Resin composition, coated and dried article, melt-kneaded article, optical filter, image display device, solid-state imaging element, squaric acid compound, and method for producing squaric acid compound

Abstract

Provided are a resin composition, a coated and dried product or a melt-kneaded product, an optical filter including the same, an image display device and a solid-state imaging element including the optical filter, and an octahydroxy acid compound represented by a specific formula and a method for producing the same, the resin composition containing an octahydroxy acid compound and a resin, wherein the octahydroxy acid compound includes at least one selected from octahydroxy acid compounds represented by a specific formula.

Description

Technical Field

[0001] This invention relates to a resin composition suitable as a constituent material of filters, a coated dried product or melt-mixed product, filters using the same, and image display devices and solid-state imaging elements using the same filters. Furthermore, this invention relates to a squaric acid compound suitable as a light-absorbing component of the aforementioned resin compositions, and a method for manufacturing the same. Background Technology

[0002] Squaric acid compounds can absorb light with specific wavelengths, and therefore are promising compounds for optical applications such as organic pigments. For example, applications have been proposed in the optical applications of charge-generating materials for photoreceptors for electrophotography (e.g., Patent Document 1), dyes (e.g., dyes for toners in electrophotography (Patent Document 2)), and light-absorbing agents for filters installed in image display devices (e.g., Patent Document 3).

[0003] In image display devices, liquid crystal displays (LCDs) are increasingly used due to their low power consumption and space-saving design. Since the liquid crystal panel itself is a non-emissive element that displays images, a backlight unit is arranged on the back of the liquid crystal panel. This backlight unit uses a white LED as the light source, which generates white light by mixing blue light emitted from a blue light-emitting diode (LED) with light emitted from a yellow or green phosphor and a red phosphor. For this backlight unit using a white LED, a technique has been proposed to improve the color reproduction area by blocking (absorbing) unwanted wavelengths of light emitted from the white LED. Various filters (light-absorbing films) containing pigments and resins such as squaric acid compounds have been proposed as light filters (light-absorbing films) to block (absorb) unwanted wavelengths of light.

[0004] Squamous acid compounds are fluorescent pigments with high fluorescence quantum yield, but because they are easily oxidized (decomposed) by light (irradiation), their function as pigments is impaired. Therefore, they are difficult to apply to applications that require high lightfastness (image display devices, inkjet pigments, etc.) that can maintain high light-blocking performance (light absorption energy) even when exposed to light.

[0005] As a filter to improve this reduced lightfastness, for example, Patent Document 3 proposes a filter made of a resin composition containing a compound represented by a specific general formula and a resin having a specific squaric acid compound structure and a metallocene structure.

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 60-169453

[0009] Patent Document 2: Japanese Patent Application Publication No. 2009-036811

[0010] Patent Document 3: International Publication No. 2019 / 167930A1 Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] When a resin solution, which is made by dissolving common squaric acid compounds and resins in an organic solvent, is used for film preparation, the film preparation state and the state of the squaric acid compounds are prone to deviation (uniformity), which can impair the light absorption energy of the filter.

[0013] The objective of this invention is to provide a filter capable of highly absorbing (blocking) target wavelength light, such as unwanted wavelengths of incident light, and also exhibiting excellent lightfastness. Furthermore, the objective of this invention is to provide a resin composition, a coated dried product, or a melt-mixed product suitable as a forming material for the aforementioned filter, and a squaric acid compound suitable as a light-absorbing component of the resin composition, coated dried product, or melt-mixed product, and a method for manufacturing the same. Additionally, the objective of this invention is to provide an image display device and a solid-state imaging element equipped with the aforementioned filter.

[0014] means for solving technical problems

[0015] Based on in-depth research into the aforementioned issues, the inventors discovered that squaric acid compounds having specific chemical structures represented by formula (1) or formula (3) possess an intramolecular betaine structure and exhibit sufficient solubility (solubility) relative to the organic solvent used in the film formation of the filter, while suppressing association caused by the high planarity of the squaric acid compound. Further research based on this insight revealed that when a resin composition combining the aforementioned squaric acid compound and a resin is dissolved in an organic solvent for film formation, a coated dry product (film, etc.) that suppresses deviations in the film formation state and the state of the squaric acid compound can be formed. The resulting film (filter) selectively and effectively absorbs light of a specific wavelength and maintains high light absorption energy even after light irradiation, exhibiting excellent lightfastness. Furthermore, it was discovered that a melt-blended compound obtained by melt-blending a squaric acid compound and a resin also selectively and effectively absorbs light of a specific wavelength, exhibiting excellent lightfastness, similar to the coated dry product.

[0016] This invention was made based on these insights and through repeated research.

[0017] That is, the above-mentioned issues can be addressed through the following methods.

[0018] <1> A resin composition comprising a squaric acid compound and a resin.

[0019] The squaric acid compound includes at least one selected from the squaric acid compounds represented by formula (1) and the squaric acid compounds represented by formula (3).

[0020] [Chemical Formula 1]

[0021]

[0022] In equation (1), R 1 ~R 4 This indicates that it can have substituents, alkyl, or aryl groups. Wherein, R... 1 ~R 4 At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group. R 5 and R 6 Indicates -NR 9 R 10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N Represents a hydrogen atom or an alkyl or aryl group that may have substituents. R 7 and R 8 This represents a substituent, where m and n are integers from 0 to 3.

[0023] Among them, the squaric acid compound represented by formula (1) has at least one branched alkyl group with more than 4 carbon atoms.

[0024] [Chemical Formula 2]

[0025] Dye-(Q 1 ) n1 Equation (3)

[0026] In equation (3), Dye represents the structural part from which n1 hydrogen atoms are removed from the squaric acid compound represented by equation (4) below, and Q 1 This represents a group represented by the following formula (4M). n1 is an integer from 1 to 6.

[0027] [Chemical Formula 3]

[0028]

[0029] In equation (4), R 1 ~R 4 This indicates that it can have substituents, alkyl, or aryl groups. Wherein, R... 1 ~R 4At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group. R 5 and R 6 Indicates -NR 9 R 10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N Represents a hydrogen atom or an alkyl or aryl group that may have substituents. R 7 and R 8 This represents a substituent, where m and n are integers from 0 to 3.

[0030] [Chemical Formula 4]

[0031]

[0032] In equation (4M), L represents a single bond or a divalent linker that is not conjugated with Dye. R 1m ~R 9m Represents a hydrogen atom or substituent. M represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V, or Pt. * indicates the bonding portion with Dye.

[0033] <2> according to <1> The resin composition, wherein,

[0034] The squaric acid compound represented by formula (1) is represented by the following formula (2).

[0035] [Chemical Formula 5]

[0036]

[0037] In equation (2), R 2 and R 4 Indicates an alkyl group. R 11 and R 12 Represents a substituent, where p and q are integers from 0 to 5. R 5 ~R 8 The meanings of m and n are the same as those of R in equation (1). 5 ~R 8 The meanings of , m and n are the same.

[0038] Among them, the squaric acid compound represented by formula (2) has at least one branched alkyl group with more than 4 carbon atoms.

[0039] <3> according to <1> or <2> The resin composition, wherein,

[0040] R 2 R 4 R 9 and R 10 At least one of them contains a branched alkyl group having 4 or more carbon atoms.

[0041] <4> according to <1> The resin composition, wherein,

[0042] The squaric acid compound represented by formula (4) is represented by the following formula (5).

[0043] [Chemical Formula 6]

[0044]

[0045] In equation (5), R 2 and R 4 Indicates an alkyl group. R 11 and R 12 Represents a substituent, where p and q are integers from 0 to 5. R 5 ~R 8 The meanings of m and n are the same as those of R in equation (4). 5 ~R 8 The meanings of , m and n are the same.

[0046] <5> according to <1> or <4> The resin composition, wherein,

[0047] The squaric acid compound represented by formula (4) or the squaric acid compound represented by formula (5) has at least one branched alkyl group having more than 4 carbon atoms.

[0048] <6> according to <1> , <4> or <5> The resin composition, wherein,

[0049] In formula (4M), M stands for Fe.

[0050] <7> according to <1> to <6> The resin composition described in any one of the following statements, wherein,

[0051] The glass transition temperature of the resin is -80 to 200℃.

[0052] <8> according to <1> to <7> The resin composition described in any one of the following statements, wherein,

[0053] The resin is selected from at least one of polystyrene resin, cellulose acylated resin, poly(meth)acrylic resin, polyester resin, cycloolefin resin, and polycarbonate resin.

[0054] <9> according to <1> to <8> The resin composition described in any one of the following statements contains a solvent with a boiling point below 200°C, wherein the resin and the squaric acid compound are dissolved in the solvent.

[0055] <10> A coating drying agent, which is made by applying the above-mentioned... <9> The resin composition is prepared by coating and drying on a substrate.

[0056] <11> A melt-mixed compound, which is as described above <1> to <8> The melt blend of the resin composition described in any one of the above statements.

[0057] <12> A filter comprising the above <1> to <7> The resin composition described in any one of the following statements, <10> The coating dried material or <11> The aforementioned melt-mixed compound.

[0058] <13> according to <12> The filter is in the form of a membrane or thin film.

[0059] <14> An image display device comprising the above-mentioned <12> or <13> The aforementioned filter.

[0060] <15> A solid-state imaging element comprising the above-mentioned <12> or <13> The aforementioned filter.

[0061] <16> A squaric acid compound, which is represented by the following formula (1) or the following formula (3).

[0062] [Chemical Formula 7]

[0063]

[0064] In equation (1), R 1 ~R 4 This indicates that it can have substituents, alkyl, or aryl groups. Wherein, R... 1 ~R 4 At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group. R 5 and R 6 Indicates -NR 9 R 10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N Represents a hydrogen atom or an alkyl or aryl group that may have substituents. R 7 and R 8 This represents a substituent, where m and n are integers from 0 to 3.

[0065] Among them, the squaric acid compound represented by formula (1) has at least one branched alkyl group with more than 4 carbon atoms.

[0066] [Chemical Formula 8]

[0067] Dye-(Q 1 ) n1 Equation (3)

[0068] In equation (3), Dye represents the structural part from which n1 hydrogen atoms are removed from the squaric acid compound represented by equation (4) below, and Q 1 This represents a group represented by the following formula (4M). n1 is an integer from 1 to 6.

[0069] [Chemical Formula 9]

[0070]

[0071] In equation (4), R 1 ~R 4 This indicates that it can have substituents, alkyl, or aryl groups. Wherein, R... 1 ~R 4 At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group. R 5 and R 6 Indicates -NR 9 R 10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N Represents a hydrogen atom or an alkyl or aryl group that may have substituents. R 7 and R 8 This represents a substituent, where m and n are integers from 0 to 3.

