Resins for optical materials used in infrared sensors or infrared communication devices, resin compositions, films, optical materials, optical lenses, and optical waveguides

Abstract

To provide a resin having a high refractive index and excellent transparency and chemical resistance in applications of an optical material used in an infrared sensor or an infrared communication apparatus in a wavelength region of 800 to 1600 nm.SOLUTION: A resin for an optical material used in an infrared sensor or an infrared communication apparatus has a refractive index of 1.65 or more at 23°C and a wavelength of 850 nm. The resin satisfies the following (1) and (2) when a film with a thickness of 1.0 μm is formed. (1) The maximum absorbance at 400-780 nm is 1.0 or more; (2) the absorbance at 820 nm is less than 0.3.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin for an optical material used in an infrared sensor or an infrared communication device, a resin composition, a film, an optical material, an optical lens, and an optical waveguide. [Background technology]

[0002] Traditionally, a surface protective layer made of an inorganic or organic material has been applied to the surface of glass, films, and sheets used in sensor elements such as CCDs and CMOSs, and display elements such as displays. In recent years, coating layers, such as those consisting of alternating high-refractive-index and low-refractive-index layers, have been used on the surface protective layer to provide functions such as anti-reflection and optical waveguide. Among these, high-refractive-index layers include high-refractive-index inorganic films formed by vapor deposition of ceramics such as titania, zirconia, and alumina, and high-refractive-index organic films made of aromatic resins, depending on the purpose. However, the use of high-refractive-index inorganic films has presented problems such as insufficient adhesion to the substrate and film fragility. Therefore, high-refractive-index organic films have become more widely used in recent years.

[0003] Furthermore, organic electroluminescence (hereinafter referred to as OLED) panels, which are attracting attention as next-generation displays, have a laminated structure consisting of inorganic layers made of silicon oxide, silicon nitride, alumina, etc., and organic layers made of organic sealing materials whose main components are acrylic resin or epoxy resin, in order to prevent deterioration of the OLED elements due to penetration of moisture or gas from outside. These inorganic and organic layers are laminated alternately. Here, the smaller the difference in refractive index between the inorganic and organic layers, the more improved the light extraction efficiency, so the higher the refractive index of the organic layer, the better. Therefore, there is a demand for organic sealing materials with a high refractive index.

[0004] Furthermore, in recent years, molded articles produced using three-dimensional modeling devices have been widely used in the medical and optical fields. Photocurable resins are used as molding resins for three-dimensional modeling (Patent Document 1, Patent Document 2). In particular, for molded articles of lenses used in medical devices, microscopes, various cameras, and the like, photo-lithography resins with high refractive indexes are required to make the lenses thinner.

[0005] As high refractive index organic materials for the surface protection layer as described above, organic sealants for organic EL panels, and resins for stereolithography, resins containing sulfur and resins such as fluorene having a conjugated aromatic ring structure are known (Patent Documents 2, 3, and 4).

[0006] Recently, sensing and communication using near-infrared rays are becoming widespread, such as solid-state imaging devices for photographing subjects at night, infrared sensors such as Lidar used for distance measurement, and infrared communication devices that use light propagating through optical waveguides. For lenses and other devices used to focus these rays, it is important to use optical materials with a high refractive index in the near-infrared region. One method for achieving this is to add a dye or pigment to a resin to form a film, thereby achieving a high refractive index in the near-infrared region. However, achieving a higher refractive index requires increasing the dye concentration in the film, and dyes have not been able to achieve sufficient transparency due to factors such as crystal precipitation, while pigments have not been able to achieve sufficient transparency due to factors such as dispersibility. Furthermore, when used in lenses or optical waveguides, melt molding is required, which is difficult with compositions containing high concentrations of dye or pigment (Patent Documents 5, 6, 7, and 8). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-157543 [Patent Document 2] Japanese Patent Application Publication No. 2019-019245 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-281787 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-168721 [Patent Document 5] International Publication No. 2019 / 065475 [Patent Document 6] International Publication No. 2020 / 085499 [Patent Document 7] International Publication No. 2020 / 138050 [Patent Document 8] International Publication No. 2018 / 092600 Summary of the Invention [Problem to be solved by the invention]

[0008] Among sensing and communication using near-infrared rays, sensing and communication using light rays in the 800 to 1600 nm range have become particularly widespread in recent years. For optical lenses that focus these rays and for optical waveguides that propagate these rays, it is important to use optical materials with high refractive indexes and high transparency and durability. However, at present, there has been little progress in the development of high refractive index materials with sufficient durability.

[0009] In view of the above problems, the present invention aims to provide a resin that has a high refractive index and excellent transparency and chemical resistance when used as an optical material for infrared sensors or infrared communication devices in the wavelength region of 800 to 1600 nm. [Means for solving the problem]

[0010] That is, the present invention is A resin for optical materials used in infrared sensors or infrared communication devices, The refractive index at 23°C and a wavelength of 850 nm is 1.65 or more, The resin satisfies the following (1) and (2) when a film having a thickness of 1.0 μm is formed. (1) The maximum absorbance in the range of 400 to 780 nm is 1.0 or more. (2) Absorbance at 820 nm is less than 0.3

[0011] The present invention also relates to the above resin, which contains a structural unit represented by the following general formula (1) and / or a structural unit represented by the following general formula (2). General formula (1) [ka] In general formula (1), A1 is a residue of a compound having absorption in the range of 400 to 780 nm, and the maximum molar absorption coefficient of the structural unit represented by general formula (1) in the range of 400 to 780 nm is 2000 L / (mol cm) or more. X1 is a divalent bonding group. R 111 is a hydrogen atom or a methyl group. General formula (2) [ka] (In general formula (2), A2 is a residue of a compound having absorption in the range of 400 to 780 nm, and the maximum molar absorption coefficient of the structural unit represented by general formula (2) in the range of 400 to 780 nm is 2000 L / (mol cm) or more. X2 is a divalent bonding group.)

[0012] The present invention also relates to the above resin, which contains the structural unit represented by general formula (1) and / or the structural unit represented by general formula (2) in an amount of 65 mass % or more based on the total mass.

[0013] The present invention also relates to the above resin, wherein A1 in general formula (1) and / or A2 in general formula (2) is at least one residue selected from the group consisting of a xanthene residue, a cyanine residue, a phthalocyanine residue, a naphthalocyanine residue, a squarylium residue, a diketopyrrolole residue, an anthraquinone residue, a dioxazine residue, a dipyrromethene residue, a quinophthalone residue, and an azo residue.

[0014] The present invention also relates to the above resin used to form an optical lens or an optical waveguide.

[0015] The present invention also relates to a resin composition containing the above resin, a curing agent, and a solvent.

[0016] The present invention also relates to a film containing the above resin or the above resin composition.

[0017] The present invention also relates to an optical material containing the above resin or the above resin composition.

[0018] The present invention also relates to an optical lens comprising the above resin or the above resin composition.

[0019] The present invention also relates to an optical waveguide containing the above resin or the above resin composition.

[0020] The present invention also relates to an infrared sensor or an infrared communication device comprising the above-mentioned film, optical material, optical lens, or optical waveguide. [Effects of the Invention]

[0021] According to the present invention, it is possible to provide a resin and a resin composition that can be used as a material having a high refractive index and excellent transparency and chemical resistance when used as an optical material for an infrared sensor or an infrared communication device in the wavelength region of 800 to 1600 nm.

[0022] The resin and resin composition of the present invention are suitable for use as optical materials in infrared sensors or infrared communication devices that require a high refractive index in the wavelength region of 800 to 1600 nm, and are particularly suitable for use as optical materials in optical films, optical lenses, optical waveguides, etc. Among these, they are particularly suitable for use in forming optical lenses or optical waveguides. DETAILED DESCRIPTION OF THE INVENTION

[0023] <Regarding the resin and resin composition of the present invention> The resin for optical materials used in the infrared sensor or infrared communication device of the present invention is The refractive index at 23°C and a wavelength of 850 nm is 1.65 or more, When a film with a thickness of 1.0 μm was formed, (1) The maximum absorbance in the range of 400 to 780 nm is 1.0 or more. (2) Absorbance at 820 nm is less than 0.3 Meet the following.

