Dye composition, film, optical filter, and near-infrared absorbing compound

Abstract

The present invention relates to a near-infrared absorbing compound represented by general formula (1) and a dye composition containing the near-infrared absorbing compound. In general formula (1), each of R1-R8 independently represents a group selected from the group consisting of a phenyl group having a substituent having a sigma p value of-0.5 or more in accordance with the Hamilt equation, an optionally substituted aryl group having 7-20 carbon atoms, and an optionally substituted heteroaryl group, and two or more of R1-R8 may be linked to each other to form a ring. R9-R13 represent a monovalent substituent, and each of the five n independently represents an integer of 0-4. M is 1 or 2, and X represents a non-nucleophilic anion.

Description

Technical Field

[0001] This invention relates to a pigment composition, a membrane, a filter, and a near-infrared absorbing compound. Background Technology

[0002] In recent years, attention has been paid to near-infrared absorbing compounds and various compositions containing near-infrared absorbing compounds that are useful in applications such as filters such as thermal absorption filters, bandpass filters, and optical filters, inks for invisible printing, and infrared absorbing coatings for anti-laser reflection.

[0003] As near-infrared absorbing compounds, anthocyanins, metal complexes such as oximes or thiols, naphthoquinone compounds, phthalocyanine compounds, naphthophthalocyanine compounds, and diammonium compounds are known, but they have problems such as low durability and low thermal stability.

[0004] As compounds with near-infrared absorption and invisibility, for example, aryl-substituted ammonium compounds and aminoaryl-substituted ammonium compounds are known (see Japanese Patent Application Publication No. 2002-275134 and Japanese Patent Application Publication No. 2006-137935).

[0005] Furthermore, compounds with a diammonium skeleton have been proposed as near-infrared absorbing compositions with good light and heat resistance, and compounds with aryl groups substituted at the terminal nitrogen have also been shown (see Japanese Patent Application Publication No. 2017-116775). However, as counter anions, only monovalent chloride ions, fluoride ions, etc., have been shown. Summary of the Invention

[0006] The technical problem to be solved by the invention

[0007] However, the ammonium compounds described in Japanese Patent Application Publication Nos. 2002-275134 and 2006-137935 have amino-substituted aryl groups, making it difficult to separate them as compounds with a defined oxidation number by using multiple oxidation numbers from 1 to 6. Furthermore, in practical applications, there is sometimes a problem that the absorption spectrum changes due to the change in oxidation number over time.

[0008] Among the ammonium compounds described in Japanese Patent Application Publication No. 2017-116775, monovalent anions such as chloride ions and fluoride ions can be cited as counterions. However, there are concerns that diammonium compounds with the cited nucleophilic anions may decompose at room temperature. Therefore, from a stability point of view, they are unsuitable for practical applications.

[0009] One embodiment of the present invention aims to provide a pigment composition having absorption in the long-wavelength infrared region and containing a thermally stable compound, a film as a cured product of the pigment composition, and a filter containing the film.

[0010] Another embodiment of the present invention aims to solve the problem of providing an infrared absorbing compound that has absorption in the long-wavelength infrared region and is thermally stable.

[0011] means for solving technical problems

[0012] The methods used to solve the above problems include the following approaches.

[0013] <1> A pigment composition comprising a compound represented by the following general formula (1).

[0014] [Chemical Formula 1]

[0015]

[0016] In general formula (1), R1, R2, R3, R4, R5, R6, R7, and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or higher that conforms to the Hammett equation, aryl groups with 7 to 20 carbon atoms that can have substituents, and heteroaryl groups that can have substituents. R1, R2, R3, R4, R5, R6, R7, and R8 can be the same as each other or different, and two or more can be linked together to form a ring. In general formula (1), R9, R... 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They can be the same as each other, or they can be different.

[0017] m is 1 or 2. X - This indicates a nonnucleophilic anion.

[0018] <2> A pigment composition comprising a compound represented by the following general formula (2).

[0019] [Chemical Formula 2]

[0020]

[0021] In general formula (2), R1, R2, R3, R4, R5, R6, R7, and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or higher that conforms to the Hammett equation, aryl groups with 7 to 20 carbon atoms that can have substituents, and heteroaryl groups that can have substituents. R1, R2, R3, R4, R5, R6, R7, and R8 can be the same as each other or different, and two or more can be linked together to form a ring. In general formula (2), R9, R... 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They can be the same as each other, or they can be different.

[0022] X - This indicates a nonnucleophilic anion.

[0023] <3> according to <1> or <2> The pigment composition described above as an image forming material.

[0024] <4> according to <1> or <2> The pigment composition further comprises a resin.

[0025] <5> A membrane comprising <4> The pigment composition described above.

[0026] <6> A filter comprising <5> The membrane mentioned above.

[0027] <7> A near-infrared absorbing compound, represented by the following general formula (1).

[0028] [Chemical Formula 3]

[0029]

[0030] In general formula (1), R1, R2, R3, R4, R5, R6, R7, and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or higher that conforms to the Hammett equation, aryl groups with 7 to 20 carbon atoms that can have substituents, and heteroaryl groups that can have substituents. R1, R2, R3, R4, R5, R6, R7, and R8 can be the same as each other or different, and two or more can be linked together to form a ring. In general formula (1), R9, R... 10 R 11 R 12 and R 13Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They can be the same as each other, or they can be different.

[0031] m is 1 or 2, X - This indicates a nonnucleophilic anion.

[0032] <8> A near-infrared absorbing compound, represented by the following general formula (2).

[0033] [Chemical Formula 4]

[0034]

[0035] In general formula (2), R1, R2, R3, R4, R5, R6, R7, and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or higher that conforms to the Hammett equation, aryl groups with 7 to 20 carbon atoms that can have substituents, and heteroaryl groups that can have substituents. R1, R2, R3, R4, R5, R6, R7, and R8 can be the same as each other or different, and two or more can be linked together to form a ring. In general formula (2), R9, R... 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They can be the same as each other, or they can be different.

[0036] X - This indicates a nonnucleophilic anion.

[0037] Invention Effects

[0038] According to one embodiment of the present invention, a pigment composition having absorption in the long-wavelength infrared region and containing a thermally stable compound is provided, a film as a cured product of the pigment composition, and a filter containing the film are provided.

[0039] According to another embodiment of the present invention, an infrared absorbing compound that has absorption in the long-wavelength infrared region and is thermally stable is provided. Attached Figure Description

[0040] Figure 1This is the absorption spectrum of compound A-1 in chloroform solution.

[0041] Figure 2 This is the absorption spectrum of compound B-1 in a chloroform solution. Detailed Implementation

[0042] The present invention will now be described in detail.

[0043] In this invention, "total solids content" refers to the total mass of the components from which the solvent has been removed from all components of the composition. Furthermore, as described above, "solids content" refers to the components from which the solvent has been removed; for example, it can be solid or liquid at 25°C.

[0044] In the designation of groups (atomic groups) in this invention, the absence of labels indicating substituted and unsubstituted groups includes labels without substituents, and also includes labels with substituents. For example, "alkyl" means not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups).

[0045] In this invention, unless otherwise stated, "exposure" includes not only exposure using light, but also depiction using particle beams such as electron beams and ion beams. Furthermore, examples of light used in exposure include bright-line spectra of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other activated light or radiation.

[0046] In this invention, "(meth)acrylate" means either or both of acrylate and methacrylate, "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, and "(meth)acryloyl" means either or both of acryloyl and methacryloyl.

[0047] In this invention, the symbols "R1, R2, R3, R4, R5, R6, R7 and R8" recorded in the general formula are sometimes abbreviated as "R1~R8", and "R9, R..." are abbreviated as "R1~R8". 10 R 11 R 12 and R 13 "Abbreviated as "R9~R" 13 ".

[0048] In this invention, Me represents methyl, Et represents ethyl, Pr represents propyl, Bu represents butyl, Ac represents acetyl, Bn represents benzyl, and Ph represents phenyl.

[0049] In this invention, the term "process" is included not only in the context of an independent process, but also in the context of a process that cannot be clearly distinguished from other processes, as long as the intended function of the process is achieved.

[0050] In this invention, "mass%" and "weight%" have the same meaning, and "parts of mass" and "parts of weight" have the same meaning.

[0051] In this invention, the numerical range represented by “~” indicates the range of values ​​before and after “~” as the minimum and maximum values, respectively.

[0052] Furthermore, in this invention, the amount of each component contained in the composition refers to the total amount of the multiple substances, unless otherwise stated.

[0053] In the numerical ranges described in stages in this invention, the upper or lower limit value of a single numerical range can be replaced with the upper or lower limit value of other numerical ranges described in stages. Furthermore, the upper or lower limit value of the numerical ranges described in this invention can be replaced with the values ​​shown in the embodiments.

[0054] Furthermore, in this invention, a combination of two or more preferred methods is a more preferred method.

[0055] In this invention, the long-wavelength infrared region refers to the wavelength region of 1150 nm to 2000 nm. Hereinafter, infrared absorbing compounds that have absorption in the wavelength region of 1150 nm to 2000 nm will sometimes be referred to as "near-infrared absorbing compounds".

[0056] Unless otherwise specified, the transmittance in this invention is the transmittance at 25°C.

[0057] In this invention, the weight-average molecular weight and number-average molecular weight of the resin are defined as polystyrene conversion values ​​determined by gel permeation method (GPC).

[0058] In this invention, when the content of "structural units" in the resin is specified by molar ratio, the meaning of "structural unit" is the same as that of "monomer unit". However, the "monomer unit" in this invention can be modified after polymerization through polymer reactions or the like.

[0059] "Room temperature" refers to the ambient temperature without special temperature control. In this invention, unless otherwise stated, it refers to "25°C".

[0060] <Pigment Composition>

[0061] The first embodiment of the pigment composition according to the present invention (hereinafter also referred to as "composition (1)") contains a compound represented by the following general formula (1) (hereinafter also referred to as "specific compound (1)").

[0062] [Chemical Formula 5]

[0063]

[0064] In general formula (1), R1, R2, R3, R4, R5, R6, R7 and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or more that conform to the Hammett equation, aryl groups having 7 to 20 carbon atoms that may have substituents, and heteroaryl groups that may have substituents. Two or more of R1, R2, R3, R4, R5, R6, R7 and R8 may be linked together to form a ring.

[0065] R1, R2, R3, R4, R5, R6, R7, and R8 represent phenyl groups having a substituent with a σp value of -0.5 or more as a Hammett equation and aryl groups selected from those having 7 to 20 carbon atoms. From the viewpoint of the stability of the specific compound (1), it is preferable to have a phenyl group having a substituent with a σp value of -0.5 or more as a Hammett equation or an aryl group having 10 to 20 carbon atoms that may have a substituent. More preferably, it is a phenyl group having a substituent with a σp value of -0.5 or more as a Hammett equation, a naphthyl group that may have a substituent, or an anthracene group that may have a substituent. Even more preferably, it is a phenyl group having a substituent with a σp value of -0.5 or more as a Hammett equation.

[0066] From the viewpoint of synthetic applicability, it is preferred that R1, R2, R3, R4, R5, R6, R7 and R8 in general formula (1) are phenyl groups with substituents having a σp value of -0.5 or more in the Hammett equation.

[0067] The substituents in the phenyl group are those with a σp value greater than -0.5 that conforms to the Hammett equation. Here, the Hammett substituent constant σ is explained. The Hammett equation is an empirical rule proposed by L. P. Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, and its validity is now widely recognized.

[0068] The substituent constants derived from the Hammett equation include σp and σm values, which can be found in many general books. For example, they are detailed in JA Dean's 12th edition of "Lange's Handbook of Chemistry," 1979 (McGraw-Hill), or "Chemical Fields" supplement, No. 122, pp. 96-103, 1979 (Nankodo), and Chem. Rev., 1991, Vol. 91, pp. 165-195.

[0069] In the above general formula (1), a substituent with a Hammett substituent constant σp value of -0.5 or higher indicates a transformation from a weak electron-donating group to an electron-withdrawing group.

[0070] From the viewpoint of the stability of a particular compound (1), the σp value of the Hammett equation is preferably -0.40 or more, more preferably -0.35 or more, and even more preferably -0.30 or more.