[0072] [Chemical Formula 10]

[0073]

[0074] In equation (4M), L represents a single bond or a divalent linker that is not conjugated with Dye. R 1m ~R 9m Represents a hydrogen atom or substituent. M represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V, or Pt. * indicates the bonding portion with Dye.

[0075] <17> according to <16> The aforementioned squaric acid compound, wherein,

[0076] The squaric acid compound represented by formula (1) is represented by the following formula (2).

[0077] [Chemical Formula 11]

[0078]

[0079] In equation (2), R 2 and R 4 Indicates an alkyl group. R 11 and R 12 Represents a substituent, where p and q are integers from 0 to 5. R 5 ~R 8 The meanings of m and n are the same as those of R in equation (1). 5 ~R 8 The meanings of , m and n are the same.

[0080] Among them, the squaric acid compound represented by formula (2) has at least one branched alkyl group with more than 4 carbon atoms.

[0081] <18> according to <16> The aforementioned squaric acid compound, wherein,

[0082] The squaric acid compound represented by formula (4) is represented by the following formula (5).

[0083] [Chemical Formula 12]

[0084]

[0085] In equation (5), R 2 and R 4 Indicates an alkyl group. R 11 and R 12 Represents a substituent, where p and q are integers from 0 to 5. R 5 ~R 8 The meanings of m and n are the same as those of R in equation (4). 5 ~R 8 The meanings of , m and n are the same.

[0086] <19> A method for producing a squaric acid compound, wherein a compound represented by formula (A) is reacted with squaric acid or a compound represented by formula (B) to produce a squaric acid compound represented by formula (1).

[0087] [Chemical Formula 13]

[0088]

[0089] In equations (A), (B), and (1), R 1 ~R 4This indicates that it can have substituents, alkyl, or aryl groups. R 5 and R 6 Indicates -NR 9 R 10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N Represents a hydrogen atom or an alkyl or aryl group that may have substituents. R 7 and R 8 This represents a substituent, where m and n are integers from 0 to 3.

[0090] Among the compounds represented by formula (A) that react with squaric acid, R 1 and R 2 At least one of them is aryl, R 1 and R 2 At least one of them is an alkyl group, having at least one branched alkyl group having 4 or more carbon atoms.

[0091] In compounds that react with each other and are represented by formula (A) or formula (B), R 1 ~R 4 At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group, having at least one branched alkyl group having 4 or more carbon atoms.

[0092] The squaric acid compound represented by formula (1) has at least one branched alkyl group with more than 4 carbon atoms.

[0093] Invention Effects

[0094] This invention provides a filter capable of highly absorbing (blocking) target wavelength light, such as unwanted wavelengths of incident light, and exhibiting excellent lightfastness. Furthermore, this invention provides a resin composition, a coated dried product or melt-mixed product suitable as a forming material for the aforementioned filter, and a squaric acid compound suitable as such a light-absorbing component, and a method for manufacturing the same. In addition, this invention provides an image display device and a solid-state imaging element incorporating the aforementioned filter.

[0095] The above-described features and other features and advantages of the present invention will become more apparent from the accompanying drawings and from the following description. Attached Figure Description

[0096] Figure 1 This is a schematic diagram illustrating one embodiment of a liquid crystal display device equipped with the filter of the present invention. Detailed Implementation

[0097] In the compounds (pigments) represented by the chemical structural formulas described in this invention or specification, the cations exist in a delocalized manner, and multiple tautomer structures exist. Therefore, in this invention, when at least one tautomer structure of a certain pigment is applied to a chemical structural formula defined by various general formulas, a certain pigment is defined as a pigment represented by each general formula. Thus, a pigment represented by a specific general formula can be called a pigment capable of having at least one tautomer structure represented by that specific general formula. In this invention, as long as at least one of its tautomer structures is applied to that general formula, the pigment represented by the general formula can adopt any tautomer structure.

[0098] In this invention, the numerical range indicated by "~" includes the values ​​recorded before and after it as a lower limit and an upper limit. Furthermore, in this invention, when multiple numerical ranges are set for the content, physical properties, etc., of a compound, the upper and lower limits of the numerical range are not limited to specific combinations of upper and lower limits, but can be set as numerical ranges formed by appropriately combining the upper and lower limits of each numerical range.

[0099] In this invention, when there are multiple substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) represented by specific symbols, or when multiple substituents, etc. are specified simultaneously or selectively, it means that each substituent, etc., may be the same as or different from each other. The same applies to the number of substituents, etc. Furthermore, when multiple substituents, etc., are close (especially adjacent), it means that they can be connected to each other or fused together to form a ring.

[0100] In this invention, the term "compound" is used not only to refer to the compound itself, but also to include its salts and its ions. Furthermore, it refers to a modification of a portion of the structure without impairing the target effect. Examples of salts of compounds include, for example, acid addition salts of compounds formed by the compound and inorganic or organic acids, or base addition salts of compounds formed by the compound and inorganic or organic bases. Examples of ions of compounds include, for example, ions formed when the salts of the aforementioned compounds dissolve in water or solvents.

[0101] In this specification, for substituents that are not explicitly stated as substituted or unsubstituted (the same applies to linking groups), it means that the group may contain any substituents, to the extent that the desired effect is not impaired. The same meaning applies to compounds or repeating units that are not explicitly stated as substituted or unsubstituted.

[0102] In this invention, when specifying the number of carbon atoms (also called the carbon number) of a certain group, this number of carbon atoms refers to the total number of carbon atoms in the entire group. That is, when the group is in the form of having substituents, it refers to the total number of carbon atoms including the substituents. In this case, when a group has a metallocene structure (group) as a substituent, the number of carbon atoms forming the metallocene structure is not included in the number of carbon atoms of the group.

[0103] In this invention, when a group can form both acyclic and cyclic skeletons, unless otherwise specified, the group includes both acyclic skeleton groups and cyclic skeleton groups. For example, unless otherwise specified, alkyl refers to linear alkyl, branched alkyl, and cyclic (cyclo)alkyl groups. When a group forms a cyclic skeleton, the lower limit of the number of carbon atoms in the cyclic skeleton group is independent of the lower limit of the specifically stated number of carbon atoms in the group, preferably 3 or more, and more preferably 5 or more.

[0104] In this invention, the term "(meth)acrylic acid" is used to encompass both methacrylic acid and acrylic acid.

[0105] [Resin Composition]

[0106] The resin composition of the present invention contains a squaric acid compound represented by formula (1) or formula (3) below and a resin as an adhesive. The squaric acid compound and the resin contained in the resin composition of the present invention may be one or more types.

[0107] As represented by formula (1) or formula (3) described later, the squaric acid compound has a squaric acid structural portion that absorbs in a specific wavelength region of visible light, and also has a branched alkyl group having 4 or more carbon atoms or a specific metallocene structural portion. As described later, squaric acid compounds with this structure enable filters to exhibit high light absorption energy and excellent lightfastness. Furthermore, in squaric acid compounds having a metallocene structural portion represented by formula (3), the metallocene structural portion inhibits the decomposition of the squaric acid compound when excited by light absorption, thereby further improving lightfastness.

[0108] Furthermore, in the preferred embodiment where the squaric acid compound represented by formula (3) has at least one branched alkyl group having four or more carbon atoms, the above-mentioned properties are further enhanced.

[0109] In the squaric acid compounds represented by formula (1) and formula (3), the decomposition of the squaric acid compounds can be effectively suppressed by a preferred method of forming intramolecular hydrogen bonds in the squaric acid compounds.

[0110] Therefore, the resin composition of the present invention is suitable as a forming material for components that absorb light with wavelengths of 670 to 740 nm, such as filters of the present invention (filters comprising squaric acid compounds and resins), and, as described later, is suitable as a forming material for near-infrared cutoff filters.

[0111] The resin composition of the present invention, as long as it is a composition containing a squaric acid compound and a resin, can take on an appropriate form depending on the application, the manufacturing method of the filter, etc. Examples include (simple) mixtures obtained by dry mixing of the squaric acid compound and the resin using conventional methods; liquid compositions obtained by wet mixing of the squaric acid compound, the resin, and the solvent using conventional methods, containing a solvent described later and dissolving the squaric acid compound and the resin in the solvent; coated dried products (usually film-like or thin-film molded articles) obtained by coating and drying the liquid composition; and molten mixtures (also called melt-cured products) obtained by melting and mixing the squaric acid compound and the resin and then cooling and solidifying them. Here, the solvent may remain in the coated dried product as long as it does not impair the effects of the present invention; the residual amount of solvent can, for example, be set to 5% by mass or less in the coated dried product. The coated dried product and the melt-mixed product differ from simple mixtures of squaric acid compound and resin in that the resin forms a (continuous) matrix. That is, the coated dry product is a substance in which the squaric acid compound and the resin are temporarily dissolved in a solvent and mixed, and the resin (containing the squaric acid compound) precipitates (cures) in the mixed state. On the other hand, the melt-mixed product is a substance in which the squaric acid compound and the resin are temporarily melted and melt-mixed, and the resin (containing the squaric acid compound) cools and solidifies in the molten mixed state. The resin composition of the present invention, especially the liquid composition, as described later, can suppress deviations during film formation and photo-oxidative decomposition of the squaric acid compound. Furthermore, the coated dry product and the melt-mixed product of the present invention suppress deviations such as the state of the squaric acid compound, do not impair light absorption energy, and exhibit high lightfastness by suppressing oxidative decomposition caused by light irradiation. In addition, the methods and conditions for coating drying and melt mixing will be described later.

[0112] The resin compositions of the present invention, especially the coated dried material and the melt mixture, can be cured materials, preferably uncured materials.

[0113] <Squamous acid compounds>

[0114] The squaric acid compound (also referred to as the squaric acid compound of the present invention) contained in the resin composition of the present invention is a pigment compound represented by the following formula (1) or the following formula (3).

[0115] The squaric acid compound represented by formula (1) below (sometimes referred to as compound (1)) has the chemical structure represented by formula (1) and is a compound incorporating at least one branched alkyl group having four or more carbon atoms. On the other hand, the squaric acid compound represented by formula (3) (sometimes referred to as compound (3)) is a compound incorporating a specific metallocene structure in the chemical structure represented by formula (4), and is more preferably a compound incorporating at least one branched alkyl group having four or more carbon atoms.

[0116] Both compounds (1) and (3) exhibit sharp absorption spectra, with maximum absorption wavelengths in the 670–740 nm wavelength region, preferably in the 680–720 nm wavelength region. These wavelength regions are located near the boundary between the near-infrared and visible regions, and are wavelengths of light that should be absorbed as unwanted light in applications such as displays and sensors. Therefore, filters containing these compounds are preferably used as light-shielding components (optical parts) in displays with LED backlights, for example, as filters in image display devices. Furthermore, the filter of the present invention is preferably used as a near-infrared cutoff filter, which performs visibility correction for solid-state imaging elements using silicon photodiodes that sense infrared light in the light-receiving section.

