Composition, optical member, and method for manufacturing them

Abstract

To provide a composition which is excellent in dispersibility of a light absorber, an optical member which is excellent in surface uniformity of optical characteristics, and a method for manufacturing them.SOLUTION: A composition contains a phosphonic acid, a dispersant, a light absorber formed of copper ions, a resin, and an organic solvent, wherein at least a part of the light absorber is coupled to the resin.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a composition, an optical member, and a method for producing the same. [Background technology]

[0002] Digital cameras and the like use imaging elements such as CCD and CMOS. Since these imaging elements are sensitive to near-infrared light, near-infrared absorbing film is placed on the light-receiving surface side of the imaging element to block near-infrared light. As a near-infrared absorbing film, for example, a film in which a near-infrared absorbing agent is dispersed in a resin is known.

[0003] For example, Patent Document 1 discloses a specific liquid composition for optical filters that contains a light absorber formed from a specific phosphonic acid having an aryl group and copper ions, an alkoxysilane, etc., and a phosphoric acid ester as a composition capable of suppressing aggregation of the light absorber.

[0004] Furthermore, Patent Document 2 discloses a composition for optical filters that contains a specific phosphonic acid or sulfonic acid, a phosphate ester, an alkoxysilane, and copper ions and has a viscosity of 1 to 200 mPa s, as a composition that can form an optical filter having a desired haze. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2020-24447 A [Patent Document 2] JP 2020-64315 A Summary of the Invention [Problem to be solved by the invention]

[0006] In view of film-forming properties, optical filters usually contain a light absorbent and a resin. The optical filter and the composition for manufacturing the optical filter are required to have the light absorbent uniformly dispersed in the resin. On the other hand, in order to ensure optical properties, the optical filter is required to have a certain degree of thickness, and the composition is required to have a certain degree of viscosity, such as a paste.

[0007] An object of the present disclosure is to provide a composition having excellent dispersibility of a light absorbent, an optical member having excellent surface uniformity of optical properties, and methods for producing the same. [Means for solving the problem]

[0008] A composition according to one embodiment of the present disclosure comprises: a light absorber formed by a phosphonic acid, a dispersant, and copper ions; Contains a resin and an organic solvent, At least a portion of the light absorbing agent is bonded to the resin.

[0009] A method for producing a composition according to one embodiment of the present disclosure includes the steps of: A method for producing any of the above compositions, comprising the steps of: The method includes preparing a mixed solution of the light absorbent and the resin, and heating the mixed solution at 80° C. or higher.

[0010] The optical member according to one embodiment of the present disclosure comprises: a light absorber formed by a phosphonic acid, a dispersant, and copper ions; A resin, At least a portion of the light absorbing agent is bonded to the resin. Effect of the Invention

[0011] The present disclosure can provide a composition having excellent dispersibility of a light absorbent, an optical member having excellent surface uniformity of optical properties, and a method for producing the same. [Brief description of the drawings]

[0012] [Figure 1]1 is a spectral transmittance spectrum of the coating film of Example 1. [Diagram 2] 1 is a spectral transmittance spectrum of the coating film after the humidity resistance test in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The composition, optical member, and production method thereof according to the present disclosure will be described below in order. In this disclosure, a "compound represented by formula (1)" may be referred to as a "compound (1)". A "group represented by formula (2)" may be referred to as a "group (2)". The same applies to other compounds. In the present disclosure, "curing" includes curing via a crosslinking reaction as well as curing (solidification) resulting from removal of the solvent. Furthermore, unless otherwise specified, the symbol "~" indicating a numerical range includes the lower limit and the upper limit.

[0014] [Composition] The composition of the present disclosure is characterized in that it contains a light absorber formed by phosphonic acid, a dispersant, and copper ions, a resin, and an organic solvent, and at least a portion of the light absorber is bonded to the resin.

[0015] A light absorbent containing phosphonic acid has a problem that the light absorbent is bonded to itself, aggregates, and the dispersibility is reduced. In the composition of the present disclosure, the light absorbent is bonded to the resin, and aggregation is suppressed, and a composition with excellent dispersibility is obtained. Therefore, the dispersibility of the light absorbent can be improved even if the light absorbent is, for example, a high concentration, and the amount of organic solvent used can be reduced, and the light absorbent is excellent in dispersibility even in a paste form. When the light absorbing agent is used to form an optical member, it is easy to adjust the optical characteristics and the thickness of the coating film, and it is possible to easily manufacture an optical member having desired optical characteristics. In addition, the obtained optical member has excellent surface uniformity of optical performance. The bonding site between the light absorber and the resin is not particularly limited, but in terms of ease of synthesis, spectroscopic characteristics, etc., it is preferable that the phosphonic acid constituting the light absorber is bonded to the OH group of the resin by a chemical reaction. Examples of the OH group of the resin include a hydroxyl group (-COH) and a silanol group (-SiOH), and the silanol group may be protected by an alkyl group, etc.

[0016] The composition of the present disclosure contains at least a light absorbent, a resin, and an organic solvent, and may further contain other compounds, etc., within the scope of the effects of the present invention. Each component will be described below.

[0017] <Phosphonic acid> The phosphonic acid can be appropriately selected from the viewpoint of the optical properties of the light absorbent, and one type can be used alone or two or more types can be used in combination. From the viewpoint of the infrared absorbing ability of the light absorbent, the phosphonic acid is preferably a compound represented by the following formula (3).