[0071] Examples of substituents with a σp value of 0.5 or higher in the Hammett equation include hydroxyl (-0.37), methoxy (-0.27), methyl (-0.17), chloro (-0.23), cyano (0.66), carboxyl (-COOH: 0.45), alkoxycarbonyl (e.g., -COOMe (0.45), aryloxycarbonyl (e.g., -COOPh (0.44), carbamoyl (-CONH2 (0.36)), alkylcarbonyl (e.g., -COMe (0.50)), arylcarbonyl (-COPh (0.43)), alkylsulfonyl (e.g., -SO2Me (0.72)), arylsulfonyl (e.g., -SO2Ph (0.68)), trifluoromethyl (0.54), and nitro (0.78). Furthermore, the values ​​shown in parentheses following the examples of substituents are the σp values ​​in the Hammett equation.

[0072] When R1, R2, R3, R4, R5, R6, R7, and R8 in general formula (1) are phenyl groups or aryl groups with 7 to 20 carbon atoms that may have substituents, it is preferable that two of R1 to R8 are substituents with a Hammet substituent constant σp of -0.5 or more; more preferably, it is preferable that four of R1 to R8 are substituents with a Hammet substituent constant σp of -0.5 or more; and even more preferably, it is preferable that all of R1 to R8 are substituents with a Hammet substituent constant σp of -0.5 or more. As described above, it is preferable that R1, R2, R3, R4, R5, R6, R7, and R8 are all phenyl groups with a Hammet equation σp value of -0.5 or more.

[0073] There are multiple substituents with Hammett substituent constants σp values ​​greater than -0.5. They can be the same or different from each other, but from the point of view of synthetic applicability, it is preferred that all of them be the same substituent.

[0074] When R1, R2, R3, R4, R5, R6, R7, and R8 represent aryl groups with 7 to 20 carbon atoms that can have substituents, examples of aryl groups with 7 to 20 carbon atoms are preferred, and more preferably aryl groups with 10 to 20 carbon atoms. Specifically, examples of aryl groups with 7 to 20 carbon atoms include naphthyl, anthraceneyl, and pyreneyl.

[0075] Substituents that are aryl groups with 7 to 20 carbon atoms and have substituents can also be exemplified by R9, R2, etc., as shown below. 10 R 11 R 12 and R 13 The exemplified substituents are monovalent.

[0076] From the viewpoint of synthetic applicability, the substituents with a monovalent valence are preferably selected from alkyl, hydroxy, alkoxy, alkoxycarbonyl and alkylcarbonyloxy groups.

[0077] When R1, R2, R3, R4, R5, R6, R7, and R8 represent heteroaryl groups that may have substituents, examples of heteroaryl groups include those with 1 to 20 carbon atoms, and more preferably those with 1 to 12 carbon atoms. Examples of heteroatoms included in the ring of the heteroaryl group include nitrogen atoms, oxygen atoms, sulfur atoms, etc.

[0078] As heteroaryl groups, examples include imidazolyl, pyridinyl, quinolinyl, furanyl, thiophene, benzoxazolyl, benzimidazolyl, benzothiazolyl, naphthothiazolyl, benzoxazolyl, m-carbazolyl, acrylonitrile, etc.

[0079] As a substituent when a heteroaryl group has substituents, examples similarly include R9 and R shown below. 10 R 11 R 12 and R 13 The exemplified substituents are monovalent.

[0080] From the viewpoint of synthetic applicability, the substituents with a monovalent valence are preferably selected from alkyl, aryl, alkoxy, alkoxycarbonyl, halogen atoms and alkylamino groups.

[0081] The heteroaryl groups having substituents in R1 to R8 are preferably 1 to 8, more preferably 4 to 8, and even more preferably 8, meaning that all heteroaryl groups have substituents.

[0082] The monovalent substituents of the heteroaryl group may be the same or different, but from the point of view of synthetic applicability, they are preferably the same.

[0083] In general formula (1), R9, R 10 R 11 R 12 and R 13 Let each substituent represent a monovalent substituent independently, and let n be an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They can be the same as each other, or they can be different.

[0084] From the viewpoint of synthetic applicability, examples of monovalent substituents include alkyl, alkoxy, hydroxy, mercapto, halogen, cyano, sulfonyl, carboxyl, nitro, hydroxamic acid, sulfinyl, acyl, alkoxycarbonyl, acyloxy, amide, alkoxycarbonylamino, sulfonylamino, aminosulfonyl, carbamoyl, alkylthio, sulfonyl, sulfinyl, and urea.

[0085] The preferred number of carbon atoms in the alkyl group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of alkyl groups include methyl, ethyl, isopropyl, tert-butyl, n-pentyl, cyclopropyl, and cyclopentyl.

[0086] The preferred number of carbon atoms in the alkoxy group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of alkoxy groups include methoxy, ethoxy, and butoxy.

[0087] Examples of halogen atoms include, for example, fluorine atoms and chlorine atoms.

[0088] The preferred number of carbon atoms in the acyl group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of acyl groups include acetyl, formyl, and pivaloyl.

[0089] The preferred number of carbon atoms in the alkoxycarbonyl group is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. Examples of alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl.

[0090] The preferred number of carbon atoms in the acyloxy group is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. Examples of acyloxy groups include acetoxy groups.

[0091] The preferred number of carbon atoms in the amide group is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. Examples of amide groups include acetamido and isopropylamino.

[0092] The preferred number of carbon atoms in the alkoxycarbonyl amino group is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. Examples of alkoxycarbonyl amino groups include methoxycarbonyl amino groups.

[0093] The preferred number of carbon atoms in the sulfonamide is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of sulfonamides include methanesulfonamide and isopropylsulfonamide.

[0094] The preferred number of carbon atoms in the aminosulfonyl group is 0 to 20, more preferably 0 to 10, and even more preferably 0 to 6. Examples of aminosulfonyl groups include aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, and phenylaminosulfonyl.

[0095] The preferred number of carbon atoms in the carbamoyl group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Examples of carbamoyl groups include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl.

[0096] The preferred number of carbon atoms in the alkylthio group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of alkylthio groups include methylthio and ethylthio.

[0097] The preferred number of carbon atoms in the sulfonyl group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Examples of sulfonyl groups include methanesulfonyl and toluenesulfonyl.

[0098] The preferred number of carbon atoms in the sulfinyl group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Examples of sulfinyl groups include methanesulfonyl and benzenesulfonyl groups.

[0099] The preferred number of carbon atoms in the urea group is 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Examples of urea groups include urea, methylurea, and phenylurea.

[0100] In general formula (1), m is 1 or 2, and from the viewpoint of the stability of a particular compound (1), m is preferably 2.

[0101] X in general formula (1) - This indicates a nonnucleophilic anion. That is, a specific compound (1) is a compound that has a nonnucleophilic anion.

[0102] Here, the non-nucleophilicity of the anion refers to the property that the anion does not nucleophilically attack the pigment, i.e., the pigment matrix of the specific compound (1). When a pigment compound has a nucleophilic anion, depending on the heating conditions, the nucleophilic anion may sometimes attack the pigment matrix and cause the pigment to decompose, thus raising concerns about stability. On the other hand, by having a non-nucleophilic anion in the specific compound (1), the attack of the anion on the pigment matrix can be suppressed, thereby suppressing the decomposition of the specific compound (1) and maintaining thermal stability.

[0103] As an example of a nonnucleophilic anion, one can cite, for example, the known nonnucleophilic anion described in paragraph

[0075] of Japanese Patent Application Publication No. 2007-310315, which is incorporated herein by reference.

[0104] As a non-nucleophilic anion, preferred examples include imide anions (e.g., bis(sulfonyl)imide anion), tri(sulfonyl)methane anion, tetraarylborate anion, and B-(CN) anion. n1 (ORa) (4-n1) (Ra represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms, n1 represents 1 to 4), PF n2 R P (6-n2) (R P (representing fluorinated alkyl groups with 1 to 10 carbon atoms, n2 representing integers from 1 to 6), and BFn3R P (4-n3) (R P (This indicates a fluorinated alkyl group with 1 to 10 carbon atoms, where n3 represents an integer from 1 to 4).

[0105] From the viewpoint of better stability of a specific compound (1), bis(alkylsulfonyl)amide anion, tri(alkylsulfonyl)methyl anion, and BF4 are preferably examples of non-nucleophilic anions. - PF6 - SbF6 - Perchlorate anion, cyclopentadienyl, B(CN)4 - B(Ph)4 - and B(C6F5)4 - More preferably, bis(alkylsulfonyl)amide anion, tri(alkylsulfonyl)methyl anion, and BF4 are examples. - PF6 - SbF6 - Perchloric acid anion, B(CN)4 - B(Ph)4 - and B(C6F5)4 -Further preferred examples include bis(alkylsulfonyl)amide anion, tri(alkylsulfonyl)methyl anion, SbF6-, perchlorate anion, and B(Ph)4-. - B(CN)4 - and B(C6F5)4 - .

[0106] The position of the cation in the diammonium compound skeleton of a specific compound (1) is not particularly limited, and various forms can be adopted if conjugated compounds are considered. Among them, it is preferred that any nitrogen atom in the diammonium skeleton is a cation.

[0107] From the viewpoint of the contribution rate of the conjugated structure that a particular compound (1) can take, for example, when m is 2, it is possible to make N the structure represented by the following formula (1-1). + When N becomes a cation moiety and m is 1, it is possible to achieve a structure as represented by the following formula (1-2), N + It becomes a cation moiety. However, as mentioned above, the location of the cation moiety that contributes to the interaction between the diimide framework and the anion is not limited to the examples below.

[0108] [Chemical Formula 6]

[0109]

[0110] In equations (1-1) and (1-2) above, R1~R8, R9~R 13 , n and X - The meanings are the same as those of R1~R8 and R9~R in the above general formula (1). 13 , n and X - The meanings are the same, and the preferred examples are also the same.

[0111] The second embodiment of the pigment composition according to the present invention (hereinafter also referred to as "composition (2)") comprises a compound represented by the following general formula (2) (hereinafter also referred to as "specific compound (2)").

[0112] [Chemical Formula 7]

[0113]

[0114] In general formula (2), R1, R2, R3, R4, R5, R6, R7 and R8 each independently represent a phenyl group selected from substituents having a σp value of -0.5 or more that conforms to the Hammett equation, an aryl group having 7 to 20 carbon atoms that may have substituents, or a heteroaryl group that may have substituents. Two or more of R1, R2, R3, R4, R5, R6, R7 and R8 may be linked together to form a ring.

[0115] In general formula (2), R9, R 10 R 11 R 12 and R 13 Each substituent is represented independently, and the five n's represent integers from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They can be the same as each other, or they can be different.

[0116] X - This indicates a nonnucleophilic anion.

[0117] In a second embodiment of the pigment composition according to the present invention, a specific compound (2) is included instead of a specific compound (1) in the first embodiment of the pigment composition according to the present invention. The specific compound (2) is a compound in which m is 2 in the specific compound (1).

[0118] In general formula (2), R1, R2, R3, R4, R5, R6, R7 and R8, R9, R 10 R 11 R 12 and R 13 , n and X - The meanings of are the same as those in general formula (1), and the preferred examples are also the same.

[0119] Specific compounds (1) and specific compounds (2) can, for example, synthesize intermediate X-1 by the following scheme, and synthesize from the obtained intermediate. Compound A-1 is a compound contained in specific compound (1), and compound B-1 is a compound contained in specific compound (2).

[0120] [Chemical Formula 8]

[0121]

[0122] In addition, hereafter, either or both of the specific compound (1) and specific compound (2) of the present invention will sometimes be referred to as "the specific compound of the present invention". And, either or both of the composition (1) and composition (2) of the present invention will sometimes be referred to as "the composition of the present invention".

[0123] The specific compounds of the present invention preferably have a maximum absorption wavelength in the infrared region of 700 nm to 2500 nm, and more preferably have a maximum absorption wavelength in the near-infrared region of 1150 nm to 2000 nm.

[0124] The near-infrared absorbance of specific compounds is evaluated as follows.

[0125] For a specific compound, dilute with chloroform to a concentration of 3.0 × 10⁻⁶. -5 The concentration was mol / L, and the absorbance of the obtained sample solution was measured in a 1 mm quartz cell using a spectrophotometer (UV-3600 Plus, manufactured by SHIMADZU CORPORATION). The wavelength of maximum absorption (λmax) was determined from the absorption spectrum of the sample solution.

[0126] The reason why the compositions (1) and (2) of the present invention containing specific compounds have absorption and thermal stability in the long-wavelength infrared region is speculated as follows.