[0117] Typically, squaric acid compounds are easily oxidized and decomposed through light absorption, making them unsuitable for applications such as image display devices requiring high lightfastness. Furthermore, during film formation, solutions (liquid compositions) containing squaric acid compounds and resins are prone to deviations in film formation state and the state of the squaric acid compound (also known as film-forming deviations), leading to reduced light absorption energy. In contrast, the squaric acid compounds of the present invention, having chemical structures represented by the following formulas, solve the problem of photo-oxidative decomposition of squaric acid compounds as described above, while simultaneously suppressing film-forming deviations and overcoming the disadvantage of reduced light absorption energy. The reason for this is not yet clear, but it is inferred below.

[0118] Squaric acid compounds are typically highly planar and difficult to dissolve in organic solvents, and even when dissolved, they readily form various associative forms such as H-associations. The formation of these associative compounds not only broadens the absorption spectrum of squaric acid compounds and reduces their lightfastness, but also introduces deviations in the film-forming state and the state in which the squaric acid compounds exist. However, both compounds (1) and (3) employ a combination of at least one alkyl and one aryl group from alkyl and aryl groups, using a total of four substituents comprised of two disubstituted amino groups in the squaric acid structural portion. Furthermore, compound (1) has at least one branched alkyl group with four or more carbon atoms, and compound (3) has a specific metallocene structural portion. It is believed that by possessing this structure, compounds (1) and (3) readily dissolve in organic solvents, and even when dissolved at high concentrations, they are difficult to form associative compounds due to moderate steric hindrance. Furthermore, it is believed that their compatibility with resins can also be improved. Therefore, both compounds can suppress deviations during film formation, enabling the filter to exhibit high light absorption energy while maintaining excellent lightfastness. In particular, compound (3) with a specific metallocene structure can highly suppress the decomposition of squaric acid compounds, thereby further improving lightfastness. Although the reason is not yet clear, it is believed to be caused by the deactivation of the excited state of compound (3) and the following reverse electron movement. That is, when compound (3) is photoexcited, the electron-donating metallocene structure can rapidly inject electrons into the squaric acid compound structure corresponding to "Dye" in formula (3), thereby deactivating the activated state. Therefore, the decomposition of compound (3) caused by photoexcitation can be suppressed. Furthermore, since fluorescence deactivation caused by electron transfer usually occurs when the pigment is in an unstable state (anionic radical) when there is an excess of electrons, this promotes the decomposition of the pigment. However, compound (3) also promotes the reverse electron movement from the anionic radicalized pigment structure to the metallocene structure. It is believed that the above-mentioned effect of squaric acid compounds is exerted not only in liquid compositions but also in melt blends.

[0119] Furthermore, the resin composition of the present invention can be used to manufacture filters with various compound concentrations depending on the purpose.

[0120] (The squaric acid compound represented by formula (1))

[0121] First, the squaric acid compound represented by formula (1) will be explained.

[0122] One form of the squaric acid compound contained in the resin composition of the present invention is a squaric acid compound (1) represented by the following formula (1). The compound (1) has at least one branched alkyl group having 4 or more carbon atoms. That is, as a group represented by each symbol in the following formula (1), the group represented by each symbol has at least one branched alkyl group having 4 or more carbon atoms as a substituent.

[0123] The compound (1) is formed by appropriately selecting the groups represented by the symbols in the formula from the range described below, but preferably having a symmetrical structure relative to the carbon 4-membered ring (the benzene ring having R5 and the benzene ring having R6 have the same chemical structure).

[0124] [Chemical Formula 14]

[0125]

[0126] In equation (1), R 1 ~R 4 Each can independently represent an alkyl or aryl group that may have substituents. Wherein, R 1 ~R 4 At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group. R 5 and R 6 Indicates -NR 9 R 10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N Represents a hydrogen atom or an alkyl or aryl group that may have substituents. R 7 and R 8 This represents a substituent, where m and n are integers from 0 to 3.

[0127] Can be used as R 1 ~R 4 The alkyl group can be any of straight chain, branched chain, or cyclic chain, preferably straight chain or branched chain, and especially preferably branched chain.

[0128] The number of carbon atoms in the alkyl group is not particularly limited, but is generally preferably selected from the range of 1 to 40. The lower limit is more preferably 3 or more, further preferably 5 or more, and especially preferably 8 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of carbon atoms in the branched alkyl group is more preferably selected from the range of 3 to 40 within the above range. In the branched alkyl group, the lower limit of the number of carbon atoms is generally more preferably 4 or more, especially preferably 6 or more, and most preferably 8 or more. The upper limit is generally more preferably 35 or less, especially preferably 30 or less. From the viewpoint of optical properties such as light absorption energy and lightfastness, as well as solubility in organic solvents and compatibility with resins, the number of carbon atoms in the branched alkyl group is more preferably in the range of 6 to 35, especially preferably in the range of 8 to 30, and most preferably in the range of 8 to 24. On the other hand, from the comprehensive viewpoint of maintaining optical properties, solubility, and compatibility while including ease of synthesis (cost), the range of 6 to 24 is more preferably, especially preferably in the range of 8 to 16.

[0129] The branched number of alkyl groups is preferably 2 to 10, more preferably 2 to 8.

[0130] Can be used as R 1 ~R 4 The aryl group can be a monocyclic group or a polycyclic group (fused ring structure, bridged ring structure, etc.), preferably a monocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 30, more preferably 6 to 20, even more preferably 6 to 12, and especially preferably 6. Examples of aryl groups include those containing benzene rings and naphthalene rings, and more preferably groups containing benzene rings.

[0131] Can be used as R 1 ~R 4 The alkyl and aryl groups can each have at least one substituent X. When multiple substituent Xs are present, adjacent substituents can bond to each other to form a ring structure. There is no particular limitation on the number of substituent Xs in one alkyl group; for example, it can be set to be the same as p in formula (2) described later. There is no particular limitation on the bonding position of the substituent Xs in the alkyl group, and it can be appropriately determined. Furthermore, there is no particular limitation on the number of substituent Xs in one aryl group and the bonding position of the substituent Xs; they are the same as p and q in formula (2) described later, as well as the substitution positions.

[0132] -Substituent X-

[0133] There are no particular limitations on the substituent X, and examples include alkyl (methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, trifluoromethyl, etc.), cycloalkyl (cyclopentyl, cyclohexyl, etc.), alkenyl (vinyl, allyl, etc.), alkynyl (ethynyl, propargyl, etc.), aryl (phenyl, naphthyl, etc.), heteroaryl (furanyl, thiophene, pyridinyl, pyridinyl, triazolyl, imidazole, pyrazolyl, thiazolyl, benzimidazole, benzoxazolyl, benzothiazolyl, quinazolinyl, phthaloyl, etc.), and heterocyclic groups (also known as (non-aromatic) heterocyclic groups, for example,Pyrroloalkyl, imidazoalkyl, morpholinyl, oxazolidinyl, etc.), alkoxy (methoxy, ethoxy, propoxy, etc.), cycloalkoxy (cyclopentoxy, cyclohexyloxy, etc.), aryloxy (phenoxy, naphthoxy, etc.), heteroaryloxy (aromatic heterocyclic thiols), heterocyclic thiols (non-aromatic heterocyclic thiols), alkylthio (methylthio, ethylthio, propylthio, etc.), cycloalkoxy (cyclopentylthio, cyclohexylthio, etc.), arylthio (phenylthio, naphthio, etc.), heteroarylthio (aromatic heterocyclic thiols), heterocyclic thio (non-aromatic heterocyclic thiols), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octoxycarbonyl, etc.), aryloxycarbonyl (phenoxycarbonyl, naphthoxycarbonyl, etc.), phosphoryl ( Dimethoxyphosphoryl, diphenylphosphoryl), aminosulfonyl (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, phenylaminosulfonyl, 2-pyridylaminosulfonyl, etc.), acyl (acetyl, ethylcarbonyl, propylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy (acetoxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, phenylcarbonyloxy, etc.), acylamino (acetylamino, ethylcarbonylamino, butylcarbonylamino, octylcarbonylamino, phenylcarbonylamino, etc.), amide (methylcarbonylamino, ethyl... Carbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), sulfonamide (methylsulfonylamino, octylsulfonylamino, 2-ethylhexylsulfonylamino, trifluoromethylsulfonylamino, etc.), carbamoyl (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), urea (methylurea, ethylurea). The following groups are listed: pentylurea, cyclohexylurea, octylurea, dodecylurea, phenylurea, naphthylurea, 2-pyridylaminourea, etc.; alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, etc.); arylsulfonyl groups (phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.); amino groups (amino, ethylamino, dimethylamino, butylamino, dibutylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, aniline, naphthylamino, 2-pyridylamino, etc.); alkylsulfonyloxy groups (methanesulfonyloxy); cyano, nitro, halogen atoms (fluorine, chlorine, bromine, etc.); hydroxyl, sulfonyl, carboxyl, etc.

[0134] There is no particular limitation on the number of carbon atoms in the above-mentioned group that serves as substituent X, and it can be set within the following range, for example.

[0135] The number of carbon atoms of the above alkyl group can be set to the number that can be used as R. 1 ~R 4 The number of carbon atoms in the aryl group can be within the same range as, or different from, 1 to 20 (preferably 1 to 15, more preferably 1 to 8). The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8. The number of carbon atoms in the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkyl, alkenyl, and alkynyl groups can be any of straight-chain, branched, or cyclic, preferably straight-chain or branched.

[0136] The aforementioned aryl group comprises a monocyclic or fused-ring group, preferably with 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. The aforementioned heteroaryl group comprises a monocyclic or fused-ring group, preferably a monocyclic group or a group comprising a fused-ring group with 2 to 8 rings, more preferably a monocyclic group or a group comprising a fused-ring group with 2 to 4 rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. Examples of heteroatoms constituting the ring of the heteroaryl group include nitrogen atoms, oxygen atoms, sulfur atoms, etc. The heteroaryl group is preferably a group comprising a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The meaning of heterocyclic group is the same as that of heteroaryl group described above, except that it lacks aromaticity.

[0137] The meaning of alkyl in substituents containing alkyl groups such as alkoxy groups is the same as the meaning of alkyl groups described above. Furthermore, the meaning of aryl or heteroaryl in substituents containing aryl or heteroaryl groups such as aryloxy or heteroaryl groups is the same as the meaning of aryl or heteroaryl groups described above.

[0138] As can be used as R 1 ~R 4 The alkyl and aryl groups may have substituents X, preferably alkyl, aryl, acyl, alkoxy, amide or sulfonamide.