[0018] [ka] however, R 21 -R 33 , -Ar 31 , -OR 33 , -OAr 31 , -OR 34 -Ar 31 , -OCOR 33 , or -OCOAr 31 and R 33 represents an alkyl group which may have a substituent, Ar 31 represents an aryl group which may have a substituent, R 34 is an alkylene group which may have a substituent.

[0019] R 33From the viewpoints of compatibility with resins and optical properties, the alkyl group is preferably a linear or branched alkyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, and even more preferably 1 to 12 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, and a hexyl group. The alkyl group may be substituted with a hydrogen atom. Examples of the substituent include a halogen atom and a hydroxyl group. Examples of the halogen atom include F, Cl, Br, and I.

[0020] Ar 1 is an aryl group which may have a substituent. The aryl group is a residue obtained by removing one hydrogen atom from a monocyclic or bicyclic to hexacyclic polycyclic aromatic hydrocarbon. From the viewpoint of improving the visible light transmittance, the aryl group is preferably a monocyclic or bicyclic to tricyclic polycyclic aromatic hydrocarbon, and more preferably a phenyl group or a naphthyl group. The aryl group may further be substituted with a hydrogen atom. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, and a hydroxyl group. The alkyl group in the substituent may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, and the hydrogen atom may be substituted with a halogen atom or a hydroxyl group.

[0021] R 4 In terms of compatibility with resins and optical properties, the alkylene group is preferably a straight-chain alkylene group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group. The alkylene group may have a hydrogen atom substituted therein. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, and a hydroxyl group. The alkyl group in the substituent may be straight-chain or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, and the hydrogen atom may be substituted therein with a halogen atom or a hydroxyl group.

[0022] Specific examples of phosphonic acids include methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid, tridecylphosphonic acid, tetradecylphosphonic acid, pentadecylphosphonic acid, hexadecylphosphonic acid, heptadecylphosphonic acid, and octadecylphosphonic acid.

[0023] <Dispersant> In the present disclosure, a dispersant is a compound that constitutes a part of the light absorber and improves the dispersibility of the light absorber. The dispersant may affect the spectral properties of the light absorber. From the viewpoints of dispersibility and dispersion stability of the light absorbent, compatibility with the resin, and infrared absorbing ability of the light absorbent, the dispersant preferably contains a compound represented by the following formula (1).

[0024] [ka] however, R 1 is a group represented by the following formula (2): R 2 is a hydroxyl group, -R 3 , -Ar 1 , -OR 3 , -OAr 1 , -OR 4 -Ar 1 , -OCOR 3 , -OCOAr 1 , -R 4 -N(R 5 )2, or -R 1 and R 3 represents an alkyl group which may have a substituent, Ar 1 represents an aryl group which may have a substituent, R 4 represents an alkylene group which may have a substituent, R 5represents a hydrogen atom or an alkyl group which may have a substituent, [ka] R 10 represents an alkylene group which may have a substituent or an arylene group which may have a substituent, R 11 represents a single bond or an alkylene group which may have a substituent, R 12 represents an alkylene group which may have a substituent, or an arylene group which may have a substituent, provided that R 13 R binds to 12 is a single bond, R 13 is a hydrogen atom, -R 14 , or -R 15 OH, R 14 represents an alkyl group which may have a substituent, R 15 represents a single bond or an alkylene group which may have a substituent, n is an integer equal to or greater than 1, * is a bond to P, When a formula contains a plurality of the same symbols, the plurality of the same symbols may represent the same group or different groups.

[0025] The compound (1) has a structure in which one or two groups containing a polyester represented by formula (2) are bonded to a phosphorus atom. It is presumed that the light absorber exists as a complex in which the compound (1) is coordinated to a copper ion. Therefore, it is presumed that the group (2) is easily arranged on the outside of the copper ion in the light absorber, which improves compatibility with various resins and provides a light absorber with excellent dispersibility.

[0026] R in formula (1) 1 is group (2). R in group (2) 11 R is a single bond or an alkylene group which may have a substituent. 11 When is a single bond, the O atom is bonded to the P atom of formula (1). R 11 When is an alkylene group, R 11 The C atom in the formula (1) is bonded to the P atom in the formula (1). R 11 In terms of compatibility with resins and ease of synthesis, the alkylene group is preferably a straight-chain alkylene group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group. The alkylene group may have a hydrogen atom substituted therein. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, and a hydroxyl group. The alkyl group in the substituent may be straight-chain or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, and the hydrogen atom may be substituted therein with a halogen atom or a hydroxyl group. Examples of halogen atoms include F, Cl, Br, and I.