[0127] The specific compounds of this invention exhibit good near-infrared absorption by having an aryl isocyclic structure or a heteroaryl group on the nitrogen atom of the diamine backbone. Furthermore, the counter ion, which serves as the counter ion of the pigment backbone containing the diamine backbone, possesses a non-nucleophilic anion, thus suppressing nucleophilic attack caused by the counter ion even under heating conditions, resulting in good thermal stability of the compound.

[0128] Furthermore, the presence of substituents such as aryl groups bonded to the nitrogen atom of the diimide skeleton, or the presence of heteroaryl groups on the nitrogen atom of the diimide skeleton, enhances the affinity for solvents, resins, and other components contained in the composition. Additionally, the diimide skeletons are less likely to approach each other, resulting in better uniform dispersion of specific compounds in the composition when used as a pigment composition. Moreover, it is believed that substituents such as aryl groups bonded to the nitrogen atom of the diimide skeleton with a Hammett equation σp value of -0.5 or higher further reduce the likelihood of oxidation reactions, enabling the synthesis of divalent and monovalent cations and reducing the likelihood of thermal oxidative decomposition.

[0129] That is, it is believed that in the specific compounds of the present invention, the pigment nucleus having a diammonium skeleton has a non-nucleophilic anion, and the diammonium skeleton has aryl or heteroaryl substituents with a σp value of -0.5 or more in the Hammett equation, which can solve the above-mentioned problems.

[0130] The following are specific examples of particular compounds in this invention, but the particular compounds in this invention are by no means limited to the examples shown below.

[0131] [Chemical Formula 9]

[0132]

[0133] [Chemical Formula 10]

[0134]

[0135] [Chemical Formula 11]

[0136]

[0137] [Chemical Formula 12]

[0138]

[0139] [Chemical Formula 13]

[0140]

[0141] [Chemical Formula 14]

[0142]

[0143] [Chemical Formula 15]

[0144]

[0145] [Chemical Formula 16]

[0146]

[0147] [Chemical Formula 17]

[0148]

[0149] [Chemical Formula 18]

[0150]

[0151] [Chemical Formula 19]

[0152]

[0153] [Chemical Formula 20]

[0154]

[0155] [Chemical Formula 21]

[0156]

[0157] [Chemical Formula 22]

[0158]

[0159] [Chemical Formula 23]

[0160]

[0161] [Chemical Formula 24]

[0162]

[0163] The compositions of the present invention, by comprising at least one of the specific compounds having the above-mentioned properties, exhibit excellent near-infrared absorption and thermal stability, and are therefore suitable for a variety of applications.

[0164] The content of a specific compound in the composition is appropriately selected according to the intended use of the composition.

[0165] The specific compounds exhibit good affinity, compatibility, and dispersibility with various solvents, resins, etc. Therefore, the compositions of the present invention can be aqueous or non-aqueous compositions.

[0166] The components that can be included in the composition of the present invention will be described below.

[0167] <Aquatic System Composition>

[0168] (Aqueous solvent)

[0169] When the composition of the present invention is an aqueous composition, the composition may contain an aqueous solvent. The composition may be a substance formed by dissolving or dispersing the specific compound described herein in an aqueous carrier.

[0170] Examples of aqueous solvents include water, hydrophilic organic solvents, and mixed solvents that are mainly water with added hydrophilic organic solvents.

[0171] In this invention, "a solvent with water as the main component" refers to a solvent that contains more than 30% by mass of water relative to the total aqueous solvent.

[0172] Examples of hydrophilic organic solvents include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.

[0173] Polyols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol, pentanediol, glycerol, glycerol, thiodiethylene glycol, etc.

[0174] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether, and other glycol derivatives.

[0175] Ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morphine, N-ethylmorphine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine, and other amines.

[0176] Formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolone, 1,3-dimethyl-2-imidazolinone, acetonitrile, acetone, etc.

[0177] The aqueous solvent preferably contains 30% to 100% by mass of water in the total solvent, more preferably 50% to 100% by mass of water.

[0178] (Water-based resin)

[0179] The aqueous composition may further comprise an aqueous resin. Examples of aqueous resins include water-soluble resins dissolved in water, water-dispersible resins dispersed in water, colloidal dispersion resins, or mixtures of these resins.

[0180] Specifically, examples of water-based resins include acrylic resins, styrene-acrylic resins, vinyl resins, polyurethane resins, polyester resins, polyamide resins, fluorinated resins, and various other water-based resins. Furthermore, one embodiment of a water-based resin is a water-soluble resin that dissolves in water, such as gelatin, polyvinyl alcohol, and carboxymethyl cellulose.

[0181] The above-mentioned water-based resin can be used as an adhesive resin.

[0182] The specific compounds of the present invention have good solubility in solvents, and therefore, by configuring a composition containing an adhesive resin, a near-infrared absorbing layer can be formed.

[0183] The aqueous composition of the present invention may contain only one type of aqueous resin or may contain two or more types of aqueous resin.

[0184] When the water-based resin is used as the adhesive resin for forming the layer, the molecular weight of the polymer is not particularly limited; generally, a weight-average molecular weight of about 3,000 to 1,000,000 is preferred. When the weight-average molecular weight is within the above range, the coating layer obtained using the composition of the present invention has sufficient strength and good coating surface properties.

[0185] (Non-aqueous composition)

[0186] When the composition of the present invention is a non-aqueous composition, the composition may be a substance formed by dissolving or dispersing the specific compound described herein in a non-aqueous carrier.

[0187] Resins used as non-aqueous carriers include, for example, petroleum resins, casein, shellac, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenolic resins, alkyd resins, polyester resins, unsaturated polyester resins, amino resins, epoxy resins, vinyl resins, vinyl chloride, vinyl chloride-vinyl acetate copolymers, acrylic resins, methacrylic resins, polyurethane resins, silicone resins, fluororesins, drying oils, synthetic drying oils, styrene / maleic acid resins, styrene / acrylic resins, polyamide resins, polyimide resins, polyester resins, benzoguanamine resins, melamine resins, urea-formaldehyde resins, chlorinated polypropylene, butyral resins, and vinylidene chloride resins.

[0188] As a non-aqueous carrier, photocurable resin or thermocurable resin can be used.

[0189] When adjusting non-aqueous compositions, solvents used for dissolving or dispersing in non-aqueous carriers include, for example, aromatic solvents such as toluene, xylene, and methoxybenzene; acetate solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxyethyl propionate; alcohol solvents such as methanol and ethanol; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, and pyridine; lactone solvents such as γ-butyrolactone; and carbamates such as a 18:52 mixture of methyl carbamate and ethyl carbamate.

[0190] The compositions of the present invention can also be prepared by dispersion using a dispersion device when containing the specific compounds described and an aqueous or non-aqueous medium.

[0191] As a dispersion device that can be used in the preparation of dispersions, a known dispersion device can be appropriately selected and used. Examples of dispersion devices include ball mills, sand mills, bead mills, roller mills, jet mills, paint mixers, grinders, ultrasonic dispersers, dispersers, etc.

[0192] The compositions of the present invention have good near-infrared absorption and good thermal stability, and therefore can be used for a variety of applications.

[0193] The uses of the compositions of the present invention are not particularly limited and can be used in inks, filters, such as infrared cut-off filters, dyeing solutions for fibers, photothermal conversion, etc.

[0194] Furthermore, in addition to the above-mentioned uses, the compositions of the present invention, due to their absorption in the near-infrared region where they have excellent human penetration, can also be used for diagnostic marking or photodynamic therapy.

[0195] The formulation of the compositions of the present invention may be appropriately adjusted according to the intended use. Various compounds may be included in the compositions of the present invention within a range that does not impair the effects of specific compounds of the present invention that exhibit good near-infrared absorption.

[0196] The pigment composition of the present invention preferably further comprises a resin. That is, the pigment composition of the present invention is preferably a resin composition.

[0197] The specific compounds of this invention exhibit excellent absorption capacity in the near-infrared region with wavelengths exceeding 1150 nm and good heat resistance. Therefore, the compositions of this invention containing the specific compounds can become resin compositions with excellent absorption capacity in the near-infrared region with wavelengths exceeding 1150 nm and excellent heat resistance.

[0198] Hereinafter, the compositions of the present invention containing resin will sometimes be referred to as "resin compositions of the present invention".

[0199] The resin composition of the present invention can be a composition in a solution state containing a solvent.

[0200] Furthermore, the resin composition of the present invention can be a compound.

[0201] Furthermore, in this invention, a compound refers to a substance obtained by mixing a specific compound with a resin. That is, the compound in this invention refers to a composition in which a specific compound is mixed and dispersed in a resin, and is described as a substance different from the liquid composition obtained by dissolving or dispersing the specific compound and the resin in the solvent described above.

[0202] The compound used in the resin composition of the present invention is preferably granules. Here, granules refer to materials in which the compound is granulated (granulated) into a predetermined shape such as spheres, ellipsoids, cylinders, or prisms. Furthermore, the granules are preferably masterbatch granules. Masterbatch granules are also called master batches. In addition, masterbatch granules refer to particulate matter that typically contains a desired compound compounded in the resin at a high concentration, and the concentration of that compound in the resin is adjusted to the desired concentration by compounding with the resin.

[0203] In this invention, masterbatch particles refer to materials in which a high concentration of a specific compound and other components, such as additives like ultraviolet absorbers, are dispersed in a resin. These particles are used to mix the resin and the like with the masterbatch particles at a specified ratio when forming a molded body, and to prepare a resin or the like containing the specific compound at a specified concentration.

[0204] The resin composition of the present invention may contain only one of the specific compounds described herein, or it may contain two or more compounds.

[0205] The content of a specific compound in the total solids component of the above resin composition is preferably 0.01% to 20% by mass.

[0206] The content of the specific compound relative to the total solids content of the resin composition is more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more.

[0207] The content of the specific compound relative to the total solids content of the resin composition is more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0208] In one embodiment, when the resin composition of the present invention is used as a compound, from the viewpoint of better uniform dispersion of the specific compound in the resin, the content of the specific compound in the resin composition is preferably 0.01% to 5% by mass or less, and more preferably 0.01% to 2% by mass or less.

[0209] When the above resin composition contains two or more specific compounds, the above content refers to the total amount of the two or more specific compounds.

[0210] (resin)

[0211] The resin contained in the resin composition of the present invention will be described.

[0212] As a resin, it is possible to appropriately select from resins that meet various physical properties such as transparency, refractive index, and processability, depending on the application or purpose.

[0213] Examples of resins include (meth)acrylic resins, olefin-thiol resins, polyester resins, polycarbonate resins, vinyl polymers (e.g., polydiene resins, polyolefin resins, polystyrene resins, polyvinyl ether resins, polyvinyl alcohol resins, polyvinyl ketone resins, polyvinyl fluoride resins, and polybrominated vinyl resins), polysulfide resins, polystyrene resins, polyurethane resins, polysulfonate resins, nitrosopolymer resins, polysiloxane resins, polysulfide resins, polysulfide ester resins, polysulfone resins, polysulfonamide resins, polyamide resins, polyimide resins, polyurea resins, polyphosphonium olefin resins, polysilane resins, polysilazane resins, and polyfuran resins. Esters, polybenzoxazole resins, polyoxadiazole resins, polybenzothiazide-phenothiazine resins, polybenzothiazide resins, polypyrazine-quinoxaline resins, polyquinoxaline resins, polybenzimidazole resins, polyoxyisoindoline resins, polydioxoisoindoline resins, polytriazine resins, polypyridazine resins, polypiperazine resins, polypyridine resins, polypiperidine resins, polytriazole resins, polypyrazole resins, polypyrrolidone resins, polycarboborane resins, polyoxabicyclononane resins, polydibenzofuran resins, polynaphthalene dicarboxylate, polyacetal resins, polyimide resins, polyamide-imide resins, olefin resins, cyclic olefin resins, epoxy resins, cellulose acylate resins, etc.

[0214] As a (meth)acrylic resin, examples include polymers comprising structural units derived from (meth)acrylic acid and / or its esters. Specifically, examples include polymers obtained by polymerizing at least one compound selected from the group consisting of (meth)acrylic acid, (meth)acrylates, (meth)acrylamide, and (meth)acrylonitrile.