[0139] R 1 ~R 4 At least one of them is aryl, and at least one is alkyl. It can be used as R 1 ~R 4 The number of aryl groups is set to three or less, preferably two or three, more preferably two. On the other hand, it can be used as R... 1 ~R 4 The number of alkyl groups is set to three or less, preferably one or two, more preferably two. In R 1 ~R 4 Examples of R that have two alkyl groups and one aryl group respectively can be cited.1 and R 2 For aryl, R 1 and R 3 These are the two modes, one for aryl groups. In R... 1 ~R 4 When there are multiple alkyl or aryl groups, the multiple alkyl or aryl groups can be the same or different.

[0140] From the perspective of ease of synthesis, R is preferred. 1 and R 3 For aryl, R 2 and R 4 The most preferred form is alkyl, specifically R. 1 and R 3 For the same aryl group, R 2 and R 4 They are the same alkyl group.

[0141] R 5 and R 6 Represent -NR independently 9 R 10 Here, R 9 and R 10 Each is independently selected from hydrogen atoms, -COR N -COOR N -CON(R) N )2 and -SO2R N In -NR 9 R 10 In, R bonded to the same nitrogen atom 9 and R 10 Appropriate choices can be made, but R atoms bonded to the same nitrogen atom are preferred. 9 and R 10 One of them is a hydrogen atom. Thus, it forms an intramolecular hydrogen bond with the oxygen atom bonded to the four-membered carbon ring, making compound (1) itself more rigid and significantly improving its lightfastness. R 9 and R 10 Another one selected from -COR N -COOR N -CON(R) N )2 and -SO2R N Preferred -COR N or -SO2R N In compound (1), R 5 and R 6 For different structures of -NR 9 R 10 Preferably, -NR with the same structure 9 R 10 .

[0142] The above R N Represents a hydrogen atom, alkyl, or aryl group, preferably alkyl or aryl in compound (1), more preferably alkyl. Can be used as R N There are no particular restrictions on the alkyl and aryl groups, but they are preferably respectively combined with those that can be used as the above-mentioned R 1 ~R 4 The alkyl and aryl groups have the same meaning. They can be used as R. N The alkyl and aryl groups may have substituents. Preferably, such substituents are groups selected from the substituents X described above, wherein halogen atoms (especially fluorine atoms), alkyl groups, alkoxy groups, aryl groups, aryloxy groups, acyl groups, etc., are preferred. Halogen-substituted alkyl groups can be alkyl groups in which only a portion of the hydrogen atoms are substituted, or they can be perhalogenated alkyl groups in which all hydrogen atoms are substituted.

[0143] -CON(R N )2 has 2 R N They can be the same or different.

[0144] R 7 and R 8 Substituents are represented independently. As can be used as R 7 and R 8 The substituents are not particularly limited, and for example, groups selected from the substituents X mentioned above can be cited. Preferably, they are alkenyl, halogen, alkyl, acyl, alkoxy, amide, sulfonamide, or hydroxyl.

[0145] Can be used as R 7 and R 8 Substituents can form rings. For example, multiple R groups... 7 and R 8 They can bond with each other to form a fused ring together with the benzene ring. For example, compound A-15 described later is bonded to two vinyl groups that are bonded to the same benzene ring to form a benzene ring (i.e., a naphthalene ring) that is condensed with the aforementioned benzene ring. There are no particular limitations on the ring formed at this time; it can be a hydrocarbon ring or a heterocyclic ring, and it can be an aliphatic ring or an aromatic ring.

[0146] Can be used as R 7 and R 8 The substituents may further have substituents. Examples of substituents that may be further included are groups selected from the substituents X described above.

[0147] m and n are independent integers from 0 to 3, preferably 0 or 1.

[0148] When m and n are 2 or 3, multiple R 7 and R 8 They can be the same or different.

[0149] In compound (1), a branched alkyl group having at least 4 or more carbon atoms is used as a substituent, either as a group represented by any of the symbols in formula (1) above or as a substituent of any group represented by any of the symbols. There is no particular limitation as long as the branched alkyl group has 4 or more carbon atoms, but it is preferred to use a group that can be used as R above. 1 ~R 4 The branched alkyl groups have the same range of carbon atoms.

[0150] There is no particular limitation on the total number of branched alkyl groups in compound (1), but from the viewpoint of optical properties and solubility, it is preferred to have 2 or more, more preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 4.

[0151] In compound (1), the branched alkyl group is preferably R. 1 ~R 4 R 7 R 8 R 9 and R 10 Incorporated as at least one of them or as a substituent on at least one of them, more preferably as R 1 ~R 4 R 9 and R 10 Compiled into at least one of them, and further preferred as R 2 R 4 R 9 and R 10 It is included by at least one of them.

[0152] In compound (1), the groups represented by the symbols in formula (1) can be appropriately combined and applied, and preferably the preferred groups are combined and applied together.

[0153] -Squamous acid compounds represented by formula (2)-

[0154] The above-mentioned compound (1) is preferably a squaric acid compound (sometimes referred to as compound (2)) represented by the following formula (2). Wherein, the squaric acid compound represented by formula (2) has at least one branched alkyl group having 4 or more carbon atoms.

[0155] [Chemical Formula 15]

[0156]

[0157] In equation (2), R 2 and R 4 Each alkyl group can be represented independently. R 11 and R 12 Represents a substituent, where p and q are integers from 0 to 5. R 5 ~R 8The meanings of , m and n are the same as those of R in the above formula (1). 5 ~R 8 The meanings of , m and n are the same.

[0158] Can be used as R 2 and R 4 The meaning of alkyl and the use of R in formula (1) 1 ~R 4 The meaning of alkyl is the same.

[0159] R 11 and R 12 Substituents are represented independently. As can be used as R 11 and R 12 Substituents, meanings and uses as R 1 ~R 4 The meaning of substituents that alkyl and aryl groups can have is the same. Specifically, groups selected from the substituents X mentioned above can be cited. Preferably, they are alkyl, aryl, acyl, alkoxy, amide, or sulfonamide.

[0160] p and q are each independently an integer from 0 to 5, preferably 0 to 3, more preferably 0 to 2, and even more preferably 1. When p and q are integers of 2 or more, multiple R... 11 and R 12 They can be the same or different. R 11 and R 12 There are no particular restrictions on the bonding position. For example, the carbon atom (1 position) of the ring structure bonded to the nitrogen atom of each benzene ring can be any one of the ortho (2 position), meta (3 position), or para (4 position), preferably para.

[0161] R 5 ~R 8 The meanings of , m and n are respectively related to R in equation (1). 5 ~R 8 The meanings of , m and n are the same.

[0162] In compound (2), a substituent is a group represented by each symbol in the above formula (2), or a branched alkyl group having at least 4 carbon atoms on each symbol.

[0163] The meaning of the number of carbon atoms in the branched alkyl group and the total number of branched alkyl groups in compound (2) are the same as the meaning of the number of carbon atoms in compound (1) and the total number of branched alkyl groups in compound (1).

[0164] In compound (2), the branched alkyl group is preferably R. 2 R 4 R 7 R 8R 9 R 10 R 11 and R 12 Incorporated as at least one of them or as a substituent on at least one of them, more preferably as R 2 R 4 R 9 and R 10 Compiled into at least one of them, in R 2 R 4 R 9 and R 10 Further optimization of R 2 and R 4 It is included by at least one of them.

[0165] In compound (2), the groups represented by the symbols in formula (2) can be appropriately combined and applied, and preferably the preferred groups are combined and applied together.

[0166] The following are specific examples of squaric acid compounds represented by formula (1), but the present invention is not limited to these. Furthermore, the following specific examples are shown as tautomer structures of squaric acid compounds represented by formula (1). And, in the following specific examples, -C a H (2a+1) The alkyl group indicated is a straight-chain alkyl group, and Me indicates methyl.

[0167] [Chemical Formula 16]

[0168]

[0169] [Chemical Formula 17]

[0170]

[0171] (The squaric acid compound represented by formula (3))

[0172] Another form of the squaric acid compound contained in the resin composition of the present invention is a squaric acid compound (3) represented by the following formula (3). This compound (3) has at least one group represented by the following formula (4M). That is, it is a compound obtained by replacing at least one hydrogen atom in the compound represented by formula (4M) with a group represented by formula (4M). In this compound (3), it is preferable that the substituents are branched alkyl groups having at least 4 or more carbon atoms on each group represented by the following formula (4).

[0173] The compound (3) is constructed by appropriately selecting the groups represented by the symbols in the formula from the range described below, but preferably having a symmetrical structure relative to the carbon 4-membered ring in formula (4) (having R 5 benzene ring and having R6 The benzene rings have the same chemical structure.

[0174] [Chemical Formula 18]

[0175] Dye-(Q 1 ) n1 Equation (3)

[0176] In formula (3), Dye represents the structural part from which n1 hydrogen atoms are removed from the squaric acid compound (sometimes called compound (4)) represented by the following formula (4), and Q 1 This represents a group represented by the following formula (4M). n1 is an integer from 1 to 6.

[0177] -Squamous acid compounds represented by formula (4)-

[0178] Compound (4) of Dye, which introduces compound (3), is represented by the following formula (4).

[0179] [Chemical Formula 19]

[0180]

[0181] In equation (4), R 1 ~R 4 This indicates that it can have alkyl or aryl groups that have substituents. Wherein, R... 1 ~R 4 At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group. R 5 and R 6 Indicates -NR 9 R 10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N Represents a hydrogen atom or an alkyl or aryl group that may have substituents. R 7 and R 8 This represents a substituent, where m and n are integers from 0 to 3.

[0182] Compound (4) is the same as compound (1) except that it may not have a branched alkyl group with more than 4 carbon atoms. That is, R in formula (4) 1 ~R 8 The meanings of , m and n are respectively the same as R in equation (1). 1 ~R 8 The meanings of , m and n are the same.

[0183] Among them, the group represented by formula (4M) is introduced into a component that can be used as R. 1 ~R 4 In the case of alkyl groups, the alkyl group is preferably a straight-chain alkyl group, and the number of carbon atoms is preferably in the range of 1 to 10 within the above range, and more preferably in the range of 2 to 6.

[0184] Furthermore, when the group represented by formula (4M) is introduced into the -NR group... 9 R 10 In this case, it can be used as R 9 and R 10 -COR N -COOR N -CON(R) N )2 and -SO2R N The R it possesses N Preferably, it contains hydrogen atoms or alkyl groups.

[0185] Compound (4) may not have a branched alkyl group with 4 or more carbon atoms, but it is preferred to have at least one branched alkyl group with 4 or more carbon atoms. The meaning of compound (4) having a branched alkyl group with 4 or more carbon atoms is the same as the meaning of compound (1) having a branched alkyl group with 4 or more carbon atoms. In this case, compound (4) is preferably the same as compound (1).