[0024] <Optical properties of resin> The resin of the present invention is characterized in that when a film having a thickness of 1 μm is formed, the maximum absorbance in the absorption spectrum from 400 to 780 nm is 1.0 or more. After extensive research, the inventors discovered that a resin with very high absorption in the 400-780 nm wavelength range, which is close to 800-1600 nm, can achieve a high refractive index in the 800-1600 nm wavelength range. This makes it possible to obtain a high refractive index film without using sulfur atoms or iodine, which are known to contribute to a high refractive index. Regarding the degree of absorption, the maximum absorbance in the 400-780 nm range in the absorption spectrum of a 1 μm-thick coating film must be 1.0 or higher, preferably 2.0 or higher, more preferably 3.0 or higher, and even more preferably 4.0 or higher.

[0025] Furthermore, the resin of the present invention is characterized in that, when formed into a film with a thickness of 1 μm, its absorption spectrum exhibits an absorbance of less than 0.3 at 820 nm. This is because, in order to minimize light loss when used as a high-refractive index material for concentrating 800-1600 nm light rays used in sensing or for propagating 800-1600 nm light rays used in communications, it is important to transmit as much light as possible, i.e., to have low absorption. Preferably, the absorbance is less than 0.2, and more preferably less than 0.1.

[0026] The resin of the present invention has a refractive index at 23°C and a wavelength of 850 nm of 1.65 or more, more preferably 1.7 or more, even more preferably 1.8 or more, and most preferably 1.9 or more. There is no particular upper limit to the refractive index, but it is preferably 2.5 or less, and more preferably 2.4 or less.

[0027] The resin of the present invention preferably contains a structural unit represented by the following general formula (1) and / or a structural unit represented by the following general formula (2). General formula (1) [ka] In general formula (1), A1 is a residue of a compound having absorption in the range of 400 to 780 nm, and the maximum molar absorption coefficient of the structural unit represented by general formula (1) in the range of 400 to 780 nm is 2000 L / (mol cm) or more. X1 is a divalent bonding group. R 111 is a hydrogen atom or a methyl group. General formula (2) [ka] (In general formula (2), A2 is a residue of a compound having absorption in the range of 400 to 780 nm, and the maximum molar absorption coefficient of the structural unit represented by general formula (2) in the range of 400 to 780 nm is 2000 L / (mol cm) or more. X2 is a divalent bonding group.)

[0028] When the resin of the present invention contains structural units represented by general formula (1) and / or structural units represented by general formula (2), the structural units represented by general formula (1) and / or structural units represented by general formula (2) preferably account for 65 mass % or more, more preferably 70 mass % or more, and even more preferably 80 mass % or more of the total mass of the resin. When a resin contains a structural unit represented by general formula (1), in order to have a high refractive index in the 800 to 1600 nm wavelength range, it is essential that the resin has high absorbance in the 400 to 780 nm wavelength range, which is close to this wavelength range. It is important that the proportion of structural units of general formula (1) having a compound residue A1 with strong absorption in the 400 to 780 nm range is high. By having the structural units of general formula (1) account for 65 mass% or more of the total mass, a film can be obtained that exhibits sufficiently high absorbance in the 400 to 780 nm range, which is close to the 800 to 1600 nm wavelength range. The same applies when the resin contains a structural unit represented by general formula (2). The upper limit of the content of the structural units of general formula (1) and general formula (2) is not particularly limited, but is preferably 95% by mass or less from the viewpoint of solubility in general-purpose solvents such as methyl ethyl ketone, and more preferably 90% by mass or less.

[0029] <Embodiments of general formula (1)> Next, the case where the resin of the present invention contains a structural unit represented by general formula (1) will be described. A1 is a residue of a compound that has absorption in the range of 400 to 780 nm, and when general formula (1) is used as a structural unit, the maximum molar absorption coefficient in the range of 400 to 780 nm is 2000 L / (mol cm) or more. As long as A1 satisfies this condition, it may have any structure, but is preferably at least one residue selected from the group consisting of xanthene residues, cyanine residues, phthalocyanine residues, naphthalocyanine residues, squarylium residues, diketopyrrolole residues, anthraquinone residues, dioxazine residues, dipyrromethene residues, quinophthalone residues, and azo residues, more preferably at least one residue selected from the group consisting of xanthene residues, cyanine residues, phthalocyanine residues, naphthalocyanine residues, and squarylium residues, and particularly preferably an aluminum phthalocyanine residue.

[0030] <Unsaturated Monomer (a1) Represented by General Formula (3)> In order to obtain a resin containing a structural unit represented by general formula (1), it is effective to synthesize the resin using an unsaturated monomer (a1) represented by general formula (3) as a polymerization component.

[0031] General formula (3) [ka] (A1 is a residue of a compound having absorption in the range of 400 to 780 nm, and the maximum molar absorption coefficient of the structural unit represented by general formula (1) in the range of 400 to 780 nm is 2000 L / (mol cm) or more. X1 is a divalent linking group. R 111 is a hydrogen atom or a methyl group.

[0032] X1 is preferably an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkenylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, or may further be a compound group in which a plurality of these are bonded together. These compound groups may have -O-, -C(=O)-, -NH-, -OC(=O)-, -C(=O)O-, -C(=O)NH-, -NHC(=O)-, -NHC(=O)O-, or -OC(=O)-NH- at the end or between carbon atoms, and a hydrogen atom may be substituted with a halogen atom. Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a tert-butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadecylene group, and an icosylene group.

[0033] Examples of alkenylene groups having 2 to 20 carbon atoms include vinylene, propenylene, butenylene, pentenylene, and hexenylene groups. Examples of cycloalkylene groups having 3 to 20 carbon atoms include cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene groups. Examples of cycloalkenylene groups having 3 to 20 carbon atoms include cyclopropenylene, cyclopentenylene, and cyclohexenylene groups. Examples of aryl groups having 6 to 20 carbon atoms include aromatic hydrocarbon groups such as phenyl, tolyl, xylyl, benzyl, and phenethyl groups.

[0034] The alkylene group having 1 to 20 carbon atoms includes those in which the hydrogen moiety is substituted. Examples thereof include a 1-bromomethylene group, a 2-bromoethylene group, a 2-chloroethylene group, a 2-iodoethylene group, a 3-bromopropylene group, a 4-bromobutylene group, a 1-bromobutylene group, a 5-bromopentylene group, a 6-bromohexylene group, a 7-bromoheptylene group, an 8-bromooctylene group, a 9-bromononylene group, a 10-bromodecylene group, an 11-bromoundecylene group, a 12-bromododecylene group, a 13-bromotridecylene group, a 14-bromotetradecylene group, a 15-bromopentadecylene group, a 16-bromohexadecylene group, a 17-bromoheptadecylene group, an 18-bromooctadecylene group, a 19-bromononadecylene group, and a 20-bromoicosylene group.

[0035] The cycloalkylene group having 3 to 20 carbon atoms includes those in which a hydrogen atom is substituted, such as a 2-bromocyclopropylene group, a 2-bromocyclopentylene group, and a 4-bromocyclohexylene group.

[0036] The arylene group having 6 to 20 carbon atoms includes those in which a hydrogen moiety is substituted. Examples thereof include aromatic hydrocarbons such as a monobromophenylene group, a dibromophenylene group, a monochlorophenylene group, a monobromotolylene group, a monobromoxylylene group, a monobromobenzylene group, and a monobromophenethylene group.

[0037] The unsaturated monomer (a1) represented by general formula (3) has a dye skeleton that absorbs light in the range of 400 to 780 nm. As the dye skeleton that absorbs light in the range of 400 to 780 nm, at least one dye skeleton selected from the group consisting of a xanthene skeleton, a cyanine skeleton, a phthalocyanine skeleton, a naphthalocyanine skeleton, a squarylium skeleton, a diketopyrrolole skeleton, an anthraquinone skeleton, a dioxazine skeleton, a dipyrromethene skeleton, a quinophthalone skeleton, and an azo skeleton is particularly preferred, and at least one dye skeleton selected from the group consisting of a xanthene skeleton, a cyanine skeleton, a phthalocyanine skeleton, a naphthalocyanine skeleton, and a squarylium skeleton is more preferred. Examples of the unsaturated monomer (a1) are shown below, but the present invention is not limited to these.

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] <Other Polymer Components> When obtaining a resin containing a structural unit represented by general formula (1), other unsaturated monomers (b1) may be used as polymerization components in addition to the unsaturated monomer (a1) represented by general formula (3). The other unsaturated monomers (b1) may be used alone or in combination.