[0215] Polyester resins include polymers obtained by reacting polyols (e.g., ethylene glycol, propylene glycol, glycerol, and trimethylolpropane) with polyacids (e.g., aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid, and dicarboxylic acids in which the hydrogen atoms of these aromatic rings are replaced by methyl, ethyl, or phenyl compounds, etc.), aliphatic dicarboxylic acids with 2 to 20 carbon atoms (e.g., adipic acid, sebacic acid, and dodecanedicarboxylic acid), or alicyclic dicarboxylic acids (e.g., cyclohexanedicarboxylic acid, etc.)), and polymers obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone monomers (e.g., polycaprolactone). Specific examples of polyester resins include polyethylene terephthalate and polyethylene naphthalate.

[0216] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, cresol varnish type epoxy resin, and aliphatic epoxy resin.

[0217] Epoxy resins can be commercially available products, and the following resins can be cited as examples of commercially available products.

[0218] Examples of commercially available bisphenol A epoxy resins include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009 and jER1010 (all manufactured by Mitsubishi Chemical Corporation), and EPICLON860, EPICLON1050, EPICLON1051 and EPICLON1055 (all manufactured by DICCorporation).

[0219] Examples of commercially available bisphenol F epoxy resins include jER806, jER807, jER4004, jER4005, jER4007 and jER4010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON (registered trademark) 830 and EPICLON835 (all manufactured by DIC Corporation), and LCE-21 and RE-602S (all manufactured by Nippon Kayaku Co., Ltd.).

[0220] Examples of commercially available phenolic varnish-type epoxy resins include jER152, jER154, jER157S70 and jER157S65 (manufactured by Mitsubishi Chemical Corporation), and EPICLONN-740, EPICLON N-770 and EPICLON N-775 (manufactured by DIC Corporation).

[0221] Examples of commercially available cresol varnish-type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (all manufactured by DIC Corporation), as well as EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).

[0222] Examples of commercially available aliphatic epoxy resins include the ADEKA RESIN EP series (e.g., EP-4080S, EP-4085S, and EP-4088S; manufactured by ADEKA CORPORATION), Celoxide (registered trademark) 2021P, Celoxide2081, Celoxide2083, Celoxide2085, EHPE3150, EPOLEAD PB 3600 and EPOLEAD PB4700 (all manufactured by Daicel Corporation), Denacol EX-212L, EX-214I, EX-216L, EX-321I, and EX-850L (all manufactured by Nagase ChemteX Corporation), and the ADEKA RESIN EP series (e.g., EP-4000S, EP-4003S, EP-4010S, and EP-4011S, etc.; manufactured by ADEKA). (manufactured by CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501 and EPPN-502 (all manufactured by ADEKA CORPORATION), and jER1031S (manufactured by Mitsubishi Chemical Corporation), etc.

[0223] Examples of other commercially available epoxy resins include Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOFCORPORATION and are epoxy-containing polymers).

[0224] As a cellulose acylated resin, the cellulose acylated resin described in paragraphs

[0016] to

[0021] of Japanese Patent Application Publication No. 2012-215689 is preferably used.

[0225] As a polyester resin, commercially available products such as the VILON (registered trademark) series (e.g., VILON500) manufactured by Toyobo Co., Ltd. can also be used.

[0226] As commercially available (meth)acrylic resins, the SK Dyne series from Soken Chemical & Engineering Co., Ltd. (e.g., SK Dyne-SF2147, etc.) can also be used.

[0227] As a polystyrene resin, a resin containing 50% by mass or more repeating units derived from styrene monomers is preferred, a resin containing 70% by mass or more repeating units derived from styrene monomers is more preferred, and a resin containing 85% by mass or more repeating units derived from styrene monomers is even more preferred.

[0228] Specific examples of styrene monomers include styrene and its derivatives. Here, styrene derivatives are compounds to which other groups are bonded, such as alkylstyrene like o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, and p-ethylstyrene, as well as substituted styrene such as hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, and p-chlorostyrene, which have hydroxyl, alkoxy, carboxyl, or halogen groups introduced onto the benzene ring of styrene.

[0229] Furthermore, polystyrene resins may also contain repeating units derived from monomers other than styrene-based monomers. Examples of other monomers include alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methylphenyl methacrylate, and isopropyl methacrylate; unsaturated carboxylic acid monomers such as methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, and cinnamic acid; anhydrides, i.e., unsaturated dicarboxylic acid anhydrides, such as maleic anhydride, itaconic acid, ethyl maleic acid, methyl itaconic acid, and chloromaleic acid; unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; and conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene.

[0230] Commercially available polystyrene resins include: AS-70 (acrylonitrile-styrene copolymer resin) manufactured by NIPPONSTEEL & SUMIKINCHEMICAL CO., LTD.; SMA2000P (styrene-maleic acid copolymer) manufactured by KAWAHARA PETROCHEMICAL CO., LTD.; CLEAREN 530L and CLEAREN 730L manufactured by Denka Company Limited; TUFPRENE 126S and ASAPRENE T411 manufactured by Asahi Kasei Corporation; KRATON D1102A and KRATON D11 16A manufactured by KRATONPOLYMERS JAPAN LTD.; Styrolux S and Styrolux T manufactured by STYROLUTION; Asaflex 840 and Asaflex 860 manufactured by Asahi Kasei Corporation; and PS Japan. Examples of commercially available hydrogenated polystyrene resins include Asahi Kasei Corporation's 679, HF77, SGP-10, 475D, H0103, and HT478; DIC Corporation's Dick Styrene XC-515, Dick Styrene XC-535, and Dick Styrene GH-8300-5; Tuftec H series manufactured by Asahi Kasei Corporation; KRATON G series manufactured by Shell Japan Limited; DYNARON (hydrogenated styrene-butadiene random copolymer) manufactured by JSR Corporation; and SEPTON manufactured by Kuraray Co., Ltd. Furthermore, examples of commercially available modified polystyrene resins include Asahi Kasei Corporation's Tuftec M series; Epofriend manufactured by DAICL CORPORATION; polar-modified DYNARON manufactured by JSR Corporation; and RESEDA manufactured by TOAGOSEI CO., LTD.

[0231] Examples of cyclic olefin resins include polymers containing structural units derived from norbornene compounds (R1), polymers containing structural units derived from monocyclic cyclic olefin compounds other than norbornene compounds (R2), polymers containing structural units derived from cyclic conjugated diene compounds (R3), polymers containing structural units derived from vinyl alicyclic hydrocarbon compounds (R4), and hydrides of polymers containing structural units derived from each of the compounds (R1) to (R4).

[0232] In this invention, polymers containing structural units derived from norbornene compounds and polymers containing structural units derived from monocyclic cyclic olefin compounds are used in the sense of ring-opening polymers containing the aforementioned compounds.

[0233] There are no particular limitations on the cyclic olefin resin, but polymers having structural units derived from norbornene compounds as represented by formula (A-II) or formula (A-III) are preferred. Polymers having structural units represented by formula (A-II) are addition polymers of norbornene compounds, and polymers having structural units represented by formula (A-III) are ring-opening polymers of norbornene compounds.

[0234] [Chemical Formula 25]

[0235]

[0236] In the above formulas (A-II) and (A-III), m is an integer from 0 to 4, preferably 0 or 1.

[0237] R in equations (A-II) and (A-III) 3 ~R 6 Each can independently represent a hydrocarbon group with 1 to 10 hydrogen or carbon atoms.

[0238] As R 3 ~R 6 Examples of hydrocarbon groups include alkyl, alkenyl, alkynyl, and aryl groups, with alkyl or aryl groups being preferred.

[0239] X 2 and X 3 and Y 2 and Y 3 Each of these can be independently represented as a hydrogen atom, a hydrocarbon group with 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group with 1 to 10 carbon atoms substituted by a halogen atom, or -(CH2). n COOR 11 -(CH2) n OCOR 12 -(CH2) n NCO, -(CH2) nNO2、-(CH2) n CN, -(CH2) n CONR 13 R 14 -(CH2) n NR 13 R 14 -(CH2) n OZ 1 -(CH2) n W 1 or X 2 With Y 2 or X 3 With Y 3 (-CO)2O or (-CO)2NR formed by mutual bonding 15 .

[0240] Here, it can be used as X 2 X 3 Y 2 and Y 3 R in the above groups 11 ~R 15 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, Z 1 W indicates a hydrocarbon group or a hydrocarbon group substituted with a halogen. 1 Indicates Si(R) 16 ) p D (3-p) (R 16 Represents hydrocarbon groups with 1 to 10 carbon atoms, where D represents a halogen atom, -OCOR 17 or -OR 17 (R 17 (The carbon group is a hydrocarbon group with 1 to 10 carbon atoms). p is an integer from 0 to 3). n is an integer from 0 to 10, preferably from 0 to 8, and more preferably from 0 to 6.

[0241] R in equations (A-II) and (A-III) 3 ~R 6 Preferably, each atom is a hydrogen atom or -CH3, and from the viewpoint of moisture permeability, hydrogen atoms are even more preferred.

[0242] X 2 and X 3 The preferred atoms are hydrogen atoms, -CH3, and -C2H5, respectively. From the viewpoint of moisture permeability, hydrogen atoms are even more preferred.

[0243] Y 2 and Y 3 Preferably, each atom is independently a hydrogen atom, a halogen atom (especially a chlorine atom), or -(CH2)nCOOR. 11(Especially -COOCH3), from the perspective of moisture permeability, hydrogen atoms are further preferred.

[0244] Other groups can be selected appropriately.

[0245] Polymers having structural units represented by formula (A-II) or formula (A-III) may further include one or more structural units represented by the following formula (AI).

[0246] [Chemical Formula 26]

[0247]

[0248] In formula (AI), R 1 and R 2 Each independently represents a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, X 1 and Y 1 Each can be represented independently as: hydrogen atom, hydrocarbon group with 1 to 10 carbon atoms, halogen atom, hydrocarbon group with 1 to 10 carbon atoms replaced by halogen atom, -(CH2). n COOR 11 -(CH2) n OCOR 12 -(CH2) n NCO, -(CH2) n NO2、-(CH2) n CN, -(CH2) n CONR 13 R 14 -(CH2) n NRR 13 R 14 -(CH2) n OZ 1 -(CH2) n W 1 or X 2 With Y 2 or X 3 With Y 3 (-CO)2O or (-CO)2NR formed by mutual bonding 15 It can be used as X. 1 and Y 1 R in the above groups 11 ~R 15 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, Z 1 W indicates a hydrocarbon group or a hydrocarbon group substituted with a halogen. 1 Indicates Si(R) 16 ) p D (3-p) (R 16Represents hydrocarbon groups with 1 to 10 carbon atoms, where D represents a halogen atom, -OCOR 17 or -OR 17 (R 17 (A hydrocarbon group with 1 to 10 carbon atoms). p is an integer from 0 to 3). n represents an integer from 0 to 10.

[0249] The content of the structural unit represented by formula (A-II) or formula (A-III) in the cyclic polyolefin resin is preferably 90% by mass or less, more preferably 30% by mass to 85% by mass, even more preferably 50% by mass to 79% by mass, and even more preferably 60% by mass to 75% by mass.

[0250] Cyclic olefin resins are described in Japanese Patent Application Publication No. 10-007732, Japanese Patent Application Publication No. 2002-504184, and International Publication No. 2004 / 070463, and these contents can be appropriately referenced.

[0251] Cyclic olefin resins can be obtained by addition polymerization of norbornene compounds (e.g., polycyclic unsaturated compounds of norbornene) with each other.

[0252] Commercially available cyclic olefin resins can be used. Examples of commercially available cyclic olefin resins include the ARTON series manufactured by JSR Corporation (e.g., ARTON G, F, RX4500), and ZEON CORPORATION's ZEONOA (Zeonor) ZF14, ZF16, Zeonex (Zeonex) 250, 280, etc.

[0253] Furthermore, examples of cyclic olefin resins include copolymers obtained by addition copolymerization of norbornene compounds with olefins such as ethylene, propylene, and butene, butadiene, conjugated dienes such as isoprene, non-conjugated dienes such as ethylene norbornene, acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylates, methacrylates, maleimide, vinyl acetate, or vinyl chloride, etc., with copolymers with ethylene being preferred.

[0254] Examples of addition (co)polymers of this norbornene compound include those sold by Mitsui Chemicals, Inc. under the product name APEL, with different glass transition temperatures (Tg), such as APL8008T (Tg 70℃), APL6011T (Tg 105℃), APL6013T (Tg 125℃), or APL6015T (Tg 145℃). Additionally, TOPAS8007, 6013, and 6015 particles are commercially available from Polyplastics Co., Ltd. Furthermore, Appear3000 is commercially available from Ferrania.