[0027] R 10 and R 12 each independently represents an alkylene group which may have a substituent, an arylene group which may have a substituent, or a group consisting of a combination thereof. The alkylene group which may have a substituent is the same as R 11 Examples of the above-mentioned compounds include those described in the above. In the arylene group which may have a substituent, the arylene group is a residue obtained by removing two hydrogen atoms from a monocyclic or bicyclic to hexacyclic polycyclic aromatic hydrocarbon. From the viewpoint of improving the visible light transmittance, the arylene group is preferably a monocyclic or bicyclic to tricyclic polycyclic aromatic hydrocarbon, and more preferably a phenylene group or a naphthylene group. The position of the hydrogen atom to be removed in the arylene group (the position to which the ester is bonded) is not particularly limited. In the case of a phenylene group, the position may be any of the ortho position, meta position, and para position, but the para position is preferred from the viewpoint of availability of raw materials and stability of the compound. In the case of a naphthylene group, the 2,6 position, 1,5 position, 1,4 position, 2,3 position, or 2,7 position is preferred from the viewpoint of stable posture of the compound. The arylene group may further be substituted with a hydrogen atom. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, and a hydroxyl group. 11 The substituents are the same as those in the above. Examples of groups consisting of a combination of an alkylene group which may have a substituent and an arylene group which may have a substituent include structures such as *-alkylene group-arylene group-*, *-arylene group-alkylene group-arylene group, and *-alkylene group-arylene group-alkylene group-*, and specific examples include groups represented by the following formulae (A1) and (A2), where * represents a bond to an ester.

[0028] [ka]

[0029] R 10 From the viewpoint of improving compatibility with the resin, preferably is an arylene group or a group formed from a combination of an alkylene group and an arylene group, and more preferably is an arylene group. R 12 From the viewpoint of imparting flexibility to the group (2) and improving compatibility, is preferably an alkylene group or a group formed from a combination of an alkylene group and an arylene group, and more preferably an alkylene group.

[0030] R 13 represents the end of group (2), and is a hydrogen atom or -R 14 , -R 15 OH. Also, the R 14 is an alkyl group which may have a substituent, 15 represents a single bond or an alkylene group which may have a substituent. R 14From the viewpoints of compatibility with resins and ease of synthesis, the alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, and a hexyl group. The alkylene group may be substituted with a hydrogen atom. Examples of the substituent include a halogen atom and a hydroxyl group. R 15 The alkylene group which may have a substituent is the above R 11 Examples of the above-mentioned compounds include those described in the above.

[0031] In formula (2), n is the number of repeating units. n may be 1 or more, and may be appropriately adjusted depending on the resin to be combined. From the viewpoint of the infrared absorbing ability of the light absorbent, n is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. From the viewpoint of compatibility with the resin, n may be 1 or more, and sufficient compatibility is observed even when n is 1.

[0032] The (partial) molecular weight of group (2) may be appropriately adjusted depending on the resin to be combined, etc. From the viewpoint of the infrared absorbing ability of the light absorbent, the molecular weight of group (2) is preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less. On the other hand, from the viewpoint of compatibility with the resin, the molecular weight of group (2) is preferably 150 or more, more preferably 200 or more.

[0033] R in Equation (1) 2 is a hydroxyl group, -R 3 , -Ar 1 , -OR 3 , -OAr 1 , -OR 4 -Ar 1 , -OCOR 3 , -OCOAr 1 , -R 4 -N(R 5 )2, or -R 1 In addition, the above-mentioned R 3 is an alkyl group which may have a substituent, 1is an aryl group which may have a substituent, 4 is an alkylene group which may have a substituent, 5 represents a hydrogen atom or an alkyl group which may have a substituent. R 2 R 1 In the case of (1), compound (1) has two groups (2). The two groups (2) in one molecule may be the same or different. The structure of group (2) is as described above. R 3 The alkyl group which may have a substituent in R 14 Examples of the above-mentioned compounds include those described in the above.

[0034] Ar 1 is an aryl group which may have a substituent. The aryl group is a residue obtained by removing one hydrogen atom from a monocyclic or bicyclic to hexacyclic polycyclic aromatic hydrocarbon. From the viewpoint of improving the visible light transmittance, the aryl group is preferably a monocyclic or bicyclic to tricyclic polycyclic aromatic hydrocarbon, and more preferably a phenyl group or a naphthyl group. The aryl group may further be substituted with a hydrogen atom. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, and a hydroxyl group. Specific examples of the substituent include the above-mentioned R 11 The substituents are the same as those in the above.

[0035] R 4 The alkylene group which may have a substituent is the above R 11 Examples of the above-mentioned compounds include those described in the above. R 5 R is a hydrogen atom or an alkyl group which may have a substituent. 5 The alkyl group which may have a substituent in R 14 Examples of the above-mentioned compounds include those described in the above.

[0036] The compound (1) may be used alone or in combination of two or more types of compound (1) having different substituents.

[0037] <Copper ions> The light absorber contains copper ions, which are preferably supplied from a copper compound capable of producing copper ions (also referred to as a copper ion source). The copper ion source is preferably a dissociable copper compound (copper salt). The copper compound may contain either a monovalent copper ion or a divalent copper ion, and among these, a copper salt capable of supplying a divalent copper ion is preferred. Examples of copper compounds include organic salts such as copper acetate, copper citrate, copper gluconate, anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous copper ethylacetoacetate, anhydrous copper pyrophosphate, anhydrous copper naphthenate, anhydrous copper citrate, and copper acetylacetonate, or hydrates of the organic salts; inorganic salts such as copper oxide, copper chloride, copper bromide, copper iodide, copper sulfate, copper nitrate, and basic copper carbonate, or hydrates of the inorganic salts. The copper ion sources can be used alone or in combination of two or more.