[0043] Examples of other unsaturated monomers (b1) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2,2,4-trimethylcyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, and isobornyl (meth)acrylate; Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate; heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate; alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate; (N-substituted) (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine; amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; nitriles such as (meth)acrylonitrile; Examples include styrenes such as styrene, α-methylstyrene, and indene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and vinyl fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0044] Further, as the other unsaturated monomer (b1), a monomer having a hydroxyl group can be used in combination. Examples of the monomer having a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth)acrylamide-based monomers having a hydroxyl group, such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl ... Examples of the hydroxyalkyl vinyl ether monomer include N-(hydroxyalkyl)(meth)acrylamides such as N-(hydroxybutyl)(meth)acrylamide, vinyl ether monomers having a hydroxyl group, for example, hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, and 2-(or 3- or 4-)hydroxybutyl vinyl ether, and allyl ether monomers having a hydroxyl group, for example, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, and 2-(or 3- or 4-)hydroxybutyl allyl ether.

[0045] Ethylenically unsaturated monomers obtained by adding alkylene oxides and / or lactones to the above-mentioned hydroxyalkyl (meth)acrylates, alkyl-α-hydroxyalkyl acrylates, N-(hydroxyalkyl) (meth)acrylamides, hydroxyalkyl vinyl ethers, or hydroxyalkyl allyl ethers can also be used as the other unsaturated monomer (b1). Examples of the alkylene oxides to be added include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide, and combinations of two or more of these. When two or more alkylene oxides are used in combination, the bonding form may be random and / or block. Examples of the lactones to be added include δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and combinations of two or more of these. Addition of both alkylene oxides and lactones is also acceptable.

[0046] Furthermore, as the other unsaturated monomer (b1), a carboxyl group-containing ethylenically unsaturated monomer can also be used in combination. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0047] In order to obtain a resin with a higher refractive index, it is preferable to use an unsaturated monomer having an aromatic ring as another polymerization component. Preferred examples include benzyl methacrylate, benzyl acrylate, N-phenylmaleimide, styrene, 4-vinyltoluene, and 9-vinylcarbazole, and more preferred examples include styrene, 4-vinyltoluene, and 9-vinylcarbazole.

[0048] The weight-average molecular weight of the resin of the present invention can be selected from a range of about 1,000 to 200,000, and may be, for example, 2,000 to 100,000, preferably 3,000 to 50,000, more preferably 4,000 to 40,000, even more preferably 5,000 to 30,000, and particularly preferably 5,500 to 15,000. When the weight-average molecular weight is within the above range, it is possible to achieve both solubility in general-purpose solvents and solubility with optional components, such as a curing agent, when used as a high refractive index material.

[0049] (About polymerization) One example of a method for synthesizing a resin having a structural unit represented by general formula (1) is a method of polymerizing an unsaturated monomer (a1) represented by general formula (3). Of course, other unsaturated monomers (b1) may be included in the copolymer composition. Known methods such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization can be used for this purpose. Of these, free radical polymerization and living radical polymerization are preferred.

[0050] In the case of free radical polymerization, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include azo compounds and organic peroxides. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150°C, more preferably 50 to 110°C, and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

[0051] Examples of free radical polymerization methods include a method in which a solvent is placed in a reaction vessel, heated, and a mixture of unsaturated monomers is added dropwise little by little together with a polymerization initiator, and a method in which an insoluble monomer is placed in a reaction vessel together with a chain transfer agent and the like, heated, and then a polymerization initiator is added little by little.

[0052] In the present invention, the unsaturated monomer (a1) preferably has at least one dye skeleton selected from the group consisting of a xanthene skeleton, a cyanine skeleton, a phthalocyanine skeleton, a naphthalocyanine skeleton, a squarylium skeleton, a diketopyrrolole skeleton, an anthraquinone skeleton, a dioxazine skeleton, a dipyrromethene skeleton, a quinophthalone skeleton, and an azo skeleton, but in this case, the solubility in common solvents tends to be low. Therefore, a preferred method is to initially charge the unsaturated monomer (a1) together with a chain transfer agent etc. into a reaction vessel, apply heat to dissolve, and then add the polymerization initiator little by little.

[0053] By using living radical polymerization, the side reactions that occur in general radical polymerization are suppressed, and furthermore, the polymerization growth occurs uniformly, making it easy to synthesize block polymers and resins with uniform molecular weights.

[0054] Among these, atom transfer radical polymerization, which uses an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, is preferred because it can be used with a wide range of monomers and can employ a polymerization temperature that is compatible with existing equipment. Atom transfer radical polymerization can be carried out by the methods described in the following references 1 to 8, etc.

[0055] (Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329 (Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921 (Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614 (Reference 4) Macromolecules 1995,28,7901,Science,1996,272,866 (Reference 5) International Publication No. 1996 / 030421 (Reference 6) International Publication No. 1997 / 018247 (Reference document 7) Japanese Patent Application Publication No. 9-208616 (Reference 8) Japanese Patent Application Laid-Open No. 8-41117

[0056] During the polymerization, it is preferable to use an organic solvent as the polymerization solvent. Specifically, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Two or more of these polymerization solvents may be mixed and used.

[0057] In the case of living radical polymerization, the reaction temperature is, for example, 50°C to 150°C, and preferably 70°C to 120°C.

[0058] As a method for synthesizing the resin constituting the general formula (1), there is also a method in which a polymer (d1) not containing the compound residue A1 is first polymerized, and then a compound (c1) having the compound residue A1 is reacted to introduce the compound residue A1. When the compound (c1) having the compound residue A1 has a reactive functional group such as a hydroxyl group or a carboxyl group, and the polymer (d1) not containing the compound residue A1 has a functional group that reacts with such a reactive functional group, A1 can be easily introduced. When the compound (c1) having the compound residue A1 has a hydroxyl group, the polymer (d1) not containing the compound residue A1 preferably has a carboxy group and an isocyanate group. When the compound (c1) having the compound residue A1 has a carboxy group, the polymer (d1) not containing the compound residue A1 preferably has a hydroxyl group or an epoxy group. Furthermore, when the compound (c1) having the compound residue A1 or the polymer (d1) not containing the compound residue A1 has a carboxy group, the reaction product can be more easily obtained at low temperatures by adding thionyl chloride or the like to convert it into an acid chloride and then reacting it with a hydroxyl group.

[0059] <Embodiments of general formula (2)> Next, the case where the resin of the present invention contains a structural unit represented by general formula (2) will be described. Like A1, A2 is a residue of a compound that has absorption in the range of 400 to 780 nm, and when general formula (2) is used as a structural unit, the maximum molar extinction coefficient in the range of 400 to 780 nm is 2000 L / (mol cm) or more. As long as A2 satisfies this condition, it may have any structure. However, like A1, it is preferably at least one residue selected from the group consisting of xanthene residues, cyanine residues, phthalocyanine residues, naphthalocyanine residues, squarylium residues, diketopyrrolole residues, anthraquinone residues, dioxazine residues, dipyrromethene residues, quinophthalone residues, and azo residues. It is more preferably at least one residue selected from the group consisting of xanthene residues, cyanine residues, phthalocyanine residues, naphthalocyanine residues, and squarylium residues, and it is particularly preferably a xanthene residue.

[0060] In order to obtain a resin containing a structural unit represented by general formula (2), it is preferable to synthesize the resin by reacting a monomer (a2) having a compound residue A2 and two reactive functional groups such as a hydroxyl group, a carboxyl group, a carboxylic anhydride group, an epoxy group, or an isocyanate group with a monomer (b2) having X2 and two hydroxyl groups, a carboxyl group, a carboxylic anhydride group, an epoxy group, or an isocyanate group.

[0061] Examples of the monomer (a2) having the compound residue A1 and two reactive functional groups such as a hydroxyl group, a carboxyl group, a carboxylic anhydride group, an epoxy group, or an isocyanate group include the following compounds.

[0062] [ka]

[0063] [ka]

[0064] Examples of the monomer (b2) having X2 and two reactive functional groups such as a hydroxyl group, a carboxyl group, a carboxylic anhydride group, an epoxy group, or an isocyanate group include the following compounds.

[0065] Examples of monomers having two hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, cyclohexanediol, cyclohexanedimethanol, cyclohexenedimethanol, resorcinol, benzenedimethanol, dihydroxybiphenol, biphenyldimethanol, dihydroxynaphthalene, bis(hydroxymethyl)naphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene.