[0255] Furthermore, hydrides of cyclic olefin resins can be synthesized by hydrogenation following addition polymerization or ring-opening polymerization of norbornene compounds. Synthetic methods are described, for example, in Japanese Patent Application Publication Nos. 01-240517, 07-196736, 60-026024, 62-019801, 2003-159767, and 2004-309979.

[0256] The cyclic olefin resin contained in the resin composition of the present invention preferably has a molecular weight of 5,000 to 500,000, more preferably 8,000 to 200,000, and even more preferably 10,000 to 100,000.

[0257] Examples of polycarbonate resins include reactants of polyphenolic compounds with phosgene or carbonate compounds.

[0258] Examples of polyphenolic compounds include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, bisphenol Z, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, and 2,2-bis(3-isophenyl)cyclohexane. Propyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ether, etc., preferably hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bisphenol A.

[0259] Examples of carbonate compounds include phosgene, diphenyl carbonate, bis(chlorophenyl) carbonate, dinaphthalene carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate, with bis(diphenyl) carbonate, dimethyl carbonate, and diethyl carbonate being preferred.

[0260] Commercially available polycarbonate resins include PANLITE L-1250WP and PANLITE SP-1516 manufactured by TEIJIN LIMITED., Iupizeta EP-5000 and Iupizeta EP-4000 manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., and Cal ibur301-30 manufactured by Sumika Polycarbonate Ltd.

[0261] Examples of thiourethane resins include reactants of isocyanate compounds and polythiols, and reactants of thiourethane resin precursors. Commercially available thiourethane resin precursors include MR-7, MR-8, MR-10, and MR-174 manufactured by Mitsui Chemicals, Inc.

[0262] Examples of polyamide resins include aliphatic polyamide resins and aromatic polyamide resins. Examples of aliphatic polyamide resins include nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 666, nylon 610, and nylon 612. Examples of aromatic polyamide resins include resins polymerized by dehydration condensation of a diamine and a dicarboxylic acid, wherein at least one of the diamine and the dicarboxylic acid contains an aromatic ring. Specific examples of aromatic polyamide resins include condensation polymers of dimethylimine and adipic acid or adipic acid halides.

[0263] The resin is preferably selected from at least one of (meth)acrylic resins, polystyrene resins, polyester resins, polyurethane resins, thiourethane resins, polyimide resins, polyamide resins, epoxy resins, polycarbonate resins, phthalate resins, cellulose acylate resins, and cyclic olefin resins. From the viewpoint of good compatibility with specific compounds and easy acquisition of cured products with suppressed surface morphological inhomogeneity, it is more preferably selected from at least one of (meth)acrylic resins, polystyrene resins, polyester resins, polyurethane resins, cyclic olefin resins, and polycarbonate resins.

[0264] The weight-average molecular weight (Mw) of the resin contained in the resin composition of the present invention is preferably 2,000 to 2,000,000. The Mw of the resin is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 50,000 or more. The Mw of the resin is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less.

[0265] Furthermore, when using epoxy resin as the resin, the weight-average molecular weight (Mw) of the epoxy resin is preferably 100 or more, more preferably 200 to 2,000,000. The Mw of the epoxy resin is preferably 1,000,000 or less, more preferably 500,000 or less. The Mw of the epoxy resin is preferably 2,000 or more.

[0266] In this invention, the weight-average molecular weight (Mw) of the resin is a value determined by gel permeation method (GPC).

[0267] In the GPC-based assay, the HLC (registered trademark)-8020GPC (manufactured by TOSOHCORPORATION) was used as the assay apparatus, three TSKgel (registered trademark) Super Multipore HZ-H (4.6mm ID × 15cm, manufactured by TOSOH CORPORATION) columns were used as the column, and THF (tetrahydrofuran) was used as the eluent.

[0268] Furthermore, as the measurement conditions, the sample concentration was set to 0.45% by mass, the flow rate was set to 0.35 ml / min, the sample injection volume was set to 10 μL, the measurement temperature was set to 40 °C, and the measurement was performed using an RI detector.

[0269] The calibration curves were prepared using eight samples from TOSOH CORPORATION's "Standard Samples TSK standard, polystyrene": "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000" and "n-propylbenzene".

[0270] The resin composition involved in this invention may contain only one type of resin or may contain two or more types of resin.

[0271] The resin content in the resin composition involved in this invention may be appropriately determined according to the purpose and use of the composition involved in this invention.

[0272] (Other ingredients)

[0273] In addition to the specific compounds described and various solvents and resins as desired, the compositions of the present invention may further contain other components, provided that the near-infrared absorption and thermal stability of the composition are not impaired.

[0274] Other components include infrared absorbers (also called other infrared absorbers) other than the specific compounds already described, surfactants used to improve the coating surface properties during film formation, polymerizable compounds, pigment derivatives, polymerization inhibitors, solvents, sensitizers, cosensitizers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulation agents, etc.

[0275] (Other infrared absorbers)

[0276] As other infrared absorbers, near-infrared absorbers other than the specific compounds already described are preferred.

[0277] Other near-infrared absorbers include pyrrolopyrrole compounds, squaric acid compounds, anthocyanin compounds, phthalocyanine compounds, naphthalene phthalocyanine compounds, quarteriene compounds, anthocyanin compounds, ketoneonium compounds, oxacyanine compounds, imine compounds, dithiol compounds, triarylmethane compounds, pyrrole methylene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, metal oxides, and metal borides.

[0278] When including other infrared absorbers, the present invention may contain only one type of infrared absorber or two or more types. The content of other infrared absorbers is preferably less than 100% by mass, more preferably less than 50% by mass, and even more preferably 0% by mass, relative to the total amount of the specific compound of the present invention and other infrared absorbers.

[0279] (polymeric compounds)

[0280] The compositions of the present invention may contain polymerizable compounds. By further containing polymerizable compounds, the compositions of the present invention can be configured as pattern-forming compositions that are partially cured by localized energy application, such as pattern exposure.

[0281] Image Forming Materials

[0282] The image forming material of the present invention comprises a compound represented by the general formula (1) described herein (specific compound (1) of the present invention).

[0283] The image forming material of the present invention is particularly suitable for use as an image recording material that absorbs the near-infrared region.

[0284] Specific examples of image forming materials include inkjet recording materials, thermal recording materials, pressure-sensitive recording materials, recording materials using electrophotography, transfer-type silver halide photosensitive materials, printing inks, recording pens, and stamps. Among these, the image forming material of the present invention is particularly preferably used as an inkjet recording material or a recording material using electrophotography.

[0285] The image forming material of the present invention preferably comprises a liquid medium.

[0286] There are no particular limitations on the liquid medium used; for example, the same liquid medium as the solvent in the composition of the present invention can be used. Furthermore, the liquid medium used when the image forming material of the present invention is an aqueous composition will be described later.

[0287] The image forming material of the present invention may contain the compound of the present invention in a state dissolved in a liquid medium, or it may contain the compound of the present invention in a state of particles dispersed in a liquid medium as solid particles.

[0288] Image forming materials containing the compounds of the present invention as solid particles can be prepared by dispersing the compounds of the present invention in a liquid medium using a dispersion device.

[0289] There are no particular limitations on the dispersion device; any conventionally known dispersion device can be used.

[0290] Specific examples of dispersing devices include ball mills, sand mills, bead mills, roller mills, jet mills, paint mixers, grinders, ultrasonic dispersers, and dispersers.

[0291] The volume average particle size is not particularly limited, but is preferably 10 nm to 250 nm, more preferably 20 nm to 250 nm, and even more preferably 30 nm to 230 nm.

[0292] If the volume-average particle size is within the above range, the preservation stability of the image forming material becomes better, thereby enabling the acquisition of sufficient optical density.

[0293] The volume-average particle size was measured using a particle size distribution measuring device employing dynamic light scattering. For example, a particle size distribution measuring device manufactured by Microtrack Bell Co., Ltd. (product name: UPA-EX150) can be used. However, the measuring device is not limited to this.

[0294] The image forming material of the present invention may contain only one compound of the present invention, or it may contain two or more compounds.

[0295] The content of the compound of the present invention in the image forming material is not particularly limited and can be appropriately set according to the purpose. Generally, from the viewpoint of being able to fully exhibit infrared absorption capability, the content of the compound of the present invention in the image forming material is preferably 0.001% to 30% by mass relative to the total mass of the image forming material, more preferably 0.01% to 10% by mass, and even more preferably 0.05% to 5% by mass.

[0296] When the image forming material of the present invention is an aqueous composition, examples of liquid media include water and mixtures of water and organic solvents.

[0297] The water content in the liquid medium is preferably 30% to 100% by mass relative to the total mass of the liquid medium, and more preferably 50% to 100% by mass.

[0298] There are no particular limitations on the type of water. For example, from the viewpoint of having fewer impurities, distilled water, ion-exchanged water, distilled water that has undergone ion exchange, and pure water are preferred.

[0299] When the liquid medium contains organic solvents in addition to water, examples of organic solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol, pentanediol, glycerol, glycerol, dithioethylene glycol, etc.; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, etc. Alcohol monoethyl ether, ethylene glycol monophenyl ether, 3-methyl-3-methoxybutanol, 3-methoxybutanol and other diol derivatives, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine and other amine compounds, formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidinone, 1,3-dimethyl-2-imidazolinone, acetonitrile, acetone, methyl ethyl ketone, tetrahydrofuran, butyl cellosolve and other water-soluble organic solvents.

[0300] When the image forming material of the present invention is an aqueous composition, the image forming material of the present invention may further contain an aqueous resin.

[0301] Examples of water-based resins include, for example, resins dissolved in water, water-dispersible resins dispersed in water, colloidal dispersion resins, and mixtures thereof.

[0302] Here, "resin dissolved in water" refers to a resin that dissolves in water at a temperature of 25°C at a mass of 1% or more. Specific examples of resins dissolved in water include gelatin, vinyl resins (e.g., polyvinyl alcohol), and water-soluble cellulose derivatives (e.g., carboxymethyl cellulose).

[0303] Hydrophobic synthetic resins can be cited as examples of water-dispersible resins.

[0304] Specific examples of water-dispersible resins include acrylic resins, styrene-acrylic resins, vinyl resins, polyurethanes, polyesters, polyamides, and fluoropolymers.

[0305] Examples of acrylic resins include homopolymers or copolymers obtained by polymerization of at least one monomer selected from the group consisting of acrylic acid, acrylate compounds (e.g., alkyl acrylates), acrylamide, acrylonitrile, methacrylic acid, methacrylate compounds (e.g., alkyl methacrylates), methacrylamide, and methacrylonitrile.

[0306] Among these, the acrylic resin is preferably a homopolymer or copolymer obtained by polymerization of at least one monomer selected from the group consisting of acrylate compounds and methacrylate compounds, and more preferably a homopolymer or copolymer obtained by polymerization of at least one monomer selected from the group consisting of acrylate compounds having 1 to 6 carbon atoms and methacrylate compounds.

[0307] When the image forming material of the present invention further comprises an aqueous resin, the aqueous resin may be contained as an aqueous dispersion of resin particles.

[0308] As an aqueous dispersion of resin particles, commercially available products can be used.

[0309] Examples of commercially available aqueous dispersions of resin particles include Superflex 830, 460, 870, 420, and 420NS (manufactured by DKS Co., Ltd.; polyurethane), Bondic 1370NS and 1320NS (manufactured by DIC Corporation; polyurethane), Hydran Hw140SF, WLS201, WLS202, and WLS213 (manufactured by DIC Corporation; polyurethane), 0lestar UD350, UD500, and UD600 (manufactured by Mitsui Chemicals, Inc.; polyurethane), NeoRez R972, R966, and R9660 (manufactured by Kusumoto Chemicals, Ltd.; polyurethane), FINE TECH Es650 and Es2200 (manufactured by DIC Corporation; polyester), and Baironar (registered trademark) MD1100, MD1400, and MD1480 (TOYOBO). TOAGOSEI CO.,LTD. manufactures [polyester], Julimer (registered trademark) ET325, ET410, AT-613 and SEK301 [TOAGOSEI CO.,LTD. manufactures; acrylic resin], Boncoat AN1 17 and AN226 [DIC Corporation manufactures; acrylic resin], Luckstar DS616 and DS807 [DIC Corporation manufactures; styrene-butadiene rubber], Nippol LX110, LX206, LX426 and LX433 [ZEON CORPORATION manufactures; styrene-butadiene rubber] and Nippol LX513, LX1551, LX550 and LX1571 [ZEON CORPORATION manufactures; acrylonitrile-butadiene rubber].