[0038] The molar ratio of the total number of moles (T) of the dispersant and the phosphonic acid to the copper ions (T / copper ions) is preferably 1-6. The molar ratio of the dispersant to the phosphonic acid (dispersant / phosphonic acid) is preferably from 15 to 1, and more preferably from 10 to 1, from the viewpoints of compatibility and infrared absorbing ability. The molar ratio of the dispersant to the copper ions (dispersant / copper ions) is preferably from 1 / 4 to 4 / 1, and more preferably from 1 / 2 to 2 / 1. If the molar ratio of the dispersant to the copper ions is equal to or greater than the lower limit, the copper ions coordinated with one or more dispersants become the main component of the light absorber, and therefore, if the molar ratio is equal to or greater than the lower limit, the light absorber has excellent compatibility with the resin. Although not limited thereto, it has been observed that the dispersant is monodentate or bidentate with respect to the copper ion.

[0039] <Method of manufacturing light absorber> The method for producing the light absorber is not particularly limited. For example, a method of preparing a solution containing a copper ion source, a dispersant, and phosphonic acid, and reacting the copper ions, the dispersant, and the phosphonic acid in the solution can be mentioned. By the above method, the light absorber can be obtained in a good yield by a simple method.

[0040] The solvent may be appropriately selected from among solvents capable of dissolving or dispersing the copper ion source, the dispersant, and the phosphonic acid. Examples of the solvent include aromatic compounds such as benzene, toluene, and xylene; alcohols such as methanol, ethanol, and propanol; glycol ethers such as methyl cellosolve and ethyl cellosolve; ethers such as diethyl ether, diisopropyl ether, and dibutyl ether; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; and hydrocarbon solvents such as hexane. The solvent may be a single solvent or a mixture of two or more solvents. In the present production method, a mixed solvent of alcohols and the above aromatic compounds is preferred. A cyclic ester solvent such as γ-butyrolactone may also be added.

[0041] The copper ion source, the dispersant, and the phosphonic acid can be added to the above-mentioned solvent, and reacted by heating. The reaction conditions are not particularly limited, and the complex is formed, for example, by heating and stirring at 40 to 120°C for about 1 to 24 hours. After the reaction, the solution may be heated or otherwise purified to remove the solvent, if necessary. The light absorber can be suitably produced by the above-mentioned method.

[0042] The dispersant compound (1) can be synthesized, for example, according to the following scheme 1.

[0043] [ka] However, R 22 is R of compound (1). 13 is equivalent to.

[0044] In the above scheme 1, a dicarboxylic acid (compound (11)) and an alcohol (compound (12)) are dehydration-condensed to synthesize compound (21) (step (i)), and then the compound (21) is reacted with tetraphosphorus decaoxide (diphosphorus pentaoxide; compound (13) to obtain compound (2A) corresponding to compound (1) (step (ii)). Note that the reaction conditions for each step may be determined by referring to the reaction conditions for known dehydration-condensation reactions and reactions of alcohols and diphosphorus pentaoxide.

[0045] Furthermore, when synthesizing a compound (1) in which n is 2 or more, compound (12) in the above scheme 1 may be changed to a dialcohol (compound (14)) (see the following scheme 2).

[0046] [ka] However, R 23 is R of compound (1). 12 and the terminal R 23 OH is R of compound (1). 13 is equivalent to.

[0047] <Resin> The resin in the composition is a matrix resin in the optical member described later, and can be appropriately selected depending on the application of the optical member. The resin may be any of a thermoplastic resin, a thermosetting resin, and a photocurable resin. When a thermosetting resin is used, it is preferable that a thermosetting reaction does not occur when the light absorbent and the resin are bonded together. Resins that can be suitably used in the present composition include, for example, polyimide resin, polyester resin, acrylic resin, epoxy resin, polyurethane resin, silicone resin, cellulose resin, polycarbonate resin, polyethylene terephthalate (PET) resin, polycarbonate resin (PC), cycloolefin copolymer (COP), and the like. Among these, acrylic resin, epoxy resin, silicone resin, cellulose resin, polyimide resin, polycarbonate resin, and cycloolefin polymer are preferred, and acrylic resin, silicone resin, cellulose resin, and polyimide resin are more preferred from the viewpoint of better compatibility, and cellulose resin and silicone resin containing OH groups are more preferred from the viewpoint of better bonding with resins, and cellulose resin is further preferred from the viewpoint of impact resistance.

[0048] Specific examples of the cellulose resin include cellulose; cellulose esters such as acetyl cellulose and butyryl cellulose; cellulose ethers such as methyl cellulose and ethyl cellulose; carboxymethyl cellulose, nitrocellulose, etc., and these preferably have a hydroxyl group. Examples of silicone resins include resins having a siloxane bond as the main skeleton, such as organopolysiloxane, epoxy-modified silicone resin, polyester-modified silicone resin, alkyd-modified silicone resin, urethane-modified silicone resin, acrylic-modified silicone resin, etc. The silicone resin preferably has a silanol group.

[0049] In addition, from the viewpoint of further improving compatibility, the weight average molecular weight of the resin is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. Although there is no particular lower limit to the weight average molecular weight of the resin, from the viewpoint of the mechanical strength of the optical member, it is usually 1,000 or more, and preferably 2,000 or more.

[0050] <Organic solvent> The present composition contains an organic solvent from the viewpoints of facilitating kneading of the resin and the light absorbent, coatability, etc. The organic solvent may be appropriately selected based on the affinity with the resin, the viscosity required for the composition, etc. Examples of solvents capable of dissolving cellulose resins include solvents with a relative dielectric constant of 8 or more, such as N,N-dimethylformamide (DMF), methyl ethyl ketone (MEK), dichloromethane, and ethanol. In this disclosure, the relative dielectric constant is a value measured at 25° C. Examples of solvents capable of dissolving silicone resins include toluene, xylene, methoxybenzene, chloroform, acetone, methyl isobutyl ketone, and fluorine-based solvents. These can be used alone or in combination of two or more.

