferably 4 or less, and preferably 1 or 2.

As R illustrated hereinbefore⁶The group represented by the following formula is preferable.

In the following formula, R¹⁰、R¹¹And R¹³Each independently represents a group selected from the group consisting of 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, and R is¹²Is 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, from the viewpoint of easy formation of a cured product having high transparency and easy introduction into a resin, a group represented by the following formula is preferable, and a biphenyl group in which 2 b's in the following formula are 0 is more preferable.

[ chemical formula 9]

The radical R indicated above⁶Through R⁵Bonded to the main chain of the resin. R⁵Is a single bond or a 2-valent linking group.

The linking group having a valence of 2 is not particularly limited within a range not interfering with the object of the present invention. Preferred examples of the 2-valent linking group include alkylene groups having 1 to 6 carbon atoms, -O-, -S-, -CO-, -SO₂-、-CO-NH-、-CO-NH-CO-、-NH-CO-NH-、-CO-O-、-CO-O-CO-、-O-CO-O-、-SO₂A 2-valent group selected from the group consisting of-NH-and-S-S-, and a group obtained by combining 2 or more 2-valent groups selected from the aforementioned group.

R⁶Of these, a single bond, an alkylene group having 1 to 6 carbon atoms, and-CO-O-, are preferable, a single bond is more preferable, and-CO-O-, is particularly preferable, and-CO-O- (-represents R in the formula (a3) -and⁶the end of the bonded chemical bond. ). In addition, R is⁶In the case of an alkylene group, the alkylene group 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 (a3-1), R¹、R¹⁰And b are as described above, respectively.

[ chemical formula 10]

The structural unit a3 can be inserted into the resin by copolymerizing an unsaturated compound represented by the following formula (a-III) with a monomer that provides 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 ease of uniform distribution of the structural unit a1 and the structural unit a2 in the resin.

The unsaturated compound represented by the formula (a-III) is preferably a (meth) acrylate represented by the following formula (a-III-1), and more preferably 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-1a), R¹、R⁵、R⁶、R¹⁰And b are as described above, respectively.

[ 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.

Of these, (1,1 '-biphenyl-4-yl) acrylate and (1, 1' -biphenyl-4-yl) methacrylate are preferred.

The amount of the structural unit a3 in the resin a is not particularly limited within a range not interfering with 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, and particularly preferably 40 mol% or more and 50 mol% or less in all the structural units of the resin a, from the viewpoint of good curability and curability of a cured product.

< other structural units >

The resin a may contain other structural units in addition to the structural unit a1, the structural unit a2, and the structural unit A3 as long as the object of the present invention is not hindered.

Examples of the other structural unit include a structural unit derived from a (meth) acrylate. Compounds comprising structural units may be used. The (meth) acrylic acid is acrylic acid, or methacrylic acid. The (meth) acrylate is a compound represented by the following formula (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 formulae (a to IV), R^a1Is a hydrogen atom or aAnd (4) a base. R^a11Is an organic group having no active hydrogen-containing group which is reactive with the isocyanate group generated from the blocked isocyanate group in structural unit A1.

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 or a substituent other than the hydrocarbon group such as a heteroatom in the organic group. The organic group may be linear, branched, or cyclic.

As R^a11The substituent other than the hydrocarbon group in the organic group(s) 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, an alkoxyalkyl group, an alkylthio alkyl group, an aryloxyalkyl group, an arylthioalkyl group, an N, N-disubstituted amino group (-NRR ': R and R' each independently represent a hydrocarbon group), and the like. The hydrogen atoms contained in the above substituents may be substituted with hydrocarbon groups. The hydrocarbon group included in the substituent may be linear, branched, or cyclic.

As R^a11Preferably, 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, 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 a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Examples of preferred alkyl groups 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^a11When the alicyclic group or the group containing an alicyclic group is used, preferable alicyclic group includes cyclopentyl anda monocyclic alicyclic group such as cyclohexyl, and a polycyclic alicyclic group such as adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

Examples of the monomer other than the (meth) acrylate ester which provides another structural unit include allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These monomers may be used alone 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; and so on.

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

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

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

When the resin a contains other structural units in addition to the structural unit a1, the structural unit a2, and the structural unit A3, the total amount of the structural unit a1, the structural unit a2, and the structural unit A3 in the resin a is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more, based on the total structural units in the resin a.

From the viewpoint of easy achievement of both the effect of easy formation of a highly transparent cured product and good curability, it is preferable that the resin a is formed of only the structural unit a1, the structural unit a2, and the structural unit A3 without including other structural units.