[0066] Examples of monomers having two carboxyl groups include succinic acid, maleic acid, fumaric acid, hexanedioic acid, octanedioic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phenylenediacetic acid, biphenyldicarboxylic acid, and naphthalenedicarboxylic acid.

[0067] Examples of the monomer having two carboxylic acid anhydride groups include cyclohexanedicarboxylic acid dianhydride, pyromellitic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, and biphenyltetracarboxylic acid dianhydride.

[0068] Examples of monomers having two epoxy groups include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol diglycidyl ether, hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol F diglycidyl ether.

[0069] Examples of the monomer having two isocyanate groups include tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

[0070] (Reaction of Monomer (a2) with Monomer (b2)) When monomer (a2) has two hydroxyl groups, and monomer (b2) has two isocyanate groups, the two monomers can be easily reacted. The reaction proceeds when both monomers are dissolved in a solvent, mixed, stirred, and heated to approximately 80°C to 120°C. The reaction can be made to proceed more quickly by using an amine or tin catalyst. When monomer (a2) has two hydroxyl groups, and when monomer (b2) has two acid anhydride groups, they can be easily reacted. The reaction proceeds when the monomers are dissolved in a solvent, mixed, stirred, and heated to about 80 to 120°C. The reaction can be made to proceed more quickly by using an amine catalyst or other catalyst. When monomer (a2) has two hydroxyl groups, the reaction can be carried out even when monomer (b2) has two carboxyl groups. In this case, the reaction proceeds when heated to approximately 180°C to 240°C. The reaction can be made to proceed more quickly by using an amine-based catalyst. Furthermore, the carboxylic acid of monomer (b2) can be converted to an acid chloride using thionyl chloride or the like before the reaction, allowing the reaction to proceed easily at temperatures close to room temperature.

[0071] By adding a component other than the monomer (a2) to the reaction, it is possible to control the ratio of the monomer (a2) in the total mass and adjust the compatibility, solubility, etc. Examples of components other than the monomer (a2) to be added to the reaction include those exemplified as the above-mentioned monomer (b2), which have various functional groups such as a hydroxyl group, a carboxyl group, a carboxylic anhydride group, an epoxy group, an isocyanate group, etc., and therefore can be used as a substitute for the monomer (a2).

[0072] (Resin composition) The resin of the present invention can be used as a resin composition for a high refractive index material together with a curing agent and a solvent.

[0073] (hardening agent) Examples of the curing agent include polyfunctional acid anhydrides, polyfunctional epoxies, polyfunctional oxetanes, polyfunctional isocyanates, polyfunctional blocked isocyanates, polyfunctional carboxylic acids, and polyfunctional alcohols. When the resin of the present invention contains a carboxylic acid, the carboxylic acid reacts with an epoxy group, an oxetane group, or a hydroxyl group when heated, and therefore a polyfunctional epoxy, a polyfunctional oxetane, or a polyfunctional alcohol is preferred. When the resin of the present invention contains a hydroxyl group, the hydroxyl group reacts with an acid anhydride, an isocyanate, a blocked isocyanate, or a carboxylic acid upon heating, and therefore polyfunctional acid anhydrides, polyfunctional isocyanates, polyfunctional blocked isocyanates, and polyfunctional carboxylic acids are preferred. When the resin of the present invention contains a t-butyl group, isobutene is eliminated from the t-butyl group upon heating to form a carboxylic acid, and therefore, similarly to the above, polyfunctional epoxy, polyfunctional oxetane, and polyfunctional alcohol are preferred. When the resin of the present invention contains oxetane groups, polyfunctional carboxylic acids are preferred because the oxetane reacts with the carboxylic acid upon heating. When the resin of the present invention contains a blocked isocyanate, the blocked isocyanate is released from the block upon heating to become an isocyanate, which reacts with a hydroxyl group, and therefore a polyfunctional alcohol is preferred.

[0074] Examples of polyfunctional acid anhydrides include pyromellitic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA manufactured by Mitsubishi Chemical Corporation), Rikacid TMEG-100 manufactured by New Japan Chemical Co., Ltd., and 4,4'-oxydiphthalic anhydride. Examples of polyfunctional epoxy resins include bisphenol A type epoxy resins, alkane diepoxides such as 1,7-octane diepoxide, jER Cure ST11 manufactured by Mitsubishi Chemical Corporation, EHPE3150 and Celloxide 2021P manufactured by Daicel Corporation. Examples of polyfunctional oxetanes include ETERNACOLL OXBP and ETERNACOLL OXIPA manufactured by Ube Industries, Ltd. Examples of polyfunctional isocyanates include isophorone diisocyanate, tolylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate. Examples of the blocked isocyanate include Coronate 2507 and Coronate 2554 manufactured by Tosoh Corporation, and Duranate E402-B80B manufactured by Asahi Kasei Corporation. Examples of polyfunctional carboxylic acids include butanetetracarboxylic acid, and examples of polyfunctional alcohols include penerythritol, trimethylolpropane, and glycerin.

[0075] (solvent) Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, and 3-methoxybutanol. ethanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol Examples of the propylene glycol monomethyl ether acetate include dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

[0076] Among these, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone are preferably used because of their good solubility.

[0077] These organic solvents can be used alone or in combination of two or more. When a mixed solvent of two or more types is used, it is preferable that the mixed solvent contains 65 to 95% by weight of the above-mentioned preferred organic solvents.

[0078] (others) The resin composition may contain other materials as appropriate, such as a photopolymerizable monomer, a photopolymerization initiator, a sensitizer, and a leveling agent.

[0079] Examples of the photopolymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, and bisphenol A diglycidyl ether di(meth)acrylate. Examples of the acrylic acid esters and methacrylic acid esters include, but are not limited to, acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0080] Photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-benzyl-2-dimethylphenyl ketone. acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylpermethyl)benzoate benzophenone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, triazine-based compounds such as 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples of compounds that can be used include oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

[0081] Examples of sensitizers include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, polymethine dyes such as benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. compounds, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3′ or 4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 4,4′-diethylaminobenzophenone, and the like.

[0082] Particularly preferred leveling agents are those so-called surfactants having both hydrophobic and hydrophilic groups in the molecule, which have low solubility in water despite the presence of hydrophilic groups, and when added to a coloring composition, have the characteristic of low surface tension reduction. Furthermore, those that have good wettability to glass plates despite their low surface tension reduction are useful. Those that can sufficiently suppress electrostatic charge at an amount that does not cause coating film defects due to bubbling are preferably used. Dimethylpolysiloxanes having polyalkylene oxide units are preferably used as leveling agents having such preferred properties. Examples of polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxanes may have both polyethylene oxide units and polypropylene oxide units.

[0083] The bonding form of the polyalkylene oxide units with the dimethylpolysiloxane may be any of the following: a pendant type in which the polyalkylene oxide units are bonded to the repeating units of the dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide units are bonded to the terminals of the dimethylpolysiloxane, or a linear block copolymer type in which the polyalkylene oxide units are bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., and examples thereof include, but are not limited to, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

[0084] <Film containing resin or resin composition and use thereof> The resin or resin composition of the present invention can be cured by, for example, solvent evaporation, exposure to light (photocuring), or heating (thermocuring) to obtain a film containing the resin or resin composition of the present invention. The method for forming the film is not limited to the above. Examples of light rays used for exposure in photocuring include ultraviolet rays, electron beams, and X-rays. Light sources that can be used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. After exposure, post-baking may be performed to stabilize the physical properties of the cured product. The post-baking method is not particularly limited, but is typically performed at 50 to 260°C for 1 to 120 minutes using a hot plate, oven, or the like. The heating conditions for thermal curing are not particularly limited, but are usually selected appropriately from the ranges of 50 to 300° C. and 1 to 120 minutes. The heating means is not particularly limited, but examples thereof include a hot plate and an oven.

[0085] A film containing the resin or resin composition of the present invention has a high refractive index in the wavelength region of 800 to 1600 nm and is suitable as a material for forming an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device.

[0086] The resin or resin composition of the present invention can be molded into any shape, such as a dome or a sheet, to produce a film.