[0051] <Other ingredients> The composition of the present disclosure may contain other components within the range in which the effects of the present invention are exhibited. Examples of other components that may be contained in the composition include an antioxidant, a surfactant, and a silane coupling agent. The antioxidant can be appropriately selected from known antioxidants and used. Specific examples include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the surfactant include anionic, cationic, nonionic, or amphoteric surfactants. From the viewpoint of compatibility with the light absorber of the present disclosure, phosphate ester-type anionic surfactants are preferred.

[0052] The composition may contain a silane coupling agent. By using the silane coupling agent, the moisture resistance of the optical member is improved. Examples of the silane coupling agent include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, and ethyltrimethoxysilane; and phenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane. These can be used alone or in combination of two or more.

[0053] The content of the light absorbent in the composition may be appropriately adjusted depending on the application of the optical component to be obtained, etc. In order to achieve both the dispersibility of the light absorbent and the infrared absorbing ability of the optical component, the content of the light absorbent is preferably 10 to 90 mass %, more preferably 30 to 80 mass %, based on the total amount of the composition excluding the solvent. The content of the resin in the composition is preferably 10 to 90% by mass, and more preferably 20 to 70% by mass, based on the total amount of the composition excluding the solvent. The solvent is adjusted depending on the desired viscosity of the composition, etc. In order to easily form a relatively thick film, the viscosity of the composition at 25° C. is preferably 1,000 to 100,000 mPa·s, and more preferably 15,000 to 80,000 mPa·s.

[0054] [Method of producing the composition] The method for producing the composition includes preparing a mixed solution of the light absorber and the resin, and heating the mixed solution at 80° C. or higher. This method can bond the light absorber to the resin, particularly the phosphonic acid to a hydroxyl group in the resin.

[0055] The method for preparing the mixed solution is not particularly limited, and the mixed solution can be prepared by adding the light absorbent and the resin to the solvent and mixing them with a known stirrer or the like. The method for producing the light absorbent is as described above, and therefore the explanation is omitted here. The heating temperature of the mixed solution may be 80°C or higher, preferably 85 to 180°C, and more preferably 90 to 160°C. The heating time may be appropriately adjusted depending on the production amount, and can be appropriately adjusted within a range of, for example, 10 minutes to 24 hours. The mixed solvent may be stirred during heating. In addition, the above-mentioned other components may be added to the solution after the reaction, and an organic solvent may be replenished.

[0056] [Optical components] The optical member of the present disclosure contains a light absorbing agent formed by phosphonic acid, a dispersant, and copper ions, and a resin, and at least a part of the light absorbing agent is bonded to the resin. Since the light absorbing agent is uniformly dispersed in the optical member, the optical member has excellent surface uniformity of optical properties. The components in the optical member are the same as those in the above composition, and therefore the explanation thereof will be omitted here.

[0057] The shape of the optical member may be appropriately designed depending on the application, etc. For example, it may be in the shape of a lens such as a convex lens or a concave lens, a prism, or the like, or in the shape of a sheet having fine concave-convex processing such as a prism sheet or a Fresnel lens, or in the shape of a film (membrane) having a flat surface.

[0058] In the case of a film, the thickness is not particularly limited, but from the viewpoint of suppressing the occurrence of cracks and peeling due to stress, etc., it is preferably 500 μm or less, more preferably 200 μm or less, and more preferably 150 μm or less. From the viewpoint of near-infrared absorbing ability, the thickness is preferably 10 μm or more, preferably 20 μm or more, and more preferably 50 μm or more. The optical member of the present invention has sufficient optical properties if it has a thickness of the above-mentioned lower limit or more by containing the specific light absorbing agent.

[0059] Specifically, when the optical member is in the form of a film, the thickness is 130 μm or less, It is also possible to achieve a maximum transmittance of 1% or less in the wavelength range of 800 nm to 1100 nm, and an average transmittance of 85% or more in the wavelength range of 400 nm to 600 nm.

[0060] The method for producing the optical member may be appropriately selected depending on the shape of the optical member, etc. For example, in the case of lenses, prisms, etc., various molding methods such as injection molding can be used. On the other hand, a flat film-like optical component preferably includes, for example, a step of applying the present composition in a paste or varnish form on a substrate. This method makes it possible to easily form a flat film on a desired substrate. The coating of the present composition is dried and, if necessary, subjected to a curing reaction to obtain a film-like optical component. A sheet shape having fine irregularities can be obtained, for example, by shaping the coating film using a mold or the like.