The method for producing the resin a described above is not particularly limited. In general, a resin can be obtained by mixing a predetermined amount of each of the monomers providing the structural unit a1, the structural unit a2, and the structural unit A3 and, if necessary, a monomer providing another structural unit with each other, and then polymerizing the mixture in an appropriate solvent in the presence of a polymerization initiator, for example, at a temperature ranging from 50 ℃ to 120 ℃. 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, and 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 making the mass average molecular weight of the resin large to a certain extent, a cured product excellent in solvent resistance and thermal decomposition resistance is easily formed.

The solution of resin A obtained as described above may be mixed with a poor solvent such as hexane, ether, methanol, or water 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 at a temperature at which the blocked isocyanate group in the structural unit a1 is not decomposed under normal pressure or reduced pressure. In this way, the resin can be recovered as a solid powder. The powdery resin may be used as it is or may be blended in 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, and more preferably 10% by mass or more and 30% by mass or less.

< near Infrared ray absorbing dye (B) >)

The near-infrared absorbing dye (B) is a dye having absorption in the near-infrared region (having a wavelength of 780nm to 1200 nm), and has > N⁺Partial structure as shown.

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

Examples of the cyanine compound include compounds represented by the following formula (b 1-1).

[ chemical formula 13]

(in the formula (b1-1),

Z¹is represented by the following formula (b1-2) or (b1-3)) The group of the formula (I) is,

Z²is a group represented by the following formula (b1-4) or (b1-5),

R²¹～R²⁴each independently 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 R²¹And 1 or more R²²Any 2 groups in the group may be bonded to each other to form a ring,

n1 is an integer of 1 to 5 inclusive,

x1 is a 1-valent anion. )

[ chemical formula 14]

(in the formulae (b1-2) and (b1-3),

R³¹～R³⁸each independently 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,

R⁴¹～R⁴⁶each 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 (b1-4) and (b1-5), R³¹～R³⁸And R⁴¹～R⁴⁶And R in (b1-2) and (b1-3)³¹～R³⁸And R⁴¹～R⁴⁶The same is true. )

In the formula (b1-1), R is²¹～R²⁴Halogen of (2)Examples of the atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As R²¹～R²⁴The alkyl group having 1 to 20 carbon atoms may be linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and n-hexyl groups.

With respect to as R²¹～R²⁴Examples of the aryl group having 6 to 20 carbon atoms include phenyl and naphthyl.

As X1, BF may be mentioned₄ ^-、PF₆ ^-、ClO₄ ^-、I^-And the like.

In the formula (b1-1), when n1 is an integer of 2 to 5, the structures in the n1 brackets may be the same or different.

In the formulae (b1-2) and (b1-3), R is³¹～R³⁸、R⁴¹～R⁴⁶A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R in the formula (b1-1)²¹～R²⁴The same is true.

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, preferably 35 or more, and 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, with respect to 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) contains a polar term with a Hansen solubility parameter, δ p of 12 (MPa)^0.5) The above solvent (S1).

The polar term (term based on energy of dipole interaction) δ p of the Hansen Solubility Parameter can be found by using software (software name: Hansen Solubility Parameter In Practice (HSPiP)) developed by charles Hansen et al.

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

By preparing a curable composition in which such a specific solvent (S1) is blended together with the near-infrared absorbent (B) having a specific structure at a specific mass ratio, the solvent (S1) solubility of the near-infrared absorbent (B) is excellent, and the curable composition has excellent low-temperature stability.

The polar term δ p including the hansen solubility parameter is 16 or more (MPa)^0.5) The curable composition of (S1) has excellent film forming properties by spin coating, and therefore, a coating film having a uniform film thickness can be formed by spin coating, and a cured product having a uniform film thickness 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 ℃.

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

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

Typical examples thereof 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 lactam structure in its chemical structure is a solvent having a lactam skeleton which is a cyclic skeleton having a-CO-NH-bond.

The solvent containing a sultone structure in its chemical structure is a solvent containing-O-SO₂-a sultone-backbone solvent of cyclic backbone of bonds.

Preferable specific examples of the solvent (S1) include gamma-butyrolactone (Δ p: 16.6 MPa)^0.5Boiling point: 204-205 ℃), N-dimethylformamide (δ p: 13.7MPa^0.5Boiling point: 153 ℃ C.), dimethyl sulfoxide (δ p: 16.4MPa^0.5Boiling point: 189 deg.c), N-methylpyrrolidone (δ p: 12.3MPa^0.5Boiling point: 202 deg.C) and the like.

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% by mass or more, more preferably 20% by mass or more, based on the total of the mass of the solvent (S1) and the mass of the solvent (S2). The content of the solvent (S1) is preferably 80% by mass or less, more preferably 60% by mass or less, relative to 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 not interfering with the object of the present invention. The solid content concentration is, for example, preferably 5 mass% or more and 60 mass% or less, and more preferably 10 mass% or more and 50 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 can be used, for example, for improving the defoaming property at the time of producing the curable composition, further improving the stability of the curable composition, the coatability of the curable composition, and the like.