[0087] For example, molding can be performed as follows: A resin composition containing a photopolymerization initiator and a photopolymerizable monomer is potted onto a transparent substrate such as glass, and a desired molding die is pressed against the pot. The resin composition is filled into the molding die, and then cured by irradiating the mold with light. The molding die is then removed to obtain a cured product of the resin composition integrated on the transparent substrate. Alternatively, the resin composition can be filled into a transparent mold that transmits light and then photocured. This manufacturing method can be used to produce, for example, a hybrid lens. The resin or resin composition of the present invention can also be cured by itself in a molding die to form an optical component such as an optical lens. They can also be molded into microlenses. The etch-back method is known as one method for producing microlenses. A resist pattern is formed on a coating film of the resin or resin composition of the present invention, and the resist pattern is reflowed by heat treatment to form a lens pattern. The lens pattern formed by reflowing the resist pattern is used as an etching mask to etch back the underlying coating film of the resin or resin composition of the present invention, and the lens pattern shape is transferred to a film of the resin or resin composition of the present invention, thereby producing a microlens. Another method for producing microlenses involves exposing and developing the resin or resin composition of the present invention, which contains a photopolymerization initiator and an alkali-soluble resin, to form a resist pattern, and then reflowing it by heat treatment to produce a microlens. When molding into an optical waveguide, for example, a resist pattern is formed by exposing and developing a resin composition containing a photopolymerization initiator and an alkali-soluble resin, and then an adjacent resist pattern is formed by exposing and developing another resin composition or pigment composition containing a photopolymerization initiator and an alkali-soluble resin and having a different refractive index, thereby forming a core and a clad, and thus an optical waveguide can be produced.

[0088] In this specification, an optical lens for an infrared sensor or an infrared communication device refers to a lens for converging infrared rays, and examples thereof include eyeglass lenses, lenses for optical devices, lenses for optoelectronics, lenses for lasers, lenses for pickups, lenses for in-vehicle cameras, lenses for mobile phones, lenses for digital cameras, lenses for overhead projectors, and microlenses.

[0089] In this specification, an optical waveguide for an infrared sensor or an infrared communication device refers to a waveguide for propagating infrared rays, and its shape is not limited, and may be a sheet, a plate, etc. Examples of applications include cables used for optical communication in computers and sensor devices, optical interconnections used for optical communication inside devices, and materials used on the optical path when an infrared sensor or the like senses infrared rays. [Example]

[0090] The present invention will be described in more detail below, but the present invention is not limited to these examples as long as they do not deviate from the technical concept of the present invention. Note that, hereinafter, "parts by mass" will be simply abbreviated as "parts" and "% by mass" will be simply abbreviated as "%".

[0091] <Production of unsaturated monomer (a1) represented by general formula (6)> (Intermediates used in the production of monomers (a1-1) to (a1-20) and (a2-1) to (a2-7)) [ka]

[0092] [ka]

[0093] (Production of Monomers (a1-1) to (a1-20) and (a2-1) to (a2-7)) Monomer (a1-1) 58.0 parts of CI Acid Red 52 and 500 parts of chloroform were added, and 14 parts of thionyl chloride was added under ice cooling, followed by stirring for 2 hours at 50° C. The reaction mixture was added to 800 parts of water in an ice bath, and the precipitated crystals were filtered to obtain the above intermediate (1-1).

[0094] To 60.0 parts of the intermediate (1-1), 600 parts of chloroform was added, and 7.0 parts of 2-hydroxyethylamine was added under ice cooling, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 1,000 parts of water, and the precipitated crystals were filtered, washed with water, and dried at 80°C for 24 hours to obtain the intermediate (1-2).

[0095] To 600 parts of methyl ethyl ketone, 60.0 parts of intermediate (1-2), 15.5 parts of 2-isocyanatoethyl methacrylate (Karends MOI, Showa Denko K.K.), and 0.08 parts of methylhydroquinone were added, and the mixture was heated to 70°C in an oxygen atmosphere and stirred for 4 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-1).

[0096] Monomer (a1-2) 69 parts of CI Acid Red 87 and 1000 parts of water were added, and 8.0 parts of hydrochloric acid was further added to precipitate crystals, thereby obtaining the intermediate (2-1) above.

[0097] To 600 parts of cyclohexanone, 67.4 parts of intermediate (2-1), 15.0 parts of glycidyl methacrylate, 0.08 parts of methylhydroquinone, and 0.8 parts of dimethylbenzylamine were added, and the mixture was heated to 120°C in an oxygen atmosphere and stirred for 8 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-2).

[0098] Monomer (a1-3) 101.7 parts of CI Acid Red 94 and 1500 parts of water were added, and 8.0 parts of hydrochloric acid was further added to precipitate crystals, thereby obtaining the intermediate (3-1) above.

[0099] To 600 parts of cyclohexanone, 95.0 parts of intermediate (3-1), 15.0 parts of glycidyl methacrylate, 0.08 parts of methylhydroquinone, and 1.0 parts of dimethylbenzylamine were added, and the mixture was heated to 120°C in an oxygen atmosphere and stirred for 8 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-3).

[0100] Monomer (a1-4) 40 parts of CI Acid Red 88 was added to 500 parts of chloroform, and 14 parts of thionyl chloride was added under ice cooling, followed by stirring for 2 hours at 50° C. The reaction mixture was added to 800 parts of water in an ice bath, and the precipitated crystals were filtered to obtain the above intermediate (1-1).

[0101] To 39.6 parts of the intermediate (4-1), 600 parts of chloroform was added, and 7.0 parts of 2-hydroxyethylamine was added under ice cooling, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 1,000 parts of water, and the precipitated crystals were filtered, washed with water, and dried at 80°C for 24 hours to obtain the intermediate (4-2).

[0102] To 600 parts of methyl ethyl ketone, 40.0 parts of intermediate (4-2), 15.5 parts of 2-isocyanatoethyl methacrylate (Karends MOI, Showa Denko K.K.), and 0.08 parts of methylhydroquinone were added, and the mixture was heated to 70°C in an oxygen atmosphere and stirred for 4 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-4).

[0103] Monomer (a1-5) 35.2 parts of Solvent Red 23 were dissolved in 200 parts of 98% sulfuric acid and stirred at 85°C for 2 hours to carry out a sulfonation reaction. The reaction solution was then added dropwise to 3,000 parts of ice water, and the precipitated compound was filtered and washed with water to obtain a paste. The resulting paste was redispersed in 8,000 parts of water and stirred at room temperature for 1 hour. After filtering and washing, the mixture was dried at 80°C overnight to obtain the above intermediate (5-1).

[0104] 43.2 parts of the intermediate (5-1) was added to 500 parts of chloroform, and 14.0 parts of thionyl chloride was added under ice cooling, followed by stirring for 2 hours at 50° C. The reaction mixture was added to 800 parts of water in an ice bath, and the precipitated crystals were filtered to obtain the above intermediate (5-2).

[0105] To 40.0 parts of the intermediate (5-2), 600 parts of chloroform was added, and 7.0 parts of 2-hydroxyethylamine was added under ice cooling, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 1,000 parts of water, and the precipitated crystals were filtered, washed with water, and dried at 80°C for 24 hours to obtain the intermediate (5-3).

[0106] To 600 parts of methyl ethyl ketone, 40.0 parts of intermediate (5-3), 15.5 parts of 2-isocyanatoethyl methacrylate (Karends MOI, Showa Denko K.K.), and 0.08 parts of methylhydroquinone were added, and the mixture was heated to 70°C in an oxygen atmosphere and stirred for 4 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-5).

[0107] Monomer (a1-6) 41.6 parts of CI Acid Blue 25 and 500 parts of chloroform were added, and 14 parts of thionyl chloride was added under ice cooling, followed by stirring for 2 hours at 50° C. The reaction mixture was added to 800 parts of water in an ice bath, and the precipitated crystals were filtered to obtain the above intermediate (6-1).

[0108] To 40.0 parts of the intermediate (6-1), 600 parts of chloroform was added, and 7.0 parts of 2-hydroxyethylamine was added under ice cooling, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 1,000 parts of water, and the precipitated crystals were filtered, washed with water, and dried at 80°C for 24 hours to obtain the intermediate (6-2).

[0109] To 450 parts of methyl ethyl ketone, 40.0 parts of intermediate (6-2), 15.5 parts of 2-isocyanatoethyl methacrylate (Karends MOI, Showa Denko K.K.), and 0.08 parts of methylhydroquinone were added, and the mixture was heated to 70°C in an oxygen atmosphere and stirred for 4 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-6).