[0061] Since the optical member has excellent optical properties, it can be suitably used as a near-infrared absorbing film arranged on the light receiving surface side of an imaging element such as a CCD or a CMOS. In addition, since it has excellent infrared absorbing ability and high visible light transmittance, it can also be suitably used as a heat absorbing member. Furthermore, an optical member using a polyimide resin as a resin has excellent mechanical strength and heat resistance, so it can be suitably used for the above-mentioned applications. EXAMPLES

[0062] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0063] [Example 1: Production of light absorbers, compositions, and optical components] 1.60 g of copper (II) acetate monohydrate was dissolved in a mixed solution of 50 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 50 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and the solution was stirred at room temperature for 1 minute to prepare solution a. Furthermore, 0.5 g of methylphosphonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 g of a phosphoric acid ester having two polybutylene terephthalate chains were dissolved in 30 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at room temperature for 10 minutes to prepare solution b. Solution a and solution b were poured into a 500 ml recovery flask, stirred at room temperature for 1 min, and then heated in an oil bath at 70°C for 3 h with stirring. After that, impurities such as unreacted substances and by-products were removed, and the solvent was removed. After solidification, 13.0 g of methyl ethyl ketone (MEK) was added and stirred for 1 h to obtain 15.6 g of green near-infrared absorbing solution c. 15.6 g of near-infrared absorbing solution c was dissolved in 2.0 g of DMF (manufactured by Wako Pure Chemicals), and then 1.5 g of cellulose resin CAB-553-0.4 (manufactured by Eastman Chemicals) was added. The light absorber and the resin were reacted by stirring and heating at 150°C for 3 hours. After that, the solvent was removed and solidified, and then 16.0 g of MEK (manufactured by Wako Pure Chemicals) was added and stirred to obtain 20.2 g of near-infrared absorbing coating solution d (composition of the present disclosure). The viscosity of the near-infrared absorbing coating solution d was 8,500 mPa·s. The viscosity was measured at 25°C using a vibration viscometer. The near-infrared absorbing solution d was applied to a 30 mm x 30 mm glass substrate using a bar coater, and after drying in an environment of 80°C for 3 hours, a near-infrared absorbing coating film with a thickness of 0.11 mm was obtained.

[0064] [Example 2] 15.6g of the near infrared absorbing solution c of Example 1 was dissolved in 2.0g of DMF (manufactured by Wako Pure Chemicals), and then 1.5g of cellulose resin CAB-553-0.4 (manufactured by Eastman Chemicals) and 4.0g of methyltrimethoxysilane (manufactured by Wako Pure Chemicals) as a silane coupling agent were added. The light absorber and the resin were reacted by stirring and heating at 150°C for 3h. After that, the solvent was removed and solidified, and then 16.0g of MEK (manufactured by Wako Pure Chemicals) was added and stirred to obtain 22.6g of the near infrared absorbing coating solution (the composition of the present disclosure).

[0065] [Example 3] To the near-infrared absorbing solution c of Example 1 (15.6 g), 1.5 g of cellulose resin CAB-553-0.4 (manufactured by Eastman Chemical) was added, and then 3.1 g of MEK (manufactured by Wako Pure Chemical Industries) was added and stirred to obtain 20.2 g of near-infrared absorbing coating solution. In the near-infrared absorbing coating solution of Example 3, the light absorber and the resin are not bonded.

[0066] [Example 4] To 15.6 g of the near-infrared absorbing solution c of Example 1, 1.5 g of cellulose resin CAB-553-0.4 (manufactured by Eastman Chemical Co., Ltd.) and 4.0 g of methyltrimethoxysilane (manufactured by Wako Pure Chemical Co., Ltd.) as a silane coupling agent were added, and then 3.1 g of MEK (manufactured by Wako Pure Chemical Co., Ltd.) was added and stirred to obtain 24.2 g of a near-infrared absorbing coating solution. In the near-infrared absorbing coating solution of Example 4, the light absorber and the resin are not bonded.

[0067] [Example 5] 15.6g of the near infrared absorbing solution c of Example 1 was dissolved in 2.0 DMF (manufactured by Wako Pure Chemicals), and then 1.5g of cellulose resin CAB-551-0.2 (manufactured by Eastman Chemicals) was added. The light absorber and the resin were reacted by stirring and heating at 150°C for 3h. After that, the solvent was removed and solidified, and then 16.0g of MEK (manufactured by Wako Pure Chemicals) was added and stirred to obtain 19.8g of near infrared absorbing coating solution.

[0068] [Example 6] 15.6g of the near infrared absorbing solution c of Example 1 was dissolved in 2.0 DMF (manufactured by Wako Pure Chemicals), and then 1.5g of cellulose resin CAB-551-0.2 (manufactured by Eastman Chemicals) and 4.0g of methyltrimethoxysilane (manufactured by Wako Pure Chemicals) as a silane coupling agent were added. The light absorber and the resin were reacted by stirring and heating at 150°C for 3h. After that, the solvent was removed and solidified, and then 16.0g of MEK (manufactured by Wako Pure Chemicals) was added and stirred to obtain 22.3g of near infrared absorbing coating solution.

[0069] [Example 7] To the near-infrared absorbing solution c15.6g of Example 1, 1.5g of cellulose resin CAB-551-0.2 (manufactured by Eastman Chemical) was added, and then 3.0g of MEK (manufactured by Wako Pure Chemical Industries) was added and stirred to obtain 20.1g of near-infrared absorbing coating solution. In the near-infrared absorbing coating solution of Example 7, the light absorber and the resin are not bonded.

[0070] [Example 8] To 15.6 g of the near-infrared absorbing solution c of Example 1, 1.5 g of cellulose resin CAB-551-0.2 (manufactured by Eastman Chemical Co., Ltd.) and 4.0 g of methyltrimethoxysilane (manufactured by Wako Pure Chemical Co., Ltd.) as a silane coupling agent were added, and then 3.1 g of MEK (manufactured by Wako Pure Chemical Co., Ltd.) was added and stirred to obtain 24.2 g of a near-infrared absorbing coating solution. In the near-infrared absorbing coating solution of Example 8, the light absorber and the resin are not bonded.