As the surfactant, a water-soluble surfactant can be preferably used. As the surfactant, any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can be used. The surfactant may be 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 absorption filter, and methods for producing them

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.

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

The near infrared absorption filter is used as a member of various devices such as a solid-state imaging device such as a CCD and a 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 in which a solid-state imaging device is provided on a semiconductor substrate, and the like.

Examples of the method for forming the curable composition layer on the support include coating methods such as spin coating, slit coating, spraying, roll coating, dropping method, ink jet method, screen printing, and applicator method, nanoimprint method, and transfer method using a mold.

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

The curable composition layer is cured by heating. The heating conditions are not particularly limited as long as the curable composition can be cured, and for example, the heating temperature is 140 ℃ to 220 ℃ and the heating time is 1 minute to 30 minutes.

In addition, the solvent (S) is preferably removed by heating simultaneously with or separately from 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 curable composition has excellent solubility in a solvent of the near-infrared absorber, a cured product such as a thin near-infrared absorption filter having desired near-infrared absorption characteristics can be produced by increasing the concentration of the near-infrared absorber (B) in the curable composition. Further, since the curable composition has excellent low-temperature stability, even when the curable composition is stored or transferred at a low temperature, a cured product such as a near infrared absorption filter having a uniform film thickness can be obtained.

Method for storing curable composition at low temperature and method for transporting curable composition

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

In the method for conveying the curable composition, the curable composition is conveyed by a conveying machine at 10 ℃ or lower.

Here, the conveying machine is not particularly limited as long as the curable composition can be conveyed at a desired temperature. Specific examples of the conveyance device include an automobile such as a truck, a railway vehicle, a ship, an aircraft, and the like.

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 is not cured or components in the curable composition are not precipitated. The temperature for storage and transportation may be, for example, at least-22 ℃ and at least-15 ℃.

The curable composition has excellent low-temperature stability. Therefore, even when the curable composition is stored at a low temperature or the curable composition is transported by a transport machine at a low temperature, the occurrence of precipitates in the curable composition can be suppressed. Therefore, even after storage and transportation at low temperatures, 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 described above or a process route for carrying out the method for producing a near infrared absorption filter described above. 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 ℃, and specifically may be, for example, about 15 ℃ or higher and about 25 ℃ or lower.

The curable composition herein may be prepared by appropriately selecting the above-mentioned materials, and the preparation of the curable composition and the timing of providing the curable composition to the process route may be considered according to the size of the process route and the operating speed.

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

The entities used in the method for producing the cured product and the near-infrared absorption filter do not necessarily have to be the same as the entities used in the method for providing the near-infrared absorption filter.

Examples

The present invention will be specifically described below 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 ray absorption dye (B), the following cyanine compound B1 (product name: S01965, manufactured by Spectrum info corporation) was used, and the maximum concentration of the cyanine compound dissolved in the solvent shown in Table 1 was measured by stirring at 25 ℃ for 1 hour. 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 number on the lower right of the parentheses in each structural unit in the following structural formula represents 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 cyanine compound B1 (product name: S01965, manufactured by Spectrum Info Co., Ltd.) 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.

As the solvent (S2), Cyclopentanone (CP) and Propylene Glycol Monomethyl Ether Acetate (PGMEA) were used.

(production of curable composition)

The curable compositions of examples 1 to 5 and comparative examples 1 to 3 were obtained by charging a mixed solvent of the solvent (S1) and the solvent (S2), the resin a, and the cyanine compound B1 in the types and mixing ratios (mass ratios) described in table 2 into a container and stirring at 25 ℃ for 1 hour. The resin a was used in an amount such that 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)) became 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 (mass of the cyanine compound B1/mass of the resin a) was 0.015.

The curable compositions of examples 1 to 5 and comparative examples 1 to 4 were each obtained as a homogeneous solution 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 by visual observation, and the case where no precipitate was formed was evaluated as "O", and the case where precipitate was formed was evaluated as "X". The results are shown in Table 2.

[ Table 2]

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

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

Claims

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

the near infrared ray absorption dye (B) has > N⁺As to the partial structure shown in the drawings,

the solvent (S) contains a polar term with a Hansen solubility parameter, δ p of 12 (MPa)^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) has a chemical structure containing 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 comprises a solvent (S2) different from the solvent (S1),

the content of the solvent (S1) is 15% by 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 the 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 a cyanine compound, a squarylium compound, and a diimmonium compound.

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

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

8. A near-infrared absorption 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 absorption 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 ℃ or lower.

12. A method for conveying a curable composition, wherein the curable composition according to any one of claims 1 to 6 is conveyed by a conveyor at 10 ℃ or lower.

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