[0110] Monomer (a1-7) 45.8 parts of CI Acid Blue 129 and 500 parts of chloroform were added, and 14 parts of thionyl chloride was added under ice cooling, followed by stirring for 2 hours at 50° C. The reaction mixture was added to 800 parts of water in an ice bath, and the precipitated crystals were filtered to obtain the above intermediate (7-1).

[0111] To 42.0 parts of the intermediate (7-1), 600 parts of chloroform was added, and 7.0 parts of 2-hydroxyethylamine was added under ice cooling, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 1,000 parts of water, and the precipitated crystals were filtered, washed with water, and dried at 80°C for 24 hours to obtain the intermediate (7-2).

[0112] To 450 parts of methyl ethyl ketone, 42.0 parts of intermediate (7-2), 15.5 parts of 2-isocyanatoethyl methacrylate (Karends MOI, Showa Denko K.K.), and 0.08 parts of methylhydroquinone were added, and the mixture was heated to 70°C in an oxygen atmosphere and stirred for 4 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-7).

[0113] Monomer (a1-8) 54.4 parts of CI Acid Blue 1 and 500 parts of chloroform were added, and 14 parts of thionyl chloride was added under ice cooling, followed by stirring for 2 hours at 50° C. The reaction mixture was added to 800 parts of water in an ice bath, and the precipitated crystals were filtered to obtain the above intermediate (8-1).

[0114] To 52.0 parts of the intermediate (8-1), 600 parts of chloroform was added, and 7.0 parts of 2-hydroxyethylamine was added under ice cooling, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 1,000 parts of water, and the precipitated crystals were filtered, washed with water, and dried at 80°C for 24 hours to obtain the intermediate (8-2).

[0115] To 500 parts of methyl ethyl ketone, 52.0 parts of intermediate (8-2), 15.5 parts of 2-isocyanatoethyl methacrylate (Karends MOI, Showa Denko K.K.), and 0.08 parts of methylhydroquinone were added, and the mixture was heated to 70°C in an oxygen atmosphere and stirred for 4 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-8).

[0116] Monomer (a1-9) 57.6 parts of copper phthalocyanine was dissolved in 300 parts of 98% sulfuric acid and stirred at 85°C for 2 hours to carry out a sulfonation reaction. The reaction solution was then added dropwise to 3,000 parts of ice water, and the precipitated compound was filtered and washed with water to obtain a paste. The resulting paste was redispersed in 8,000 parts of water and stirred at room temperature for 1 hour. After filtering and washing, the mixture was dried at 80°C overnight to obtain the above intermediate (9-1).

[0117] 55.0 parts of the intermediate (9-1) was added to 500 parts of chloroform, and 14.0 parts of thionyl chloride was added under ice cooling, followed by stirring for 2 hours at 50° C. The reaction mixture was added to 800 parts of water in an ice bath, and the precipitated crystals were filtered to obtain the above intermediate (9-2).

[0118] To 53.0 parts of the intermediate (9-2), 600 parts of chloroform was added, and 7.0 parts of 2-hydroxyethylamine was added under ice cooling, followed by stirring at room temperature for 2 hours. The reaction mixture was added to 1,000 parts of water, and the precipitated crystals were filtered, washed with water, and dried at 80°C for 24 hours to obtain the intermediate (9-3).

[0119] To 600 parts of methyl ethyl ketone, 50.0 parts of intermediate (9-3), 15.5 parts of 2-isocyanatoethyl methacrylate (Karends MOI, Showa Denko K.K.), and 0.08 parts of methylhydroquinone were added, and the mixture was heated to 70°C in an oxygen atmosphere and stirred for 4 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-9).

[0120] Monomer (a1-10) Monomer (a1-10) was obtained in the same manner as for monomer (a1-9), except that zinc phthalocyanine was used instead of copper phthalocyanine.

[0121] Monomer (a1-11) To 600 parts of tetrahydrofuran, 50.0 parts of the intermediate (9-3) used in the synthesis of the monomer (a1-9), 20.0 parts of methacryloyl chloride, and 30.0 parts of triethylamine were added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain the monomer (a1-11).

[0122] Monomer (a1-12) In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1,250 parts of n-amyl alcohol and stirred. 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were added, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring and poured into a mixed solvent of 5,000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2,000 parts of methanol and 4,000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Next, 100 parts of chloroaluminum phthalocyanine was slowly added to 1,200 parts of concentrated sulfuric acid in a reaction vessel at room temperature. The mixture was stirred at 40°C for 3 hours, and the sulfuric acid solution was poured into 24,000 parts of cold water at 3°C. The blue precipitate was filtered, washed with water, and dried to obtain 92 parts of the above hydroxyaluminum phthalocyanine.

[0123] Next, 100 parts of the obtained hydroxyaluminum phthalocyanine and 49.5 parts of diphenyl phosphate were added to 1,000 parts of methanol in a reaction vessel, and the mixture was heated to 40° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain the above intermediate (12-1).

[0124] Monomer (a1-12) was obtained in the same manner as for monomer (a1-9), except that intermediate (12-1) was used instead of copper phthalocyanine.

[0125] Monomer (a1-13) In a reaction vessel, 100 parts of the obtained hydroxyaluminum phthalocyanine and 41.6 parts of 2-methacryloyloxyethyl acid phosphate (Light Ester P-1M, manufactured by Kyoeisha Chemical Co., Ltd.) were added to 1,000 parts of methanol, heated to 40°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain monomer (a1-13).

[0126] Monomer (a1-14) Monomer (a1-14) was obtained in the same manner as for monomer (a1-5), except that CI Basic Yellow 12 was used instead of Solvent Red 23.

[0127] Monomer (a1-15) Monomer (a1-15) was obtained in the same manner as for monomer (a1-5), except that pinacyanol iodide was used instead of Solvent Red 23.

[0128] Monomer (a1-16) Monomer (a1-15) was obtained in the same manner as for monomer (a1-5) using 2,4-bis[4-(diethylamino)-2-hydroxyphenyl]squaraine (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0129] Monomer (a1-17) To 58.0 parts of 2-[4-carboxy-7-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-1,3,5-heptatrien-1-yl]-1,3,3-trimethyl-3H-indolium iodide (Tokyo Chemical Industry Co., Ltd.), 600 parts of cyclohexanone, 15.0 parts of glycidyl methacrylate, 0.08 parts of methylhydroquinone, and 0.8 parts of dimethylbenzylamine were added, and the mixture was heated to 120°C in an oxygen atmosphere and stirred for 8 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-17).

[0130] Monomer (a1-18) Monomer (a1-18) was obtained in the same manner as for monomer (a1-9), except that CI Pigment Red 255 was used instead of Solvent Red 23.

[0131] Monomer (a1-19) 14.3 parts of 2-methylquinoline, 19.2 parts of trimellitic anhydride, 30 parts of benzoic acid, and 7.5 parts of methyl benzoate were mixed and heated to 200°C. After heating and stirring for 3 hours, the mixture was allowed to cool to 70°C, and 100 parts of methanol was added. After stirring at room temperature for 30 minutes, the mixture was filtered and washed with methanol. After drying under reduced pressure overnight, the above intermediate (19-1) was obtained.

[0132] To 30.0 parts of intermediate (19-1), 600 parts of cyclohexanone, 15.0 parts of glycidyl methacrylate, 0.08 parts of methylhydroquinone, and 0.8 parts of dimethylbenzylamine were added, and the mixture was heated to 120°C in an oxygen atmosphere and stirred for 8 hours. The reaction solution was added to 2000 parts of water, and the precipitated crystals were filtered, washed with water, and vacuum-dried at 50°C overnight to obtain monomer (a1-19).

[0133] Monomer (a1-20) Monomer (a1-20) was obtained in the same manner as for monomer (a1-5), except that CI Pigment Violet 23 was used instead of Solvent Red 23.

[0134] Monomer (a2-1) To 70.0 parts of CI Acid Red 289, 700 parts of N-methylpyrrolidone, 80.0 parts of 3-iodo-1-propanol, and 20.0 parts of potassium carbonate were added, and the mixture was heated to 80° C. and reacted for 4 hours. Thereafter, 2000 parts of water was added to precipitate crystals, thereby obtaining the intermediate (21-1).

[0135] The intermediate (21-1) was amidated with butylamine in the same manner as in the case of the monomer (a1-1) to obtain the monomer (a2-1).