[0071] [Example 9] 15.6g of the near infrared absorbing solution c of Example 1 was dissolved in 2.0 methoxybenzene (manufactured by Wako Pure Chemical Industries, Ltd.), and then 3.0g of silicone resin-containing varnish KR-300 (manufactured by Shin-Etsu Chemical Industries, Ltd.) was added. The light absorber and the resin were reacted by stirring and heating at 150°C for 3h. After that, the solvent was removed and solidified, and then 16.0g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain 20.8g of near infrared absorbing coating solution.

[0072] [Example 10] 15.6g of the near infrared absorbing solution c of Example 1 was dissolved in 2.0 methoxybenzene (manufactured by Wako Pure Chemicals), and then 3.0g of silicone resin-containing varnish KR-300 (manufactured by Shin-Etsu Chemicals) and 4.0g of methyltrimethoxysilane (manufactured by Wako Pure Chemicals) as a silane coupling agent were added. The light absorber and the resin were reacted by stirring and heating at 150°C for 3h. After that, the solvent was removed and solidified, and then 16.0g of toluene (manufactured by Wako Pure Chemicals) was added and stirred to obtain 25.2g of near infrared absorbing coating solution.

[0073] [Example 11] 3.0g of silicone resin-containing varnish KR-300 (Shin-Etsu Chemical Co., Ltd.) was added to 15.6g of the near-infrared absorbing solution c of Example 1, and then 3.0g of methoxybenzene (Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain 21.6g of a near-infrared absorbing coating solution. In the near-infrared absorbing coating solution of Example 11, the light absorber and the resin are not bonded.

[0074] [Example 12] 3.0g of silicone resin-containing varnish KR-300 (Shin-Etsu Chemical Co., Ltd.) and 4.0g of methyltrimethoxysilane (Wako Pure Chemical Co., Ltd.) as a silane coupling agent were added to 15.6g of the near-infrared absorbing solution c of Example 1, and then stirred to obtain 22.6g of a near-infrared absorbing coating solution. In the near-infrared absorbing coating solution of Example 12, the light absorber and the resin are not bonded.

[0075] [Example 13] 15.6g of the near infrared absorbing solution c of Example 1 was dissolved in 2.0 methoxybenzene (manufactured by Wako Pure Chemical Industries), then 8.0g of polyimide resin-containing varnish VR0161 (manufactured by Somar) was added, and the mixture was stirred and heated at 150°C for 3h. After that, the solvent was removed and the mixture was solidified, and 16.0g of toluene (manufactured by Wako Pure Chemical Industries) was added and stirred to obtain 20.4g of near infrared absorbing coating solution. In the near infrared absorbing coating solution of Example 13, the light absorber and the resin were not bonded.

[0076] [Example 14] 15.6g of the near infrared absorbing solution c of Example 1 was dissolved in 2.0 methoxybenzene (manufactured by Wako Pure Chemicals), then 8.0g of polyimide resin-containing varnish VR0161 (manufactured by Somar) and 4.0g of methyltrimethoxysilane (manufactured by Wako Pure Chemicals) as a silane coupling agent were added, and the mixture was stirred and heated at 150°C for 3h. After that, the solvent was removed and the mixture was solidified, and 16.0g of toluene (manufactured by Wako Pure Chemicals) was added and stirred to obtain 23.5g of a near infrared absorbing coating solution. In the near infrared absorbing coating solution of Example 14, the light absorber and the resin were not bonded.

[0077] [Example 15] To the near-infrared absorbing solution c15.6g of Example 1, 8.0g of polyimide resin-containing varnish VR0161 (manufactured by Somar) was added, and then 3.0g of methoxybenzene (manufactured by Wako Pure Chemical Industries) was added and stirred to obtain 26.6g of near-infrared absorbing coating solution. In the near-infrared absorbing coating solution of Example 15, the light absorber and the resin are not bonded.

[0078] [Example 16] 8.0g of polyimide resin-containing varnish VR0161 (manufactured by Somar) and 4.0g of methyltrimethoxysilane (manufactured by Wako Pure Chemical Industries) as a silane coupling agent were added to 15.6g of near-infrared absorbing solution c, and then stirred to obtain 27.6g of near-infrared absorbing coating solution. In the near-infrared absorbing coating solution of Example 16, the light absorber and the resin are not bonded.

[0079] Near infrared absorbing coating films were obtained in the same manner as in Example 1 using the near infrared absorbing coating solutions of Examples 2 to 16.

[0080] [evaluation] After measuring the spectral transmittance spectrum of each of the above coating films, the coating films were stored in an atmosphere of 60° C. and 90% humidity for 500 hours (hereinafter also referred to as a humidity resistance test), and the spectral transmittance spectrum after the humidity resistance test was measured. The in-plane uniformity of the transmittance after the humidity resistance test was evaluated as follows. After the humidity resistance test, the transmittance (wavelength 500 nm) of the coating film was measured at the four corners (EE (edge ​​excluded) 2 mm) and five points in the center of the coating film, and the in-plane uniformity was calculated using the following formula. The smaller the value, the better the in-plane uniformity. In-plane uniformity = (T max -T min / 2Av)×100(%) T max is the highest transmittance value among the five points, T max is the lowest transmittance value among the five points, Av represents the average transmittance at five points. The transmittance of light at wavelengths of 500 nm and 1000 nm before and after the humidity resistance test is shown in Table 1. For the coating film of Example 1, the transmittance spectrum immediately after production is shown in Figure 1, and the transmittance spectrum after the constant temperature and humidity test is shown in Figure 2.