[0310] The image forming material of the present invention preferably further comprises a surfactant.

[0311] If the image forming material of the present invention further comprises a surfactant, for example, the dispersibility of the particles can be improved. Furthermore, if the image forming material of the present invention further comprises a surfactant, for example, the quality of the formed image can be improved.

[0312] The meaning of the surfactant in the image forming material of the present invention is the same as that of the surfactant in the composition of the present invention, and the preferred methods are also the same, so the description is omitted here.

[0313] When the image forming material of the present invention is ink, the image forming material of the present invention comprises the compound of the present invention and a liquid medium.

[0314] Specific examples of inks include offset printing inks, inkjet inks, UV-curable inks, inks for notebooks (e.g., ballpoint pens), toners, inks for ink pads, inks for penetrating printing, inks for printing and dyeing, inks for letterpress printing, inks for gravure printing (e.g., gravure printing), inks for stencil printing (e.g., screen printing), and flexographic inks.

[0315] When the image forming material of the present invention is ink, the compound of the present invention is preferably dispersed in a liquid medium as solid particles, and the liquid medium is preferably water or a mixture of water and an organic solvent.

[0316] When the image forming material of the present invention is ink, the image forming material of the present invention may contain various additives as needed, as long as it does not impair the effect of the present invention.

[0317] Examples of additives include, for instance, resins, desiccant (so-called wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, preservatives, mildew inhibitors, pH adjusters, surface tension adjusters, defoamers, viscosity modifiers, dispersants, dispersion stabilizers, rust inhibitors, chelating agents, and other additives.

[0318] In addition, the purpose of using an anti-fading agent is to improve the preservation of images formed by the image forming material, i.e., ink, of the present invention.

[0319] As a resin, examples can be made of resins that are the same as those used in the compositions of the present invention.

[0320] When the image forming material of the present invention is an aqueous composition, the additives can be directly contained in the image forming material of the present invention.

[0321] There are no particular limitations on the recording medium used when forming an image using the image forming material of the present invention. Examples include ordinary uncoated paper, coated paper, resin films formed from various non-absorbent resin materials used in so-called flexible packaging, and metal foils.

[0322] Specific examples of paper include plain white outline paper, kraft paper, cardboard, high-grade paper, OCR paper, art paper, coated paper, mirror-coated paper, capacitor paper, and paraffin paper.

[0323] Specific examples of resin films include polyester film, polypropylene (PP) film, cellophane, acetate film, polycarbonate (PC) film, acrylic resin film, polyethylene terephthalate (PET) film, biaxially stretched polystyrene (OPS) film, biaxially stretched polypropylene (OPP) film, biaxially stretched nylon (ONy) film, polyvinyl chloride (PVC) film, polyethylene (PE) film, and triacetate (TAC) film.

[0324] Furthermore, examples of recording media include laminated paper coated with resin, and composite substrates with metal layers such as copper and aluminum formed on paper or resin films.

[0325] <membrane>

[0326] When the composition involved in this invention is a resin composition, the resin contained in the composition is a component that contributes to film formation, and a film is formed by the composition involved in this invention by including the resin.

[0327] The membrane of the present invention comprises the pigment composition of the present invention as described herein and further comprises a resin composition containing a resin. The membrane of the present invention may be a cured product of the pigment composition of the present invention or a film-shaped product of the pigment composition of the present invention. More specifically, as a membrane of the present invention, examples include a pigment composition of the present invention containing a resin. As one example, a membrane of a pigment composition of the present invention containing a resin kneading a specific compound (1) is formed. As another example, a membrane as a cured product of a pigment composition containing a specific compound (1), a resin, and a solvent is provided.

[0328] When the resin composition involved in this invention contains a solvent, it can be dried to form a film as a cured product.

[0329] In this invention, "drying" only requires removing at least a portion of the solvent, without completely removing it. The amount of solvent to be removed can be set as needed.

[0330] The membrane involved in this invention can be preferably used as a filter such as an infrared cutoff filter. Furthermore, it can also be used as a heat ray shielding filter or an infrared transmission filter.

[0331] The cured resin composition involved in this invention can be laminated on a support, or it can be a self-standing film that is cured on the support and then peeled off from the support.

[0332] The membrane involved in this invention can be patterned or unpatterned (flat membrane).

[0333] The thickness of the membrane in this invention is appropriately selected according to the application of the membrane, such as a filter, heat shield, photothermal conversion membrane, etc.

[0334] For example, when the membrane is used as an infrared absorption filter, the thickness of the membrane can be set to, for example, 0.1 μm to 1000 μm, preferably 0.5 μm to 500 μm.

[0335] The thickness of the membrane involved in this invention can be appropriately adjusted according to the purpose. The membrane thickness is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 20 μm or less. The lower limit of the membrane thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0336] <Filter>

[0337] The filter of the present invention comprises the membrane of the present invention described above.

[0338] The filter of the present invention can preferably be used as an infrared cut-off filter or an infrared transmission filter, and can more preferably be used as an infrared cut-off filter.

[0339] Furthermore, the method of having the film involved in the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black and colorless is also a preferred method of the filter involved in the present invention.

[0340] An infrared cut-off filter, as one type of filter according to the present invention, has the membrane according to the present invention.

[0341] Furthermore, the infrared cutoff filter involved in this invention can be a filter that only blocks a portion of the infrared wavelengths in the infrared region, or it can be a filter that blocks the entire infrared region. For example, a near-infrared cutoff filter can be cited as an example of a filter that only blocks a portion of the infrared wavelengths in the infrared region.

[0342] Furthermore, as a near-infrared cutoff filter, it is preferable to be an infrared filter with a cutoff wavelength of 1000nm to 2500nm, and more preferably an infrared filter with a cutoff wavelength range of 1100nm to 2000nm.

[0343] In addition to the aforementioned membrane, the infrared cut-off filter of the present invention may further include a copper-containing layer, a dielectric multilayer film, an ultraviolet absorption layer, etc. The infrared cut-off filter of the present invention further includes at least a copper-containing layer or a dielectric multilayer film, thereby easily obtaining an infrared cut-off filter with a wide field of view and excellent infrared shielding performance.

[0344] Furthermore, the infrared cut-off filter according to the present invention further includes an ultraviolet absorption layer, thereby enabling the formation of an infrared cut-off filter with excellent ultraviolet shielding properties. For example, the ultraviolet absorption layer described in paragraphs 0040-0070 and 0119-0145 of International Publication No. 2015 / 099060 can be referenced and incorporated herein by reference. As a dielectric multilayer film, the dielectric multilayer film described in paragraphs 0255-0259 of Japanese Patent Application Publication No. 2014-41318 can be referenced and incorporated herein by reference. As a copper-containing layer, a glass substrate made of copper-containing glass (copper-containing glass substrate) or a layer containing copper complexes (copper-containing complex layer) can also be used. Examples of copper-containing glass substrates include copper-containing phosphate glass and copper-containing fluorophosphate glass. Commercially available copper-containing glass products include NF-50 (manufactured by AGC TECHNOGLASS Co., Ltd.), BG-60, BG-61 (and above, manufactured by Schott AG), and CD5000 (manufactured by HOYA CORPORATION).

[0345] The infrared cutoff filter involved in this invention can be used in various devices such as solid-state imaging elements such as CCD (charge-coupled device) and CMOS (complementary metal-oxide-semiconductor), infrared sensors, and image display devices.

[0346] In particular, it is useful in digital cameras, smartphone cameras, mobile phone cameras, digital camcorders, wearable device cameras, personal computer cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, portable information terminals, video game consoles, portable game consoles, fingerprint authentication systems, and digital music players. Furthermore, it can also function as a heat-stop filter installed on glass panels in automobiles, buildings, and other structures.

[0347] The infrared cutoff filter according to the present invention is preferably provided in a manner in which the film obtained by using the composition according to the present invention has pixels (patterns) and at least one pixel (pattern) selected from red, green, blue, magenta, yellow, cyan, black and colorless.

[0348] There are no particular limitations on the manufacturing method of the filter involved in this invention. Preferably, it includes a step of applying the composition involved in this invention onto a support to form a composition layer and a step of curing the composition layer.

[0349] Furthermore, when the composition involved in the present invention has pattern-forming properties, the method for manufacturing the filter can also be configured as a step of applying the composition involved in the present invention to a support to form a composition layer, a step of applying energy in a patterned manner to cure, a step of removing uncured portions that have not been applied energy to form a pattern, and a method for forming a patterned filter.

[0350] In this invention, an infrared cutoff filter refers to a filter that allows light of visible wavelengths (visible light) to pass through while blocking at least a portion of light of infrared wavelengths (infrared light). An infrared cutoff filter can transmit all wavelengths of light in the visible region, or it can allow light of a specific wavelength range within the visible region to pass through while blocking light of that specific wavelength range. Furthermore, in this invention, a color filter refers to a filter that allows light of a specific wavelength range within the visible region to pass through while blocking light of that specific wavelength range. And, in this invention, an infrared transmission filter refers to a filter that blocks visible light while transmitting at least a portion of infrared light.

[0351] Photothermal Conversion Materials

[0352] The specific compound (1) of the present invention and the pigment composition of the present invention containing the specific compound (1) have very high near-infrared absorption capacity, and therefore can be preferably used as photothermal conversion materials.

[0353] As an example of photothermal conversion materials, materials for laser welding can be cited, which selectively absorb laser light and generate localized heat, thereby melting the thermoplastic resin as the substrate and enabling bonding.

[0354] In addition, it can also be used as a material for laser marking, a heating accelerator, and a drying aid for inks.

[0355] Applications of materials used in laser welding

[0356] If the specific compound (1) of the present invention and the composition containing the specific compound (1) of the present invention are used for the welding of polymer resins, the color difference between the polymer resins can be reduced by irradiation with a laser, and the joints can be reliably welded together to obtain sufficient bonding strength.

[0357] Examples of polymeric resins that can be used for bonding include, for example, polystyrene, polymethyl methacrylate, cyclic olefin polymers, polycarbonate, polyethylene terephthalate, etc.

[0358] In recent years, from the perspectives of lightweighting and cost reduction, polymer resin molded parts have been frequently used as components in various fields, including automotive parts. Furthermore, from the perspective of high productivity in polymer resin molded parts, a common approach is to pre-divide the polymer resin molded parts into multiple segments, mold these segments, and then join these segments together.

[0359] Conventionally, the bonding of polymer resins has been carried out using laser welding. In this method, a transmissive polymer resin that is transmissive to laser light and an absorbent polymer resin that is absorbent to laser light are overlapped, and then a laser is irradiated from the transmissive polymer resin side. This causes the contact surfaces of the transmissive and absorbent polymer resins to be heated and melted, thus bonding them together as a single unit.

[0360] Furthermore, in conventional laser welding methods, when joining the same or different types of polymer resins, the joined polymer resins become either laser-absorbing or non-laser-absorbing resins, resulting in color differences and limiting the applications of the joined polymer resins.

[0361] Specifically, for lasers, non-absorbent polymer resins are white or transparent laser-transmitting colors, while absorptive components are black laser-absorbing colors such as carbon black, which will create a sense of incongruity in appearance.

[0362] That is, when joining polymer resins of different colors, there are problems such as weak bonding force and protruding joints.

[0363] If at least one material selected from the specific compound (1) of the present invention and the composition of the present invention containing the specific compound (1) of the present invention is used, the near-infrared absorption capacity of the above material is very high, thus solving these problems.

[0364] In particular, it is possible to bond translucent polymer resins to each other, i.e., transparent polymer resins, using at least one material selected from the specific compound (1) of the present invention and the composition of the present invention containing the specific compound (1).

[0365] For example, the composition of the present invention is applied to the area of ​​the transmissive polymer resin to be bonded, preferably the composition comprising the resin, and interspersed with a polymer resin layer coated with another transmissive polymer resin as described above. When irradiated with a laser from one side, the laser is absorbed only at the coated area, and localized instantaneous heating occurs, thereby enabling the polymer resins to melt and bond together.

[0366] At this time, if the specific compound (1) of the present invention and the composition of the present invention are used, the near-infrared absorption capacity is high, and a strong bond can be achieved by adding a small amount, so the color difference of the coated part is not obvious.