[0136] Monomer (a2-2) Monomer (a2-2) was obtained in the same manner as for monomer (a1-1), except that azorubine was used instead of intermediate (1-1).

[0137] Monomer (a2-3) 1,4-Diaminoanthraquinone was used.

[0138] Monomer (a2-4) 48.0 parts of pianal iodide was dissolved in 200 parts of 98% sulfuric acid and 200 parts of 25% fuming sulfuric acid, and the mixture was stirred at 85°C for 4 hours to carry out a sulfonation reaction. The reaction solution was then added dropwise to 3,000 parts of ice water, and the precipitated compound was filtered and washed with water to obtain a paste. The resulting paste was redispersed in 8,000 parts of water and stirred at room temperature for 1 hour. After filtering and washing, the mixture was dried at 80°C overnight to obtain the above intermediate (24-1).

[0139] Monomer (a2-4) was obtained in the same manner as for monomer (a1-1), except that intermediate (24-1) was used instead of intermediate (1-1).

[0140] Monomer (a2-5) Monomer (a2-5) was obtained in the same manner as for monomer (a2-4), except that CI Basic Red 12 was used instead of pianal iodide.

[0141] Monomer (a2-6) Monomer (a2-6) was obtained in the same manner as for monomer (a2-4), except that CI Pigment Red 255 was used instead of pianal iodide.

[0142] Monomer (a2-7) Monomer (a2-7) was obtained in the same manner as for monomer (a2-4), except that CI Pigment Violet 23 was used instead of pianal iodide.

[0143] <Resin manufacturing> [Example 1] (Resin (R1-1)) A four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 50.0 parts of cyclohexanone, 85.0 parts of monomer (a1-1), and 15.0 parts of benzyl methacrylate. The mixture was heated to 80 °C under a nitrogen stream, and a solution of 2.8 parts of 3-mercapto-1,2-propanediol and 0.3 parts of 2,2'-azobisisobutyronitrile dissolved in 10.0 parts of cyclohexanone was added and reacted for 10 hours. The mixture was then cooled, the nonvolatile content was measured, and cyclohexanone was added to adjust the nonvolatile content to 20% to obtain resin (R1-1). GPC analysis confirmed that more than 95% of the raw materials had reacted.

[0144] [Examples 2 to 33, Comparative Examples 1 to 4] (Resin (R1-2) to (R1-37)) Resins (R1-2) to (R1-37) shown in Table 1 were produced in the same manner as for resin (R1-1). Resins (R1-2) to (R1-37) were adjusted to have a nonvolatile content of 20%, similar to resin (R1-1). The notation in Table 1 is as follows: EHMA: 2-ethylhexyl methacrylate BzMA: benzyl methacrylate St: styrene HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid OXMA: (3-ethyloxetan-3-yl)methyl methacrylate (OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd.) tBMA: tertiary butyl methacrylate

[0145] [Table 1]

[0146] (Resin (R2-1)) A four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 200.0 parts of cyclohexanone, 0.20 moles of monomer (a2-1), and 0.20 moles of isophorone diisocyanate. The mixture was heated to 100°C under a nitrogen stream, and 0.20 mmol of dibutyltin dilaurate was added and reacted for 5 hours. After cooling, the nonvolatile content was measured, and cyclohexanone was added to adjust the nonvolatile content to 20% to obtain resin (R2-1). GPC analysis confirmed that more than 95% of the raw materials had reacted.

[0147] [Examples 34 to 42, Comparative Example 10] (Resin (R2-2)~(R2-9), (R2-12)) Resins (R2-2) to (R2-9) and (R2-12) were produced as shown in Table 2 in the same manner as for resin (R2-1).

[0148] [Example 43] (Resin (R2-10)) A four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 0.20 mol of monomer (a2-1) and 0.20 mol of terephthalic acid. The mixture was heated to 230°C under a nitrogen stream and allowed to react for 5 hours while dehydrating. After cooling, the nonvolatile content was measured, and cyclohexanone was added to adjust the nonvolatile content to 20% to obtain resin (R2-10). GPC analysis confirmed that more than 95% of the raw materials had reacted.

[0149] [Example 44] (Resin (R2-11)) Resin (R2-11) was produced in the same manner as Resin (R2-10), as shown in Table 2.

[0150] [Table 2]

[0151] [Example 45] (Resin (R3-1)) A four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 200.0 parts of cyclohexanone, 82.6 parts of monomer (a2-1), 44.4 parts of isophorone diisocyanate, and 1982.6 parts of resin (R1-13). The mixture was heated to 100°C under a nitrogen stream, and 0.13 parts of dibutyltin dilaurate was added and reacted for 5 hours. After cooling, the nonvolatile content was measured, and cyclohexanone was added to adjust the nonvolatile content to 20% to obtain resin (R3-1). GPC analysis confirmed that more than 95% of the raw materials had reacted.

[0152] Resins (R1-1) to (R1-37) are resins containing structural units represented by general formula (1), resins (R2-1) to (R2-11) are resins containing structural units represented by general formula (2), and resin (R3-1) is a resin containing both structural units represented by general formula (1) and structural units represented by general formula (2). The composition of R3-1 is shown in Table 3.

[0153] [Table 3]

[0154] <Molar absorption coefficients of the structural unit represented by general formula (1) and the structural unit represented by general formula (2)> The maximum molar absorption coefficient in the range of 400 to 780 nm was calculated for the case containing the structural unit represented by general formula (1) and the structural unit represented by general formula (2).

[0155] (When containing a structural unit represented by general formula (1)) In the case of a resin containing a structural unit represented by general formula (1), the monomer (a) is synonymous with the structural unit of general formula (1), and the weight ratio of the monomer (a) is the weight ratio of the structural unit of general formula (1) in the total mass. Furthermore, when the structural unit represented by general formula (1) is contained, the maximum molar absorption coefficient in the range of 400 to 780 nm is the maximum molar absorption coefficient in the range of 400 to 780 nm of the monomer (a).

[0156] Therefore, the monomers (a1-1) to (a1-20) were dissolved in N-methylpyrrolidone to a concentration of 0.1 mmol / L, and the absorption spectrum was measured using an absorptiometer. The maximum absorbance value in the range of 400 to 780 nm was determined, and by multiplying this value by 10,000, the maximum molar extinction coefficient in the range of 400 to 780 nm was calculated. Since the structural unit represented by general formula (1) is synonymous with the monomer (a), this value indicates the maximum molar absorption coefficient in the range of 400 to 780 nm when the structural unit represented by general formula (1) is contained. The following evaluation was made regarding this. A:2000L / (mol·cm) or more B: Less than 2000 L / (mol cm) The results are shown in Table 4.

[0157] [Table 4]

[0158] (When containing a structural unit represented by general formula (2)) In the case of a resin containing a structural unit represented by general formula (2), the structural unit of general formula (2) corresponds to a structure in which a monomer (a) and a monomer that reacts with the monomer (a) are bonded together. When the structural unit represented by general formula (2) is contained, the maximum value ε of the molar absorption coefficient in the range of 400 to 780 nm is calculated by the following formula.

[0159] (Formula)ε=UM×pAbs / K UM: Molecular weight of the structural unit represented by general formula (2) K (%): Ratio of structural units represented by general formula (2) to the total mass pAbs: The maximum absorbance value from 400 to 780 nm when the absorption spectrum of a resin containing a structural unit represented by general formula (2) is measured in a 0.01 g / L solution. pAbs were measured in NMP solution. This value was evaluated as follows. A:2000L / (mol·cm) or more B: Less than 2000 L / (mol cm)

[0160] In the case of resin (R2-1), the structural unit represented by general formula (2) corresponds to a structure in which monomer (a2-1) and isophorone diisocyanate are bonded, and the proportion of the structural unit represented by general formula (2) in the total mass is 100%. In other words, K is 100. Furthermore, since the molecular weight of monomer (a2-1) is 826 and the molecular weight of isophorone diisocyanate is 222, the molecular weight UM of the structural unit represented by general formula (2) is 1048. The pAbs was determined by dissolving the resin (R2-1) in N-methylpyrrolidone at 0.01 g / L, measuring the absorption spectrum with an absorptiometer, and determining the maximum absorbance value between 400 and 780 nm. The pAbs was 0.72. From this, the maximum value ε of the molar absorption coefficient in the range of 400 to 780 nm when the structural unit represented by general formula (2) was calculated to be 75456. The same calculation was carried out for resins (R2-4) to (R2-9). The results are shown in Table 5.