[0186] In compound (4), the groups represented by the symbols in formula (4) can be appropriately combined and applied, and preferably the preferred groups are combined and applied together.

[0187] The portion (atom) from which hydrogen atoms are removed from compound (4) becomes the bond portion of L (the bond portion represented by "*" in the following formula (4M).

[0188] There are no particular restrictions on the method of removing hydrogen atoms from this compound (4), as long as a suitable hydrogen atom can be removed. For example, examples can be given of compounds derived from R. 1 ~R 8 The hydrogen atoms and R represented by any of the groups in the table 5 Or R 6 The hydrogen atoms in the bonded benzene ring are preferably composed of R 1 ~R 6 The hydrogen atoms present in each of the groups represented in the text.

[0189] There is no particular limit to the number of hydrogen atoms removed, and the meaning of n1 is the same as described later.

[0190] There are no particular restrictions on the manner in which hydrogen atoms are removed from compound (4). For example, it is preferable to remove hydrogen atoms from R. 1 and R 2The manner in which each group is removed by one hydrogen atom, from R 1 and R 3 The groups represented or derived from R 2 and R 4 The manner in which one hydrogen atom is removed from each group is indicated by R. 5 and R 6 The manner in which each group (preferably a group other than a hydrogen atom) is removed is described; furthermore, combinations of these manners are preferred, and more preferably, the manner in which one hydrogen atom is removed from R is described. 1 and R 3 The groups represented or derived from R 2 and R 4 The manner in which one hydrogen atom is removed from each group is indicated by R. 5 and R 6 The method of removing one hydrogen atom from each group, or a combination of these methods. From the viewpoint of solubility, it is preferable to remove hydrogen atoms from R. 5 and R 6 The method of removing one hydrogen atom from each group.

[0191] -Squamous acid compounds represented by formula (5)-

[0192] The above compound (4) is preferably a squaric acid compound represented by the following formula (5) (sometimes referred to as compound (5)).

[0193] [Chemical Formula 20]

[0194]

[0195] In equation (5), R 2 and R 4 Each alkyl group can be represented independently. R 11 and R 12 Represents a substituent, where p and q are integers from 0 to 5. R 5 ~R 8 The meanings of m and n are the same as those of R in equation (4). 5 ~R 8 The meanings of , m and n are the same.

[0196] Can be used as R 2 and R 4 The meaning of alkyl and the use of R in formula (1) 1 ~R 4 The meaning of alkyl is the same.

[0197] R 11 and R 12 Substituents are represented independently. As can be used as R 11 and R 12 Substituents, meanings and uses as R1 ~R 4 The meaning of substituents that alkyl and aryl groups can have is the same. Specifically, groups selected from the substituents X mentioned above can be cited. Preferably, they are alkyl, aryl, acyl, alkoxy, amide, or sulfonamide.

[0198] p and q are each independently an integer from 0 to 5, preferably 0 to 3, more preferably 0 to 2, and even more preferably 1. When p and q are integers of 2 or more, multiple R... 11 and R 12 They can be the same or different. R 11 and R 12 There are no particular restrictions on the bonding position. For example, the carbon atom (1 position) of the ring structure bonded to the nitrogen atom of each benzene ring can be either meta (3 position) or para (4 position), preferably para.

[0199] R 5 ~R 8 The meanings of , m and n are respectively related to R in equation (4). 5 ~R 8 The meanings of , m and n are the same.

[0200] Compound (5) is a preferred embodiment of compound (4), except that it may not have a branched alkyl group having 4 or more carbon atoms, and can be said to be the same as compound (2) described above. Preferably, compound (5) has at least one branched alkyl group having 4 or more carbon atoms. The meaning of compound (5) having a branched alkyl group having 4 or more carbon atoms is the same as the meaning of compound (4) having a branched alkyl group having 4 or more carbon atoms; in this case, compound (5) is preferably the same as compound (2).

[0201] In compound (5), the groups represented by the symbols in formula (5) can be appropriately combined and applied, and preferably the preferred groups are combined and applied together.

[0202] There are no particular restrictions on the manner in which hydrogen atoms are removed from compound (5), as long as a suitable hydrogen atom can be removed. For example, examples can be given of compounds derived from R. 2 R 4 ~R 8 and R 11 ~R 12 The hydrogen atoms and R represented by any of the groups in the table 5 Or R 6 Or R 11 Or R 12 The number of hydrogen atoms in the bonded benzene ring. There is no particular restriction on the number of hydrogen atoms removed, and it has the same meaning as n1 described later.

[0203] There are no particular restrictions on the manner in which hydrogen atoms are removed from compound (5), for example, preferably from R 2 and R 4 The manner in which one hydrogen atom is removed from each group is indicated by R. 5 and R 6 The manner in which each group (preferably a group other than a hydrogen atom) removes one hydrogen atom, and combinations thereof.

[0204] In equation (3), n1 represents the number of Q1 bonds with Dye, which is usually 1 or more, and can be appropriately selected from the range of the number of hydrogen atoms in compound (4). For example, n1 can be an integer from 1 to 6, preferably an integer from 1 to 4, and more preferably 1 or 2. When n1 is an integer of 2 or more, multiple Q1 bonds are bonded to Dye. 1 They can be the same or different.

[0205] Q in equation (3) 1 This represents a group represented by the following formula (4M).

[0206] [Chemical Formula 21]

[0207]

[0208] In equation (4M), L represents a single bond or a divalent linker that is not conjugated with Dye. R 1m ~R 9m Represents a hydrogen atom or substituent. M represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V, or Pt. * indicates the bonding portion with Dye.

[0209] In compound (3), the group represented by formula (4M) above is introduced into R in formula (4). 1 ~R 8 In the case of any of the groups represented in the formula (4M), L is interpreted as a single bond.

[0210] In compound (3), when L in formula (4M) is a divalent linker, Dye is a structure that cuts off the portion (atom) of the conjugated structure by linking with L. That is, when L is not a single bond but a divalent linker, the bonded portion of L with Dye does not include the conjugated structure. In other words, when the conjugated structure continues from Dye to the group (metallocene structure) represented by formula (4M) (i.e., when the conjugated structure continues from Dye to the metallocene skeleton in formula (4M), L is a single bond. Here, the conjugated structure refers to the structure of a bonded p-orbital system with non-localized electrons formed on single and multiple bonds in alternating positions, and also includes p-orbital electron-donating groups, p-orbital electron-donating atoms, or structures containing p-orbital electron-donating groups and p-orbital electron-donating atoms. Examples of p-orbital electron-donating groups include carbonyl and sulfonyl groups. A p-orbital electron-donating atom is an atom with two lone pairs of electrons, one of which occupies a p orbital. Examples of atoms that can be p-orbital electron-donating atoms include oxygen, nitrogen, or sulfur atoms. When the structure includes p-orbital electron-donating groups and p-orbital electron-donating atoms, examples can be given of structures formed by combining multiple (preferably an integer number of 2 to 10) p-orbital electron-donating atoms and p-orbital electron-donating groups. For example, divalent groups represented by -O-CO-, -NH-CO-, -NH-SO2-, -NH-CO-NH-, etc., are groups that form conjugated structures. Furthermore, in this invention, when L in formula (4M) is a single bond, the cyclopentadienyl ring directly bonded to Dye (the ring with R in formula (4M)) 1m The ring is not included in the conjugate structure conjugate with Dye.

[0211] Based on the above, there are no particular limitations on the divalent linker that can be used as L, as long as it is not conjugated with Dye. The above-mentioned conjugated structure can be included in its interior or at the cyclopentadiene ring end in formula (4M). Examples of divalent linkers include alkylene groups with 1 to 20 carbon atoms, arylene groups with 6 to 20 carbon atoms, divalent heterocyclic groups obtained by removing two hydrogen atoms from a heterocycle, -CH=CH-, -CO-, -CS-, -NR- (R represents a hydrogen atom or a monovalent substituent), -O-, -S-, -SO2-, or -N=CH-, or divalent linkers that are not conjugated with Dye and are formed by combining multiple of them (preferably 2 to 6). Preferably, the linker is a divalent linker that is not conjugated with Dye and consists of an alkylene group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a linker that is a combination of a group selected from -CH=CH-, -CO-, -NR- (R as described above), -O-, -S-, -SO2-, and -N=CH- or a combination of two or more groups selected from the group thereof. Particularly preferred are alkylene groups having 1 to 4 carbon atoms, phenylene groups, or linkers that are a combination of a group selected from -CO-, -NH-, -O-, and -SO2- or a combination of two or more groups selected from the group thereof (preferably 2 to 6) and are not conjugated with Dye. There are no particular limitations on the divalent linker formed by the combination, but it is preferred to contain a group containing -CO-, -NH-, -O-, or -SO2-. Examples of linkers include linkers containing two or more groups of -CO-, -NH-, -O-, or -SO2-, or linkers that do not conjugate with Dye. Examples of linkers containing two or more groups of -CO-, -NH-, -O-, or -SO2-, or linkers that do not conjugate with Dye. As a linking group formed by combining at least one of -CO-, -NH-, -O- and -SO2- with an alkylene or arylene group, examples can be given of linking groups formed by combining -CO-, -COO- or -CONH- with an alkylene or arylene group that are not conjugated with Dye.

[0212] There are no particular restrictions on the substituents that can be used as R; examples of the substituents X mentioned above are available.

[0213] L is a single bond or preferably a group selected from alkylene groups having 1 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R as described above), -O-, -S-, -SO2-, and -N=CH-, or a group formed by combining two or more groups selected from this group.

[0214] L may have one or more substituents. There are no particular restrictions on the substituents that L may have, for example, they have the same meaning as the substituent X mentioned above. When L has multiple substituents, the substituents bonded to adjacent atoms can bond with each other to further form a ring structure.

[0215] As for the alkylene group that can be used as L, as long as it is a group with 1 to 20 carbon atoms, it can be straight-chain, branched, or cyclic. Examples include methylene, ethylene, propylene, methyl ethylene, methyl methylene, dimethyl methylene, 1,1-dimethyl ethylene, butylene, 1-methyl propyleneene, 2-methyl propyleneene, 1,2-dimethyl propyleneene, 1,3-dimethyl propyleneene, 1-methyl butylene, 2-methyl butylene, 3-methyl butylene, 4-methyl butylene, 2,4-dimethyl butylene, etc. 1,3-Dimethylbutylene, pentylene, hexylene, heptylene, octylene, ethane-1,1-diyl, propane-2,2-diyl, cyclopropane-1,1-diyl, cyclopropane-1,2-diyl, cyclobutane-1,1-diyl, cyclobutane-1,2-diyl, cyclopentane-1,1-diyl, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane-1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, methylcyclohexane-1,4-diyl, etc.