[0367] Alternatively, the method of incorporating the specific compound (1) of the present invention into the transmissive polymer resin itself can also be considered. The method of incorporating the specific compound (1) into the resin can also achieve the same effect as the method of coating the specific compound (1) onto the resin. That is, if at least one material selected from the specific compound (1) of the present invention and the composition of the present invention containing that compound is used for laser welding applications, a strong bond between the desired resins can be achieved while maintaining high design flexibility.

[0368] <Near-infrared absorbing compounds represented by general formula (1)>

[0369] The first embodiment of the near-infrared absorbing compound of the present invention is a near-infrared absorbing compound represented by the following general formula (1).

[0370] The near-infrared absorber of the present invention described below is a novel compound that has absorption in the long-wavelength infrared region and is thermally stable.

[0371] [Chemical Formula 27]

[0372]

[0373] In general formula (1), R1, R2, R3, R4, R5, R6, R7 and R8 each independently represent a group selected from phenyl, aryl, or heteroaryl groups with substituents having a σp value of -0.5 or more that conforms to the Hammett equation, having carbon atoms of 7 to 20, and having substituents. Two or more of R1, R2, R3, R4, R5, R6, R7 and R8 can be linked together to form a ring.

[0374] R9, R 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They can be the same as each other, or they can be different.

[0375] m is 1 or 2. X - This indicates a nonnucleophilic anion.

[0376] The compound represented by the above formula (1) is the same as the specific compound (1) contained in the first embodiment (composition (1)) of the pigment composition of the present invention described above, wherein R1 to R8, R9 to R18, R9 to R18, R9 to R19 ... 13 , n, m and X - The meanings are the same as those of R1~R8, R9~R in the general formula (1) that has already been described. 13 , n and X - The meanings are the same, and the preferred examples are also the same.

[0377] <Near-infrared absorbing compounds represented by general formula (2)>

[0378] The second embodiment of the near-infrared absorbing compound of the present invention is a near-infrared absorbing compound represented by the following general formula (2).

[0379] The near-infrared absorber of the present invention described below is a novel compound that has absorption in the long-wavelength infrared region and is thermally stable.

[0380] [Chemical Formula 28]

[0381]

[0382] In general formula (1), R1, R2, R3, R4, R5, R6, R7 and R8 each independently represent a group selected from phenyl, aryl, or heteroaryl groups with substituents having a σp value of -0.5 or more that conforms to the Hammett equation, having carbon atoms of 7 to 20, and having substituents. Two or more of R1, R2, R3, R4, R5, R6, R7 and R8 can be linked together to form a ring.

[0383] R9, R 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They can be the same as each other, or they can be different.

[0384] X - This indicates a nonnucleophilic anion.

[0385] The compound represented by the above formula (2) is the same as the specific compound (2) contained in the second embodiment (composition (2)) of the pigment composition of the present invention described above, wherein R1 to R8, R9 to R18, R9 to R18, R9 to R18, R9 to R19 ... 13 , n, m and X -The meanings are the same as those of R1~R8 and R9~R in the general formula (2) that has already been described. 13 , n and X - The meanings are the same, and the preferred examples are also the same.

[0386] The novel near-infrared absorbing compounds of the present invention exhibit good absorption and thermal stability in the long-wavelength infrared region, and are therefore preferably suitable for various applications requiring near-infrared absorption.

[0387] Examples of preferred uses are illustrated in the compositions of the present invention already described.

[0388] Example

[0389] The present invention will now be described in detail with reference to embodiments, but the present invention is not limited thereto.

[0390] In this embodiment, unless otherwise specified, "%" and "parts" refer to "mass %" and "mass parts," respectively. Furthermore, in polymer compounds, unless otherwise specified, the molecular weight is the weight-average molecular weight (Mw), and the proportion of structural units is the molar percentage.

[0391] The weight-average molecular weight (Mw) is a value determined based on the gel permeation (GPC) method as a conversion value for polystyrene.

[0392] [Example 1, Example 2]

[0393] Following the above procedure, intermediate X-1 was first synthesized, followed by the synthesis of exemplary compounds (A-1) and (B-1).

[0394] [Chemical Formula 29]

[0395]

[0396] <Synthesis of Intermediate X-1>

[0397] In 25 ml of toluene, 0.19 g of palladium acetate and 6.5 g (16 equivalents) of sodium tert-butoxide were stirred at room temperature, and 0.34 g (0.4 equivalents) of tri-n-butylphosphine was added. The mixture was then heated to 60 °C and stirred for 20 minutes.

[0398] 2 g of N1,N1'-(1,4-phenyl)bis(N1-(4-aminophenyl)benzene-1,4-diamine) and 8.7 g (12 equivalents) of p-bromotoluene were added to the reaction solution, and the mixture was stirred under reflux for 3 hours. The reaction solution was cooled to 30°C, 30 ml of 20% hydrochloric acid aqueous solution and 30 ml of ethyl acetate were added, and the mixture was filtered to obtain the filtrate.

[0399] The filtrate obtained by washing with water and ethyl acetate yielded 3.4 g of aromatic amine X-1.

[0400] The proton nuclear magnetic resonance of the obtained aromatic amine X-1 ( 1 In H-NMR, solvent: deuterated chloroform (CDCl3), chemical shifts δ 7.03 (br-s, 22H), 6.96 (br-s, 30H), 2.30 (s, 24H).

[0401] <Example 1: Synthesis of Compound A-1>

[0402] 1 g of the aromatic amine (X-1) obtained above was added to 40 ml of acetonitrile, and 2.6 g (5 equivalents) of OXONE (registered trademark) persulfate compound was added as an oxidant. The mixture was stirred at room temperature for 6 hours. 80 ml (5 equivalents) of 3% sodium perchlorate aqueous solution was added to the reaction solution, and the precipitated solid was filtered off. 1.5 g of diammonium compound A-1 was obtained by washing with water.

[0403] Due to the properties of the obtained diammonium (example compound A-1), NMR could not be determined. Mass spectrometry (MS) was performed under the following conditions.

[0404] MS(m / z)=1291.63([M 2+ ClO4 - ] + )), 98.93 (ClO4) - For example, the absorption maximum wavelength of compound A-1 in chloroform solution is 1209 nm.

[0405] exist Figure 1 The absorption spectrum of an illustrative compound A-1 in a chloroform solution is shown in the figure.

[0406] <Example 2: Synthesis of Compound B-1>

[0407] 1 g of the aromatic amine (X-1) obtained above was added to 40 ml of acetonitrile, and 0.5 g (1 equivalent) of OXONE (registered trademark) persulfate compound was added as an oxidant. The mixture was stirred at room temperature for 3 hours. 80 ml (5 equivalents) of 3% sodium perchlorate aqueous solution was added to the reaction solution, and the precipitated solid was filtered and washed with water, thereby obtaining 1.6 g of cationic pigment B-1. Due to the characteristics of the obtained cationic pigment B-1, NMR could not be determined. Mass spectrometry analysis was performed in the same manner as in Example 1.

[0408] MS(m / z)=1192.65(M +), 98.93 (ClO4) - The absorption maximum wavelength of compound (B-1) in chloroform solution is 1695 nm.

[0409] exist Figure 2 The absorption spectrum of an illustrative compound B-1 in a chloroform solution is shown.

[0410] [Example 3, Example 4]

[0411] Intermediate X-3 was first synthesized by changing p-bromomethyldiisopropylbenzene used in the synthesis of intermediate X-1 to bromomethyldiisoheptane, followed by the synthesis of illustrative compounds (A-3) and (B-3).

[0412] [Chemical Formula 30]

[0413]

[0414] Synthesis of intermediate X-3

[0415] In 25 ml of toluene, 0.19 g of palladium acetate and 6.5 g (16 equivalents) of sodium tert-butoxide were stirred at room temperature, and 0.34 g (0.4 equivalents) of tri-n-butylphosphine was added. The mixture was then heated to 60 °C and stirred for 20 minutes.

[0416] 2 g of N1,N1'-(1,4-phenyl)bis(N1-(4-aminophenyl)benzene-1,4-diamine) and 10.1 g (12 equivalents) of bromotrimethylbenzene were added to the reaction solution, and the mixture was stirred under reflux for 6 hours. The reaction solution was cooled to 30°C, and 30 ml of 20% hydrochloric acid aqueous solution and 30 ml of ethyl acetate were added, followed by filtration.

[0417] The filtrate obtained by washing with water and ethyl acetate yielded 4.0 g of aromatic amine X-3.

[0418] The proton nuclear magnetic resonance of the obtained aromatic amine X-1 ( 1 In H-NMR, solvent: deuterated chloroform (CDCl3), chemical shifts δ 6.82 (s, 20H), 6.74 (s, 8H), 6.49 (d, J = 8.0 Hz, 8H), 2.24 (s, 24H), 1.97 (s, 24H), 1.73 (s, 24H).

[0419] <Example 3: Synthesis of Compound A-3>

[0420] 1 g of the aromatic amine (X-3) obtained above was added to 40 ml of acetonitrile, and 2.2 g (5 equivalents) of OXONE (registered trademark) persulfate compound was added as an oxidant. The mixture was stirred at room temperature for 6 hours. 80 ml (5 equivalents) of 3% sodium perchlorate aqueous solution was added to the reaction solution, and the precipitated solid was filtered. After washing with water, 1.6 g of diammonium compound A-3 was obtained.

[0421] Due to the properties of the obtained diammonium (exemplary compound A-3), NMR could not be determined. Mass spectrometry (MS) was performed in the same manner as in Example 1.

[0422] MS(m / z)=1516.81([M 2+ ClO4 - ] + )), 98.94 (ClO4) - ).

[0423] For example, the absorption maximum wavelength of compound A-3 in chloroform solution is 1231 nm.

[0424] <Example 4: Synthesis of Compound B-3>

[0425] 1 g of the aromatic amine (X-1) obtained above was added to 40 ml of acetonitrile, and 0.4 g (1 equivalent) of OXONE (registered trademark) persulfate compound was added as an oxidant. The mixture was stirred at room temperature for 3 hours. 80 ml (5 equivalents) of 3% sodium perchlorate aqueous solution was added to the reaction solution, and the precipitated solid was filtered and washed with water, thereby obtaining 1.6 g of cationic pigment B-1. Due to the characteristics of the obtained cationic pigment B-1, NMR could not be determined. Mass spectrometry analysis was performed in the same manner as in Example 1.

[0426] MS(m / z)=1417.85(M + ), 98.93 (ClO4) - ).

[0427] The absorption maximum wavelength of the chloroform solution of compound (B-3) is 1695 nm.

[0428] [Example 5, Example 6]

[0429] By replacing the 3% sodium perchlorate aqueous solution used in the synthesis of illustrative compounds (A-1) and (B-1) with a 3% lithium tetra(pentafluorophenyl)borate aqueous solution, illustrative compounds (A-35) and (B-35) were synthesized.

[0430] [Chemical Formula 31]

[0431]

[0432] <Example 5: Synthesis of Compound A-35>

[0433] 1 g of aromatic amine (X-1) was added to 40 ml of acetonitrile, and 2.2 g (5 equivalents) of OXONE (registered trademark) persulfate compound was added as an oxidant. The mixture was stirred at room temperature for 6 hours. 80 ml (5 equivalents) of a 3% aqueous solution of lithium tetra(pentafluorophenyl)borate was added to the reaction solution, and the precipitated solid was filtered and washed with water to obtain 2.0 g of diammonium compound A-3.

[0434] Due to the properties of the obtained diammonium (exemplary compound A-44), NMR could not be determined. Mass spectrometry (MS) was performed in the same manner as in Example 1.

[0435] MS(m / z)=1872.59([M 2+ B(C6F5)4 - ]) + ), 678.99[B(C6F5)4] - .

[0436] For example, the absorption maximum wavelength of compound A-35 in chloroform solution is 1338 nm.

[0437] <Example 6: Synthesis of Compound B-35>

[0438] 1 g of the aromatic amine (X-1) obtained above was added to 40 ml of acetonitrile, and 0.4 g (1 equivalent) of OXONE (registered trademark) persulfate compound was added as an oxidant. The mixture was stirred at room temperature for 3 hours. 80 ml (5 equivalents) of 3% sodium perchlorate aqueous solution was added to the reaction solution, and the precipitated solid was filtered and washed with water, thereby obtaining 1.6 g of cationic pigment B-1. Due to the characteristics of the obtained cationic pigment B-1, NMR could not be determined. Mass spectrometry analysis was performed in the same manner as in Example 1.