[0161] [Table 5]

[0162] <Resin evaluation> The synthesized resins were evaluated as follows.

[0163] [Example 1] Resin (R1-1) was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater while adjusting the rotation speed, and after drying at 100°C for 10 minutes, a substrate was obtained on which a film with a thickness of 1.0 μm had been formed. The absorption spectrum of the coating film on this substrate was measured using an absorptiometer, and the following items were evaluated.

[0164] (Maximum absorbance between 400 and 780 nm) 〇++: 3.0 or higher 〇+: 2.0 or more and less than 3.0 〇: 1.0 or more and less than 2.0 ×: Less than 1.0

[0165] (Absorbance at 820 nm) 〇+: Less than 0.1 ○: Less than 0.3 ×: 0.3 or more

[0166] (refractive index) Next, spectroscopic ellipsometry was performed on this substrate to determine the refractive index at 850 nm, 940 nm, and 1550 nm.

[0167] (transparency) The haze of the substrate on which the above-mentioned film having a thickness of 1.0 μm was formed was measured with a haze meter to determine the transparency. Good: Haze is less than 0.5 △: Haze is 0.5 or more and less than 1.0 ×: Haze is 1.0 or more

[0168] [Examples 2 to 45, Comparative Examples 1 to 10] The same evaluations as in Example 1 were also carried out for resins (R1-2) to (R1-35), resins (R2-1) to (R2-11), and resin (R3-1). These results are shown in Tables 6, 7 and 8.

[0169] [Table 6]

[0170] [Table 7]

[0171] [Table 8]

[0172] Comparative Examples 5 to 9 were carried out as follows. Comparative Example 5 For the following comparative colorant 1, the colorant was not dissolved, but was applied to a glass substrate in the same manner as in Example 1, and the absorption spectrum was measured for evaluation, and the refractive index was measured. (Comparative colorant 1) [ka] Comparative Example 6 For the following comparative colorant 2, the colorant was not dissolved, but was applied to a glass substrate in the same manner as in Example 1, and the absorption spectrum was measured for evaluation, and the refractive index was measured. (Comparative colorant 2) [ka] Comparative Example 7 The comparative colorant 2 was mixed with a resin in the following blending ratio, and a film was formed on a glass substrate in the same manner as in Example 1. The absorption spectrum was measured and evaluated, and the refractive index was measured. Comparison color material 2: 1.0g 9,9-bis[4-(2-(acryloyloxyethoxy)phenyl)fluorene]: 1.0g Chloroform: 100g [Comparative Example 8] A mixture of the following composition was stirred and mixed uniformly, then dispersed in an Eiger mill using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a pigment composition. ε-copper phthalocyanine: 10.0 parts DISPERBYK103 (BYK Chemie Co., Ltd.): 25.0 parts PGMAc (methoxypropyl acetate): 65.0 parts The average primary particle size of the ε-copper phthalocyanine was 50 nm. A film was formed on a glass substrate using the obtained pigment composition in the same manner as in Example 1, and the absorption spectrum was measured for evaluation, and the refractive index was measured. Comparative Example 9 Chloroaluminum phthalocyanine was used in place of the ε-copper phthalocyanine of Comparative Example 8, and the absorption spectrum was measured and judged in the same manner as in Comparative Example 8, and the refractive index was measured. The chloroaluminum phthalocyanine had an average primary particle size of 50 nm.

[0173] <Production of Resin Composition> [Example 46] To 10 g of resin (R1-19), 0.30 g of isophorone diisocyanate (IPDI) as a curing agent was added, and then 1.2 g of cyclohexanone was added and mixed to prepare a resin composition (RR1-1).

[0174] <Evaluation of Resin Composition> The resin composition (RR1-1) was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater while adjusting the rotation speed, and after drying at 100°C for 10 minutes, a substrate was obtained on which a film with a thickness of 1.0 μm was formed. The absorption spectrum of the coating film on this substrate was measured using an absorptiometer, and the following items were evaluated.

[0175] (Maximum absorbance between 400nm and 780nm) 〇++: 3.0 or higher 〇+: 2.0 or more and less than 3.0 〇: 1.0 or more and less than 2.0 ×: Less than 1.0

[0176] (Absorbance at 820 nm) 〇+: Less than 0.1 ○: Less than 0.3 ×: 0.3 or more

[0177] (refractive index) Next, spectroscopic ellipsometry was performed on this substrate to determine the refractive index at 850 nm, 940 nm, and 1550 nm.

[0178] (chemical resistance) The substrate on which the aforementioned 1.0 μm-thick film was formed was subjected to a heat treatment at 200°C for 5 minutes, and then rubbed 50 times with a hammer wrapped in gauze swollen with methyl ethyl ketone, and the coating surface was observed. The chemical resistance test was judged as follows: 〇: The coating is intact. △: Part of the coating film peels off. ×: The coating film is completely dissolved.

[0179] (transparency) The haze of the substrate on which the above-mentioned film having a thickness of 1.0 μm was formed was measured with a haze meter to determine the transparency. Good: Haze is less than 0.5 △: Haze is 0.5 or more and less than 1.0 ×: Haze is 1.0 or more

[0180] [Examples 47 to 49] As shown in Table 9, resin compositions were obtained in the same manner as in Example 46, and the absorbance, refractive index, chemical resistance, and transparency were evaluated. In Example 47, Denacol EX-321 (trimethylolpropane polyglycidyl ether manufactured by Nagase ChemteX Corporation) was used as the curing agent. In Examples 48 and 49, the chemical resistance of resins (R1-6) and (R1-7) was evaluated without adding a curing agent. The results are shown in Table 9.

[0181] [Table 9]

[0182] As described above, the resin of the present invention has a particularly high refractive index in the wavelength region of 800 to 1600 nm and can be formed into a film with excellent transparency and chemical resistance, and is therefore useful in optical material applications, particularly in optical lenses and optical waveguides.

Claims

1. A resin for optical materials used in infrared sensors or infrared communication devices, The refractive index at 23°C and a wavelength of 850 nm is 1.65 or more, A resin that satisfies the following (1) and (2) when a film having a thickness of 1.0 μm is formed. (1) The maximum absorbance in the range of 400 to 780 nm is 1.0 or more. (2) Absorbance at 820 nm is less than 0.3

2. The resin according to claim 1, comprising a structural unit represented by the following general formula (1) and / or a structural unit represented by the following general formula (2): General formula (1) 【Chemical 1】 (In general formula (1), A １ is a residue of a compound having absorption in the range of 400 to 780 nm, and the maximum molar absorption coefficient of the structural unit represented by general formula (1) in the range of 400 to 780 nm is 2000 L / (mol cm) or more. １ is a divalent linking group. １１１ is a hydrogen atom or a methyl group. General formula (2) 【Chemistry 2】 (In general formula (2), A ２ is a residue of a compound having absorption in the range of 400 to 780 nm, and the maximum molar absorption coefficient of the structural unit represented by general formula (2) in the range of 400 to 780 nm is 2000 L / (mol cm) or more. ２ is a divalent linking group.

3. The resin according to claim 2, wherein the structural unit represented by the general formula (1) and / or the structural unit represented by the general formula (2) accounts for 65 mass % or more of the total mass of the resin.

4. A in the general formula (1) １ and / or A in the general formula (2) ２ is at least one residue selected from the group consisting of a xanthene residue, a cyanine residue, a phthalocyanine residue, a naphthalocyanine residue, a squarylium residue, a diketopyrrolole residue, an anthraquinone residue, a dioxazine residue, a dipyrromethene residue, a quinophthalone residue, and an azo residue.

5. The resin according to any one of claims 1 to 4, which is used to form an optical lens or an optical waveguide.

6. A resin composition comprising the resin according to any one of claims 1 to 5, a curing agent, and a solvent.

7. A film comprising the resin according to any one of claims 1 to 5 or the resin composition according to claim 6.

8. An optical material comprising the resin according to any one of claims 1 to 5 or the resin composition according to claim 6.

9. An optical lens comprising the resin according to any one of claims 1 to 5 or the resin composition according to claim 6.

10. An optical waveguide comprising the resin according to any one of claims 1 to 5 or the resin composition according to claim 6.

11. An infrared sensor or infrared communication device comprising the film according to claim 7, the optical material according to claim 8, the optical lens according to claim 9, or the optical waveguide according to claim 10.

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