[0216] When L is used as a linker containing at least one of -CO-, -CS-, -NR- (R is as described above), -O-, -S-, -SO2- and -N=CH- in the alkylene group, the -CO- group can be incorporated into any position in the alkylene group, and there is no particular limitation on the number of times it can be incorporated.

[0217] There are no particular restrictions on whether a group can be used as an L-aryl group, as long as it is a group introduced to remove a hydrogen atom from an aryl group with 6 to 20 carbon atoms.

[0218] There are no particular limitations on the heterocyclic group that can be used as L, and groups composed of aliphatic or aromatic heterocycles can be cited as examples. Preferably, the heterocyclic group is a 5-membered or 6-membered ring. Examples of heterocyclic groups that can be used as L include groups obtained by removing two hydrogen atoms from a pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, thiazole ring, oxazole ring, triazole ring, indole ring, pseudoindole ring, indoline ring, pyridine ring, pyrimidine ring, quinoline ring, benzothiazole ring, benzoxazole ring, or pyrazolotriazole ring.

[0219] In formula (4M), the remaining part of the structure, excluding the linker L, corresponds to the structure obtained by removing one hydrogen atom from the metallocene compound (metallocene structural part). In this invention, the metallocene compound that becomes the metallocene structural part can be any known metallocene compound without particular limitation, as long as it is a compound suitable for the partial structure specified by formula (4M) (a compound in place of L that is bonded by hydrogen atoms). Hereinafter, the metallocene structural part specified by formula (4M) will be specifically described.

[0220] In formula (4M), R 1m ~R 9m These represent hydrogen atoms or substituents, respectively. As can be used as R... 1m ~R 9m The substituents can be selected from substituent X, without any particular restrictions. 1m ~R 9m The atom is preferably a hydrogen atom, halogen atom, alkyl group, acyl group, alkoxy group, amino group or amide group, more preferably a hydrogen atom, halogen atom, alkyl group, acyl group or alkoxy group, further preferably a hydrogen atom, halogen atom, alkyl group or acyl group, especially preferably a hydrogen atom, halogen atom or alkyl group, and most preferably a hydrogen atom.

[0221] As can be used as R 1m ~R 9m Alkyl groups, which can be used as R 1 The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, tert-pentyl, hexyl, octyl, and 2-ethylhexyl.

[0222] The alkyl group may have a halogen atom as a substituent. Examples of alkyl groups substituted with halogen atoms include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl.

[0223] Furthermore, it can be used as R 1mIn alkyl groups, at least one methylene group forming the carbon chain can be substituted with -O- or -CO-. Examples of alkyl groups with -O-substituted methylene groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, dibutoxy, tributoxy, 2-methoxyethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, bromomethoxy, dibromomethoxy, tribromomethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, perfluoroethoxy, perfluoropropoxy, perfluorobutoxy, and alkyl groups with substituted terminal methylene groups, as well as alkyl groups with substituted internal methylene groups in the carbon chain, such as 2-methoxyethyl. Examples of alkyl groups with -CO-substituted methylene groups include acetyl, propionyl, monochloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, propane-2-one-1-yl, butane-2-one-1-yl, etc.

[0224] In formula (4M), M is an atom capable of forming a metallocene compound, representing Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V, or Pt. Preferably, M is Fe, Ti, Co, Ni, Zr, Ru, or Os; more preferably, Fe, Ti, Ni, Ru, or Os; even more preferably, Fe or Ti; and most preferably, Fe.

[0225] As the group represented by formula (4M), L and R are preferably used. 1m ~R 9m Groups formed by combining preferred groups of M, for example, as L, can be single bonds or groups selected from alkylene groups having 2 to 8 carbon atoms, aryl groups having 6 to 12 carbon atoms, -CH=CH-, -CO-, -NR- (R as described above), -O-, -S-, -SO2-, and -N=CH-, or groups formed by combining two or more groups selected from this group, as R. 1m ~R 9m Examples of M include hydrogen atoms, halogen atoms, alkyl groups, acyl groups, or alkoxy groups. Examples of M include groups that combine with Fe.

[0226] The following are specific examples of squaric acid compounds represented by formula (3), but the present invention is not limited to these. Furthermore, the following specific examples are shown as tautomer structures of squaric acid compounds represented by formula (3). In the following specific examples, -C a H (2a+1) The alkyl group indicated is a straight-chain alkyl group, and Me indicates methyl.

[0227] [Chemical Formula 22]

[0228]

[0229] [Chemical Formula 23]

[0230]

[0231] The content of the squaric acid compound in the resin composition of the present invention is not particularly limited, and can be appropriately set considering the type or solubility of the squaric acid compound, the required optical properties, etc. The aforementioned content is preferably 0.005 to 15 parts by weight relative to 100 parts by weight of the adhesive resin described later, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 5 parts by weight. In the resin composition of the present invention, the content of the squaric acid compound can also be set to a high level, for example, 10 to 30 parts by weight.

[0232] Furthermore, the squaric acid compound is readily soluble in solvents. For example, in the "Solubility Evaluation" of the examples described later, a solubility of 0.01 parts by mass or more relative to 100 parts by mass of the toluene / cyclohexanone mixed solvent is expressed.

[0233] When the filter contains two or more alpha acid compounds, the above content is their total content.

[0234] Furthermore, in cases where the filter of the present invention also serves as a polarizing protective film or adhesive layer as described later, the content of pigment (squaric acid compound) may also be within the above-mentioned range.

[0235] (Synthesis of Squaric acid compounds)

[0236] Squamous acid compounds represented by various formulas can be synthesized according to known methods. For example, they can be synthesized according to the synthesis methods described in Patent Documents 1 to 3, and the synthesis methods described in the examples below.

[0237] As a preferred method for synthesizing (manufacturing) the squaric acid compound represented by formula (1), for example, a method can be described by reacting a compound represented by formula (A) below with squaric acid or a compound represented by formula (B) below to synthesize the compound (hereinafter, sometimes referred to as a preferred manufacturing method). Furthermore, in the following formulas, the compound that reacts with squaric acid is the compound represented by formula (A), and the combination of the compound represented by formula (A) and the compound represented by formula (B1) described later has the same meaning.

[0238] [Chemical Formula 24]

[0239]

[0240] In equations (A), (B), and (1), R 1 ~R 4 This indicates that it can have alkyl or aryl groups that have substituents. R 5 and R 6 Indicates -NR 9 R10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N Represents a hydrogen atom or an alkyl or aryl group that may have substituents. R 7 and R 8 The symbols represent substituents, where m and n are integers from 0 to 3. The symbols in equations (A), (B), and (1) are the same as the corresponding symbols in equation (1) above.

[0241] In the case where the compound represented by formula (A) reacts with squaric acid, in the combination of compounds represented by formula (A) that react with squaric acid, R 1 and R 2 At least one of them is aryl, R 1 and R 2 At least one of them is an alkyl group, and at least one of the compounds represented by formula (A) has at least one branched alkyl group having four or more carbon atoms. The compounds represented by formula (A) consisting of two molecules reacting with squaric acid preferably have the same chemical structure. Furthermore, in combinations of compounds represented by formula (A) and compounds represented by formula (B1) described later, the above-mentioned "R" is included. 1 and R 2 Replace "R" 1 ~R 4 Replace “at least one of the compounds represented by formula (A)” with “at least one of the compounds represented by formula (A) and the compounds represented by formula (B1).

[0242] When a compound represented by formula (A) reacts with a compound represented by formula (B), in the combination of compounds represented by formula (A) or formula (B) that react with each other, R 1 ~R 4 At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group, and at least one of the compounds represented by formula (A) and formula (B) has at least one branched alkyl group having four or more carbon atoms. In addition, the aminobenzene moiety in the compound represented by formula (A) and formula (B) preferably have different chemical structures.

[0243] The squaric acid compound represented by formula (1) has at least one branched alkyl group with more than 4 carbon atoms.

[0244] In the above combinations, the arrangements having aryl and alkyl groups and having at least one branched alkyl group having more than four carbon atoms are the same as those in the compounds represented by the above formula (1).

[0245] In the preferred manufacturing method described above, the compound that reacts with the compound represented by formula (A) can be selected based on the chemical structure of the manufactured squaric acid compound. For example, in the case where the squaric acid compound represented by formula (1) has a chemical structure symmetrical with respect to the carbon 4-membered ring (the compound with R in formula (1)...), 5 benzene ring and having R 6 In the case where the benzene rings have the same chemical structure, the compound represented by formula (A) can react with the compound represented by formula (B), but it is preferable to react the squaric acid with two molecules of the compound represented by formula (A) (the compound represented by formula (A) and the compound represented by formula (B1) described later). On the other hand, in the case where the squaric acid compound represented by formula (1) has a chemical structure asymmetric with respect to the four-membered carbon ring (the compound with R in formula (1)...), 5 benzene ring and having R 6 In cases where the benzene ring has a different chemical structure, it is preferable to react the compound represented by formula (A) with the compound represented by formula (B).

[0246] The conditions under which the compound represented by formula (A) reacts with squaric acid (dehydration condensation reaction) are not particularly limited as long as they are the conditions under which the reaction takes place, and can be appropriately set.

[0247] The amount of the compound represented by formula (A) used is stoichiometrically 2 moles relative to 1 mole of squaric acid, and is preferably set to 1.5 to 2.5 moles in practice.

[0248] The reaction temperature is preferably set above the boiling point (reflux temperature) of the solvent described later, for example, preferably 50 to 150°C, more preferably 80 to 120°C. The reaction time can be set, for example, 0.5 to 20 hours.

[0249] The reaction is usually carried out in a solvent. There are no particular restrictions on the solvent used, as long as it does not hinder the reaction. Among them, solvents that azeotropically react with water, which is a byproduct of the reaction, are preferred. Examples of preferred solvents include alcohols with 1 to 6 carbon atoms, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, or mixtures thereof.

[0250] In this reaction, it is preferable to remove and separate the by-product water from the reaction system, which can be done using conventional equipment, such as a Dean Stark apparatus in the case of heating reflux.

[0251] After the reaction, if the generated squaric acid compound is dissolved in the reaction solution, the compound can be precipitated as a precipitate by diluting the reaction solution with an alcohol solvent or by cooling the reaction solution. The precipitate can also be purified using conventional purification methods.

[0252] In addition, regarding reaction conditions, post-processing, etc., one can appropriately refer to well-known synthetic methods.

[0253] The conditions for reacting the compound represented by formula (A) with the compound represented by formula (B) are not particularly limited and can be appropriately set. For example, the conditions for reacting the compound represented by formula (A) with squaric acid can be given. In addition, known synthetic methods can be appropriately referenced regarding reaction conditions, post-treatment, etc.