[0081] [Table 1]

[0082] As shown in the comparison of Examples 1-2 with Examples 3-4, the comparison of Examples 5-6 with Examples 7-8, and the comparison of Examples 9-10 with Examples 11-12, it was shown that the coating film formed using the composition of the present disclosure in which at least a portion of the light absorber is bonded to the resin has excellent surface uniformity and moisture resistance in particular. As shown in Figure 1, the coating film of Example 1 had a maximum transmittance of 1% or less at wavelengths of 800 nm to 1100 nm, demonstrating excellent light absorption in a wide range of the near-infrared region. Also, as shown in Figure 2, the transmittance spectrum hardly changed even after the moisture resistance test, demonstrating excellent moisture resistance. Similarly, the coating films of Examples 2, 5 and 6, and 9 and 10 were confirmed to have a wide range of light absorption in the near-infrared region. The coating films of Examples 13 to 16, which used polyimide, were shown to be inferior in moisture resistance and surface uniformity compared to Example 1, etc., even in Examples 13 to 14, which were subjected to heat treatment, because there was no reactivity between the polyimide and the light absorber. In comparing the presence or absence of a silane coupling agent, such as in Example 1 and Example 2, it was shown that the use of a silane coupling agent tended to improve surface uniformity. From the above, it has been shown that a composition containing a light absorber formed from phosphonic acid, a dispersant, and copper ions, a resin, and an organic solvent, in which at least a portion of the light absorber is bonded to the resin, has excellent dispersibility of the light absorber, and that an optical member formed using the composition has excellent surface uniformity of optical properties, excellent moisture resistance, and excellent light absorption in a wide range of the near-infrared region.

[0083] The present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the spirit and scope of the present invention.

Claims

1. a light absorber formed by a phosphonic acid, a dispersant, and copper ions; Contains a resin and an organic solvent, A composition, wherein at least a portion of said light absorber is bound to said resin.

2. The composition according to claim 1 , wherein the resin comprises a resin having an OH group.

3. The composition according to claim 2 , wherein the phosphonic acid is bonded to an OH group of the resin.

4. The composition according to claim 1 , wherein the dispersant comprises a compound represented by the following formula (1): 【Chemistry 1】 however, R １ is a group represented by the following formula (2): R ２ is a hydroxyl group, -R ３ , -Ar １ , -OR ３ , -OAr １ , -OR ４ -Ar １ , -OCOR ３ , -OCOAr １ , -R ４ -N(R ５ ) ２ , or -R １ and R ３ represents an alkyl group which may have a substituent, Ar １ represents an aryl group which may have a substituent, R ４ represents an alkylene group which may have a substituent, R ５ represents a hydrogen atom or an alkyl group which may have a substituent, 【Chemistry 2】 R １０ represents an alkylene group which may have a substituent or an arylene group which may have a substituent, R １１ represents a single bond or an alkylene group which may have a substituent, R １２ represents an alkylene group which may have a substituent, or an arylene group which may have a substituent, provided that R １３ R bonded to １２ is a single bond, R １３ is a hydrogen atom, -R １４ , or -R １５ OH, R １４ represents an alkyl group which may have a substituent, R １５ represents a single bond or an alkylene group which may have a substituent, n is an integer of 1 or more, * is a bond to P, When a formula contains a plurality of the same symbols, the plurality of the same symbols may represent the same group or different groups.

5. The composition according to claim 1 , wherein the phosphonic acid comprises a compound represented by the following formula (3): 【Chemistry 3】 however, R ２１ is -R ３３ , -Ar ３１ , -OR ３３ , -OAr ３１ , -OR ３４ -Ar ３１ , -OCOR ３３ , or -OCOAr ３１ and R ３３ represents an alkyl group which may have a substituent, Ar ３１ represents an aryl group which may have a substituent, R ３４ is an alkylene group which may have a substituent.

6. The composition according to claim 1 , wherein the resin comprises at least one selected from a cellulose resin and a silicone resin.

7. 2. The composition according to claim 1, having a viscosity at 25° C. of 1,000 to 100,000 mPa·s.

8. A method for producing the composition according to any one of claims 1 to 7, comprising the steps of: A method for producing a composition, comprising: preparing a mixed solution of the light absorber and the resin; and heating the mixed solution at 80° C. or higher.

9. 9. The method for producing the composition according to claim 8, wherein the mixed solution is prepared by adding a resin to a solution containing a light absorber formed by phosphonic acid, a dispersant, copper ions, and an organic solvent.

10. a light absorber formed by a phosphonic acid, a dispersant, and copper ions; A resin is included, At least a portion of the light absorbing agent is bonded to the resin.

11. It is in the form of a film having a thickness of 130 μm or less, The maximum transmittance is 1% or less at wavelengths of 800 nm to 1100 nm; The optical member according to claim 10, having an average transmittance of 85% or more at wavelengths of 400 nm to 600 nm.

12. A method for producing an optical member, comprising applying the composition according to any one of claims 1 to 7 onto a substrate.

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