[0439] MS(m / z)=1192.63(M + ), 678.98[B(C6F5)4] - The absorption maximum wavelength of compound (B-35) in chloroform solution is 1821 nm.

[0440] [Examples 7 to 42]

[0441] Regarding the compounds represented by the above general formulas (1) and (2), when R1 to R8 are changed, the p-bromotoluene used as an intermediate in the synthesis (X-1) is appropriately changed to the corresponding brominated aryl compound. When X is changed, the 3% sodium perchlorate aqueous solution used in the synthesis (A-1 and B-1) is appropriately changed to synthesize the same compounds.

[0442] Following the above scheme, the specific compounds listed in Tables 1 and 2 were obtained.

[0443] [Comparative Examples 1 to 6]

[0444] The diamine compounds, which are known near-infrared absorbing compounds, are designated as Comparative Compounds 1 to 6.

[0445] Comparative compound 1: Comparative compound 1 was obtained according to the description in Japanese Patent Application Publication No. 2009-180875.

[0446] Comparative compound 2: According to Japanese Patent Application Publication No. 2017-116775, comparative compound 2 was obtained.

[0447] Comparative compound 3: According to Japanese Patent Application Publication No. 2002-275134, comparative compound 3 was obtained.

[0448] Comparative compound 4: The diammonium compound (product code T3072: structure below) manufactured by Tokyo Chemical Industry Co., Ltd. is used as comparative compound 4.

[0449] Comparative compound 5: According to Japanese Patent Application Publication No. 2006-188653, comparative compound 5 was obtained.

[0450] Comparative compound 6: According to Japanese Patent Application Publication No. 2016-45391, comparative compound 6 was obtained.

[0451] The structures of the comparative compounds are shown below.

[0452] [Chemical Formula 32]

[0453]

[0454] [Chemical Formula 33]

[0455]

[0456] <Evaluation of specific compounds>

[0457] The specific compounds and comparative compounds 1–6 obtained were evaluated using the following methods.

[0458] The results are shown in Tables 1 and 2 below.

[0459] 1. Mass spectrometric analysis of compounds using matrix-assisted laser desorption / ionization-mass spectrometry (MALDI-MS).

[0460] Each compound listed in Tables 1 and 2 below was dissolved in chloroform and mixed with a matrix chloroform solution. A 1 mL drop was applied to a plate, and after the droplet was air-dried, the MALDI-MS was measured using the apparatus described below.

[0461] • Apparatus: UltrafleXtreme (manufactured by Bruker); Ionization: posi., nega.; Measurement mode: reflected ion beam; Matrix: DCTB

[0462] The compounds listed in Tables 1 and 2 were confirmed to be either the illustrated compounds already described or the comparative compounds mentioned above.

[0463] 2. Evaluation by absorption spectroscopy

[0464] For each of the exemplary compounds listed in Tables 1 and 2 below, by diluting with chloroform to 3.0 × 10⁻⁶ -5 The sample solution was prepared using mol / L, and the near-infrared absorption was evaluated.

[0465] For each sample solution, the absorbance was measured in a 1 mm quartz cell using a spectrophotometer (UV-3600Plus, manufactured by SHIMADZUCORPORATION).

[0466] The wavelength of maximum absorption (λmax) was determined based on the absorption spectra of each sample solution. The results are recorded in Tables 1 and 2 below. Furthermore, the wavelength of λmax was evaluated according to the following criteria.

[0467] (Evaluation Criteria)

[0468] A: λmax is above 1150nm.

[0469] B: λmax is less than 1150nm.

[0470] 3. Solubility Evaluation

[0471] For each of the exemplary compounds listed in Tables 1 and 2 below, a predetermined amount of solvent, methyl ethyl ketone (MEK), was added and stirred at room temperature for 30 minutes, thereby evaluating the solubility according to the following criteria.

[0472] (Evaluation Criteria)

[0473] A: More than 1g can be stably dissolved in 300g of MEK.

[0474] B: 1g does not dissolve in 300g of MEK.

[0475] X: Decomposition was observed by absorption spectroscopy after dissolution.

[0476] 4. Thermal stability evaluation

[0477] Resin compositions were prepared by dissolving 30 mg of the exemplary and comparative compounds listed in the table below in 8.9 g of methyl ethyl ketone and 1.1 g of polystyrene resin (manufactured by Aldrich).

[0478] The obtained resin composition was spin-coated onto a glass substrate to form a coating film. The coating film was dried at 60°C for 2 minutes to produce a resin film.

[0479] A resin film formed on a glass substrate was placed on a hot plate at 180°C for 5 minutes. The rate of decrease in absorbance (λmax) of the film in the heat resistance test was measured and evaluated according to the following criteria.

[0480] (Evaluation Criteria)

[0481] A: The absorbance reduction rate of λmax is less than 5%.

[0482] B: The absorbance reduction rate of λmax is greater than 5% and less than 10%.

[0483] The absorbance reduction rate of C:λmax is greater than 10% and less than 50%.

[0484] The absorbance reduction rate of D:λmax is over 50%.

[0485] X: Insufficient solubility prevents membrane fabrication and evaluation.

[0486] [Table 1]

[0487]

[0488] [Table 2]

[0489]

[0490] The specific compounds in the examples all exhibit absorption in the near-infrared wavelength region, and have good near-infrared absorption and solvent solubility.

[0491] Furthermore, it was confirmed that the resin compositions containing the specific compounds all exhibited good thermal stability.

[0492] On the other hand, even though the diamine skeleton has an aryl group, the comparative compounds 1, 5 and 6, which do not have substituents, have poor solubility in solvents compared to the specific compounds of the examples, and cannot prepare a uniform resin composition or form a cured film, so the evaluation of thermal stability cannot be carried out.

[0493] Furthermore, the comparative compound 3, which has substituents other than the aryl group in R1 to R8 with a σp value of -0.5 or higher in the Hammett equation, was observed to decompose by absorption spectroscopy after dissolution in solvent, indicating low stability.

[0494] Although the solvent solubility of the comparative compound 4, in which R1 to R8 are substituents other than aryl and heteroaryl, is good, the absorbance at the maximum absorption wavelength decreases significantly after heating to 130°C, indicating low thermal stability of the resin composition.

[0495] Comparative compound 2 is the counter anion X - It is a nucleophilic fluoride ion, and its decomposition was observed by absorption spectroscopy after dissolving in a solvent, indicating low stability.

[0496] [Examples 43-49, Comparative Examples 7-9]

[0497] The following evaluation of the compounding process was conducted by preparing a compound, or a resin composition, of a specific compound or a comparative compound and a resin.

[0498] 5. Mixing Evaluation

[0499] Weigh the specific and comparative compounds listed in Table 3 according to the amounts specified in Table 3 below, and prepare 12.0 g of resin and pre-mixed sample samples as specified in Table 3. The resins used were polycarbonate resin (described as polycarbonate in Table 3), polystyrene resin, and acrylic resin. In Table 3, polycarbonate resin is described as polycarbonate, polystyrene resin as polystyrene, and acrylic resin as acrylic acid.

[0500] The obtained sample was fed into the feed port of a biaxial mixer (Laboplast Mill, manufactured by Toyo Seiki Seisaku-sho, Ltd.) and melt-mixed to obtain a resin composition as a compound. The obtained resin composition was pressed using a hot press to obtain a resin film with a thickness of 0.15 mm.

[0501] When using polycarbonate resin (SD PORYCA (registered trademark) 301-10, manufactured by Sumika Bayer U-PICA Co., Ltd.) as the resin, the melt mixing temperature is set to 260°C and the hot pressing temperature is set to 230°C.

[0502] When using polystyrene resin (manufactured by ALDRICH) as the resin, the melt mixing temperature is set to 200°C and the hot pressing temperature is set to 180°C.

[0503] When using an acrylic resin (G1000, manufactured by Kuraray Co., Ltd.) as the resin, the melt mixing temperature is set to 180°C and the hot pressing temperature is set to 160°C.

[0504] The transmittance of the obtained resin film at a wavelength of 1150 nm was measured using a spectrophotometer, and the measured values ​​were evaluated according to the following criteria. Table 3 is recorded as "Evaluation of Transmittance at 1150 nm". The evaluation indicates that the lower the transmittance, the better the near-infrared blocking performance. The results are shown in Table 3.

[0505] (Evaluation Criteria)

[0506] A: The transmittance at a wavelength of 1150nm is less than 10%.

[0507] B: The transmittance at a wavelength of 1150nm is greater than 10% and less than 50%.

[0508] C: The transmittance at a wavelength of 1150nm is over 50%.

[0509] [Table 3]

[0510]

[0511] Each of the specific compounds in the examples has high compatibility with the resin and is thermally stable. Therefore, even after being mixed with the resin at a temperature of 180°C to 240°C, the resin film formed from the resin composition as the compound has good near-infrared shielding properties.

[0512] On the other hand, even with an aryl group in the diammonium skeleton, due to the counterion X - The comparative compound 2, which is a nucleophilic fluoride ion, the comparative compound 3, which is a substituent other than a substituent in R1 to R8 having a σp value of -0.5 or higher according to the Hammett equation, and the comparative compound 4, which is a substituent in R1 to R8 other than aryl and heteroaryl, all have low thermal stability. Therefore, the near-infrared shielding properties of the film of the resin composition obtained under the above thermal conditions are all poor.

[0513] The inventions of Japanese Patent Application No. 2023-056456, filed on March 30, 2023, and Japanese Patent Application No. 2023-166087, filed on September 27, 2023, are incorporated herein by reference.

[0514] All documents, patent applications and technical standards described in this invention are incorporated into this invention by reference to the same extent as those specifically described therein.

Claims

1. A pigment composition comprising a compound represented by the following general formula (1), In general formula (1), R1, R2, R3, R4, R5, R6, R7, and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or more that conform to the Hammett equation, aryl groups optionally having substituents with 7 to 20 carbon atoms, and heteroaryl groups optionally having substituents. R1, R2, R3, R4, R5, R6, R7, and R8 may be the same as or different from each other, and two or more may optionally be linked together to form a ring. R9, R 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They are either the same as or different from each other. m is 1 or 2, and X represents a non-nucleophilic anion.

2. A pigment composition comprising a compound represented by the following general formula (2), In general formula (2), R1, R2, R3, R4, R5, R6, R7, and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or more that conform to the Hammett equation, aryl groups optionally having substituents with 7 to 20 carbon atoms, and heteroaryl groups optionally having substituents. R1, R2, R3, R4, R5, R6, R7, and R8 may be the same as or different from each other, and two or more may optionally be linked together to form a ring. R9, R 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9 and R's. 10 R 11 R 12 and R 13 They are either the same as or different from each other. X represents a non-nucleophilic anion.

3. The pigment composition according to claim 1 or 2, wherein it is an image forming material.

4. The pigment composition according to claim 1 or 2, further comprising a resin.

5. A film comprising the pigment composition of claim 4.

6. A filter comprising the membrane of claim 5.

7. A near-infrared absorbing compound, represented by the following general formula (1), In general formula (1), R1, R2, R3, R4, R5, R6, R7, and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or more that conform to the Hammett equation, aryl groups optionally having substituents with 7 to 20 carbon atoms, and heteroaryl groups optionally having substituents. R1, R2, R3, R4, R5, R6, R7, and R8 may be the same as or different from each other, and two or more may optionally be linked together to form a ring. R9, R 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9, R... 10 R 11 R 12 and R 13 They are either the same as or different from each other. m is 1 or 2, and X represents a non-nucleophilic anion.

8. A near-infrared absorbing compound, represented by the following general formula (2), In general formula (2), R1, R2, R3, R4, R5, R6, R7, and R8 independently represent groups selected from phenyl groups having substituents with a σp value of -0.5 or more that conform to the Hammett equation, aryl groups optionally having substituents with 7 to 20 carbon atoms, and heteroaryl groups optionally having substituents. R1, R2, R3, R4, R5, R6, R7, and R8 may be the same as or different from each other, and two or more may optionally be linked together to form a ring. R9, R 10 R 11 R 12 and R 13 Each of the five n's independently represents a monovalent substituent, and each n' independently represents an integer from 0 to 4. When n is an integer from 2 to 4, there exist multiple R9 and R's. 10 R 11 R 12 and R 13 They are either the same as or different from each other. X - This indicates a nonnucleophilic anion.

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