[0254] The compound represented by formula (B) can be synthesized by reacting the compound represented by formula (B1) with the compound represented by formula (B2).

[0255] [Chemical Formula 25]

[0256]

[0257] In equation (B1), each symbol is the same as the corresponding symbol in equation (1) above.

[0258] In formula (B2), X represents an alkoxy or halogen atom. There are no particular limitations on which alkoxy can be used as X; for example, examples of alkoxy can be used as R. 1 The alkoxy group X, which may be present in the alkyl group or the like, is preferably an alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. Examples of halogen atoms that can be used as X include halogen atoms in the substituent X, with chlorine atoms being preferred. X is preferably a methoxy, ethoxy, or chlorine atom; the two Xs may be the same or different.

[0259] The conditions under which the compound represented by formula (B1) reacts with the compound represented by formula (B2) are not particularly limited as long as they are conditions under which the reaction takes place, and can be appropriately set.

[0260] The amount of the compound represented by formula (B2) used is stoichiometrically set to 1 mole relative to 1 mole of the compound represented by formula (B1), and is preferably set to 0.8 to 1.2 moles in practice.

[0261] The reaction temperature is preferably 20–150°C, more preferably 50–120°C. The reaction time can be set, for example, to 0.5–20 hours.

[0262] This reaction is usually carried out in a solvent. There are no particular restrictions on the solvent used, as long as it does not hinder the reaction; aromatic hydrocarbon solvents mentioned above are preferred.

[0263] After the reaction between the compound represented by formula (B1) and the compound represented by formula (B2) is completed, the obtained compound is heated in water as needed in the presence of organic acids such as acetic acid and inorganic acids such as hydrochloric acid, for example, to cause hydrolysis reaction, so as to obtain the compound represented by formula (B).

[0264] The obtained compounds can also be purified using conventional purification methods.

[0265] In addition, regarding reaction conditions, post-processing, etc., one can appropriately refer to well-known synthetic methods.

[0266] By using the preferred manufacturing method described above, squaric acid compounds represented by formulas (1), (2), (4), or (5) can be synthesized. Furthermore, when synthesizing squaric acid compounds represented by formula (4) or (5), the compounds represented by formulas (A), (B), and (B1) may not have branched alkyl groups having 4 or more carbon atoms.

[0267] In the preferred manufacturing method described above, the squaric acid compound represented by the above formula (3) can be synthesized by introducing the group represented by the above formula (4M) into the compounds represented by the above formula (A), formula (B), and formula (B1) using a conventional method.

[0268] <Resin>

[0269] The resin composition of the present invention contains a resin (adhesive) (the adhesive may contain any conventional components other than polymers. Hereinafter, it is sometimes referred to as "adhesive resin").

[0270] The resin used in this invention is preferably transparent. Here, "transparent resin" means that the total light transmittance measured when forming a test piece with a thickness of 1 mm is typically 70% or more, preferably 80% or more, and more preferably 90% or more.

[0271] The resin used as a binder in the resin composition of the present invention is not particularly limited, and any common resin used as a component of a filter can be used without particular limitation. It can be appropriately selected from resins that satisfy various physical properties such as transparency, refractive index, and processability as required according to the application or purpose. The resin can be a thermoplastic resin or a thermosetting resin. Examples of resins include poly(meth)acrylic acid resins, epoxy resins, olefin-thiol resins, polycarbonate resins, polyether resins, polyaryl ester resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyaryl ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins (cyclic olefin resins), polyester resins, polystyrene resins, polyurethane resins, polythiourethane resins, cellulose acylate resins, and cyclic sulfide resins. The squaric acid compound of the present invention exhibits a certain degree of compatibility even with hydrophobic resins; therefore, hydrophobic resins can also be used as the resin used in combination.

[0272] Among the resins contained in the resin composition, polystyrene resin, cellulose acylate resin, poly(meth)acrylic acid resin, polyester resin, cycloolefin resin, and polycarbonate resin are preferred examples. From the viewpoint of further reducing the fluorescence quantum yield, polystyrene resin or cycloolefin resin is preferred.

[0273] The squaric acid compound represented by formula (1) and the squaric acid compound represented by formula (3) can be used in appropriate combinations with the above resins.

[0274] Taking a combination of squaric acid compound and resin as an example, from the viewpoint of compatibility with resin, the squaric acid compound represented by formula (1) above is preferably combined with poly(meth)acrylic acid resin, polystyrene resin, cellulose acylated resin, cyclic olefin resin, polycarbonate resin, polyester resin, etc. Furthermore, from the viewpoint of exhibiting high lightfastness, the squaric acid compound represented by formula (3) above is preferably combined with a hydrophobic resin, and more preferably with polystyrene resin, cyclic olefin resin, etc.

[0275] (Polystyrene resin)

[0276] Polystyrene, as contained in polystyrene resin, refers to a copolymer containing 50% by mass or more styrene. In this invention, only one type of polystyrene may be used, or two or more may be used in combination. Here, the styrene component is a structural unit derived from a monomer having a styrene backbone in its structure.

[0277] To control the resin composition or filter to a preferred photoelasticity and a preferred hygroscopicity, polystyrene more preferably contains 70% by mass or more of styrene, and more preferably 85% by mass or more. Furthermore, polystyrene is preferably composed solely of styrene.

[0278] Examples of polystyrene include homopolymers of styrene compounds and copolymers of two or more styrene compounds. Here, a styrene compound is a compound having a styrene skeleton in its structure, and refers to a compound that, in addition to styrene, includes a portion into which substituents are introduced, preferably other than olefinic unsaturated bonds. Examples of styrene compounds include styrene itself; alkyl styrene such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, p-ethylstyrene, and tert-butylstyrene; and substituted styrene such as hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, and p-chlorostyrene, in which hydroxyl, alkoxy, carboxyl, or halogen groups are introduced into the benzene ring. From the viewpoint of availability and material cost, the polystyrene used in this invention is preferably a homopolymer of styrene (i.e., polystyrene).

[0279] Furthermore, there are no particular limitations on the structural components other than styrene contained in the aforementioned polystyrene. That is, the polystyrene can be a styrene-diene copolymer or a styrene-polymerizable unsaturated carboxylic acid ester copolymer. Furthermore, a mixture of polystyrene and synthetic rubber (e.g., polybutadiene or polyisoprene) can also be used. Moreover, impact-resistant polystyrene (HIPS) obtained by graft polymerization of styrene and synthetic rubber is preferred. Furthermore, it is also preferred to disperse a rubbery elastomer in a continuous phase of a polymer containing a styrene component (e.g., a copolymer of a styrene component and a (meth)acrylate component), and then graft polymerize the copolymer with the rubbery elastomer to obtain polystyrene (referred to as grafted impact-resistant polystyrene "grafted HIPS"). In addition, so-called styrene-based elastomers can be suitably used.

[0280] Furthermore, the aforementioned polystyrene can be hydrogenated (it can be hydrogenated polystyrene). There are no particular limitations on the type of hydrogenated polystyrene, but it is preferable to use hydrogenated styrene-diene copolymers such as hydrogenated styrene-butadiene-styrene block copolymers (SEBS) or hydrogenated styrene-isoprene-styrene block copolymers (SEPS), which are resins in which hydrogen has been added to SBS or SIS. Only one type of hydrogenated polystyrene may be used, or two or more types may be used.

[0281] The molecular weight of the polystyrene used in this invention can be appropriately selected according to the intended use, but the mass-average molecular weight (converted from standard polystyrene) measured by gel permeation chromatography with tetrahydrofuran solution (toluene solution when the polymer is not dissolved) is typically in the range of 5,000 to 500,000, preferably 8,000 to 200,000, and more preferably in the range of 10,000 to 100,000. Polymers with molecular weights within the above range can achieve a high level and balanced balance between the mechanical strength and processability of the molded articles.

[0282] As a polystyrene, it is possible to use multiple types with different compositions and molecular weights at the same time.

[0283] Polystyrene resins can be obtained through known anionic, bulk, suspension, emulsification, or solution polymerization methods. Furthermore, in polystyrene resins, the unsaturated double bonds of the benzene rings of the conjugated diene or styrene monomer can be hydrogenated. The hydrogenation rate can be determined using nuclear magnetic resonance (NMR).

[0284] Commercially available polystyrene resins can be used, such as: "CLEAREN 530L" and "CLEAREN 730L" from Denka Company Limited; "TUFPRENE 126S" and "ASAPRENE T411" from Asahi Kasei Corporation; "Clayton D1102A" and "Clayton D1116A" from Kraton Corporation; "Styrolux S" and "Styrolux T" from Styrolution Company; "ASAFLEX 840" and "ASAFLEX 860" (all SBS) from Asahi Kasei Chemicals Corporation; "679", "HF77", and "SGP-10" from PS Japan Corporation; "DICSTYRENE XC-515" and "DICSTYRENE XC-535" (all general-purpose polystyrene: GPPS) from DIC Corporation; "475D", "H0103", and "HT478" from PS Japan Corporation; and "DICSTYRENE" from DIC Corporation. Examples of hydrogenated polystyrene resins include GH-8300-5 (HIPS). Other examples include "TUFTEC H series" from Asahi Kasei Chemicals Corporation, "Clayton G series" (SEBS) from Shell Japan Ltd., "DYNARON" (hydrogenated styrene-butadiene random copolymer) from JSR Corporation, and "SEPTON" (SEPS) from KURARAY CO., LTD. Furthermore, examples of modified polystyrene resins include "TUFTEC M series" from Asahi Kasei Chemicals Corporation, "EPOFRIEND" from Daicel Corporation, "polar group modified DYNARON" from JSR Corporation, and "RESEDA" from TOAGOSEI CO., LTD.

[0285] (Cyclic olefin resin)

[0286] As a cyclic olefin compound that forms the cyclic olefin polymer (also known as cyclic polyolefin) contained in the cyclic olefin resin, there are no particular limitations as long as it has a ring structure containing carbon-carbon double bonds. Examples include norbornene compounds, monocyclic cyclic olefin compounds other than norbornene compounds, cyclic conjugated diene compounds, or vinyl alicyclic hydrocarbon compounds.

[0287] Examples of cyclic olefin polymers contained in cyclic olefin resins include (R1) a polymer containing structural units derived from norbornene, (R2) a polymer containing structural units derived from monocyclic cyclic olefin compounds other than norbornene, (R3) a polymer containing structural units derived from cyclic conjugated diene compounds, (R4) a polymer containing structural units derived from vinyl alicyclic hydrocarbon compounds, and hydrides of polymers containing structural units derived from each of (R1) to (R4). In this invention, the polymers containing structural units derived from norbornene and the polymers containing structural units derived from monocyclic cyclic olefin compounds are ring-opening polymers containing each compound.

[0288] There are no particular limitations on the cyclic olefin polymer, but polymers having structural units derived from norbornene compounds represented by the following general formula (A-II) or (A-III) are preferred. Polymers having structural units represented by the following general formula (A-II) are addition polymers of norbornene compounds, and polymers having structural units represented by the following general formula (A-III) are ring-opening polymers of norbornene compounds.

[0289] [Chemical Formula 26]

[0290]

[0291] In general formula (A-II) or (A-III), m is an integer from 0 to 4, preferably 0 or 1.

[0292] R of formula (A-II) or (A-III) 3 ~R 6 Each can be independently represented by a hydrocarbon group containing 1 to 10 hydrogen or carbon atoms.

[0293] In this invention, the hydrocarbon group is not particularly limited as long as it contains carbon and hydrogen atoms, and examples include alkyl, alkenyl, alkynyl, aryl (aromatic hydrocarbon group), etc. Among them, alkyl or aryl are preferred.

[0294] X 2 and X 3 Y 2 and Y 3Each 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)nCOOR. 11 -(CH2)nOCOR 12 , -(CH2)nNCO, -(CH2)nNO2, -(CH2)nCN, -(CH2)nCONR 13 R 14 -(CH2)nNR 13 R 14 -(CH2)nOZ, -(CH2)nW or X 2 With Y 2 or X 3 With Y 3 (-CO)2O or (-CO)2NR formed by mutual bonding 15 .

[0295] 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 represents a hydrocarbon group or a hydrocarbon group substituted with a halogen; W represents Si(R) 16 ) p D (3-p) (R 16 Represents hydrocarbon groups with 1 to 10 carbon atoms, D represents a halogen atom, -OCOR 17 or -OR 17 (R 17 (representing 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 0 to 8, and more preferably 0 to 6.

[0296] R in general formula (A-II) or (A-III) 3 ~R 6 The preferred components are hydrogen atoms or -CH3, and from the viewpoint of moisture permeability, hydrogen atoms are even more preferred.

[0297] X 2 and X 3 The preferred atoms are hydrogen atoms, -CH3, and -C2H5, respectively. From the perspective of moisture permeability, hydrogen atoms are even more preferred.

[0298] Y 2 and Y 3 Preferably, they are hydrogen atoms, halogen atoms (especially chlorine atoms), or -(CH2)nCOOR. 11(Especially -COOCH3), from the viewpoint of moisture permeability, hydrogen atoms are even more preferred.

[0299] Other groups may be selected as appropriate.

[0300] Polymers having structural units represented by general formula (A-II) or (A-III) may further contain at least one or more structural units represented by the following general formula (AI).

[0301] [Chemical Formula 27]

[0302]

[0303] R in general formula (AI) 1 and R 2 X represents either a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, respectively. 1 and Y 1 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)nCOOR. 11 -(CH2)nOCOR 12 , -(CH2)nNCO, -(CH2)nNO2, -(CH2)nCN, -(CH2)nCONR 13 R 14 -(CH2)nNR 13 R 14 -(CH2)nOZ, -(CH2)nW or X 1 With Y 1 (-CO)2O or (-CO)2NR formed by mutual bonding 15 .

[0304] Here, 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 represents a hydrocarbon group or a hydrocarbon group substituted with a halogen; W represents Si(R) 16 ) p D (3-p) (R 16 Represents hydrocarbon groups with 1 to 10 carbon atoms, D represents a halogen atom, -OCOR 17 or -OR 17 (R 17 (Represents hydrocarbon groups with 1 to 10 carbon atoms). p is an integer from 0 to 3). n is an integer from 0 to 10.

[0305] From the viewpoint of ensuring a tight fit for the polarizer, the cyclic polyolefin having structural units represented by general formula (A-II) or (A-III) contains 90% by mass or less of structural units derived from the aforementioned norbornene compound relative to the total mass of the cyclic polyolefin, more preferably 30-85% by mass, even more preferably 50-79% by mass, and most preferably 60-75% by mass. Here, the proportion of structural units derived from the norbornene compound represents the average value in the cyclic polyolefin.

[0306] Addition (co)polymers of norbornene compounds are described in Japanese Patent Application Publication No. 10-7732, Japanese Patent Application Publication No. 2002-504184, U.S. Patent Publication No. 2004 / 229157A1, or International Patent Publication No. 2004 / 070463, etc., and reference may be made appropriately to these contents, which are incorporated herein by reference directly as part of the description.

[0307] Polymers of norbornene compounds are obtained by addition polymerization of norbornene compounds (e.g., polycyclic unsaturated compounds of norbornene) with each other.

[0308] Furthermore, as a polymer of norbornene compounds, copolymers can be obtained by addition polymerization of norbornene compounds with olefins such as ethylene, propylene, and butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylene-bis(norbornene); acrylonitrile; acrylic acid; methacrylic acid; maleic anhydride; acrylates; methacrylates; maleimide; vinyl acetate; or vinyl chloride, etc., as required. Among these, copolymers with ethylene are preferred.

[0309] Examples of addition (co)polymers of this norbornene compound include those sold by Mitsui Chemicals, Inc. under the trade name Appel, which have different glass transition temperatures (Tg), such as APL8008T (Tg 70°C), APL6011T (Tg 105°C), APL6013T (Tg 125°C), or APL6015T (Tg 145°C). Furthermore, granules such as TOPAS8007, TOPAS6013, and TOPAS6015 are sold by POLYPLASTICS CO., LTD. Additionally, Appear3000 is sold by Ferrania.

[0310] The polymers of the aforementioned norbornene compounds are commercially available. For example, they are sold by JSR Corporation under the trade name Arton, specifically Arton G, F, RX4500, and by Zeon Corporation under the trade names Zeonor ZF14, ZF16, Zeonex 250, or Zeonex 280.

[0311] Hydrogenates of polymers of norbornene compounds can be synthesized by hydrogenation following addition polymerization or translocation ring-opening polymerization of norbornene compounds. Synthetic methods are described, for example, in Japanese Patent Application Publication Nos. 1-240517, 7-196736, 60-26024, 62-19801, 2003-159767, and 2004-309979.

[0312] The molecular weight of the cycloolefin polymer used in this invention can be appropriately selected according to the intended use, but the mass-average molecular weight of polyisoprene or polystyrene converted by gel permeation chromatography of cyclohexane solution (toluene solution when the polymer is not dissolved) is typically in the range of 5,000 to 500,000, preferably 8,000 to 200,000, and more preferably in the range of 10,000 to 100,000. Polymers with molecular weights within the above range can achieve a high level and balanced balance between the mechanical strength and processability of the molded articles.

[0313] (Poly(meth)acrylic resin)

[0314] Poly(meth)acrylic acid polymers contained in poly(meth)acrylic acid resins include polymers comprising structural units derived from (meth)acrylic acid and / or its esters. Specifically, polymers obtained by polymerizing at least one compound selected from (meth)acrylic acid, (meth)acrylates, (meth)acrylamide, and (meth)acrylonitrile are examples.

[0315] As poly(meth)acrylic acid polymers, homopolymers and copolymers obtained by (co)polymerizing compounds represented by the following general formula A1 as monomer components are preferred examples.

[0316] [Chemical Formula 28]

[0317]

[0318] In general formula A1, R a1 Represents a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R a1Preferably, hydroxyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy, more preferably hydroxyl, substituted or unsubstituted alkoxy with 1 to 18 carbon atoms, or substituted or unsubstituted aryloxy with 6 to 24 carbon atoms.

[0319] R a2 Indicates a hydrogen atom, a methyl group, or an alkyl group having two or more carbon atoms. R a2 Preferably, it contains hydrogen atoms or methyl groups.

[0320] R in general formula A1 a1 and R a2 The preferred combination can be exemplified by R. a1 It is a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, and R a2 It is a combination of hydrogen atoms or methyl groups.

[0321] Specifically, the following can be cited as compounds represented by the general formula A1.

[0322] Acrylic acid compounds or methacrylic acid compounds

[0323] Acrylic compounds

[0324] Methacrylates, ethyl acrylates, (n- or iso)propyl acrylates, (n-, iso, secondary or tert-)butyl acrylates, pentyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, hydroxybenzyl acrylate, hydroxyphenyl acrylate, dihydroxyphenyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, aminosulfonyl phenyl acrylate, 2-(hydroxyphenylcarbonyl)ethyl acrylate

[0325] · Methacrylate compounds

[0326] Methyl methacrylate, ethyl methacrylate, propyl methacrylate (n- or iso-), butyl methacrylate (n-, iso-, secondary-, or tert-), pentyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphenyl methacrylate, dihydroxyphenyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, aminosulfonyl methacrylate, 2-(hydroxyphenylcarbonyl)ethyl methacrylate

[0327] Acrylamide compounds

[0328] Acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N-(hydroxyphenyl)acrylamide, N-(aminosulfonylphenyl)acrylamide, N-(benzenesulfonyl)acrylamide, N-(toluenesulfonyl)acrylamide, N,N-dimethylacrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide

[0329] Methacrylamide compounds

[0330] Methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N-phenylmethacrylamide, N-tolylmethacrylamide, N-(hydroxyphenyl)methacrylamide, N-(aminosulfonylphenyl)methacrylamide, N-(benzenesulfonyl)methacrylamide, N-(toluenesulfonyl)methacrylamide, N,N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide

[0331] As poly(meth)acrylic acid polymers, homopolymers obtained by polymerizing compounds represented by the above general formula A1 are preferred, as are 2- to 4-component (preferably 2- to 3-component) copolymers obtained by copolymerizing compounds represented by the above general formula A1 with other compounds or further compounds represented by the above general formula A1 in a molar ratio of 10-90% (preferably 20- to 80%). Examples of other compounds include substituted or unsubstituted styrene compounds, acrylonitrile, etc.

[0332] As a poly(meth)acrylic acid polymer, homopolymers obtained by polymerizing acrylates or methacrylates having 4 to 24 carbon atoms, copolymers obtained by polymerizing two or more compounds represented by the above general formula A1, and copolymers having a molar ratio of 10 to 90% acrylates and methacrylates of 2 to 30%.

[0333] The molecular weight of poly(meth)acrylic acid polymers can be appropriately selected according to the intended use, but the mass-average molecular weight of polyisoprene or polystyrene, as determined by gel permeation chromatography of cyclohexane solution (toluene solution when the polymer is not dissolved), is typically in the range of 5,000 to 500,000, preferably 8,000 to 200,000, and more preferably in the range of 10,000 to 100,000. Polymers with molecular weights within the above range can achieve a high level and balanced balance between the mechanical strength and processability of the molded articles.

[0334] (Polyester resin)

[0335] Examples of polyester polymers contained in 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 naphthalenedicarboxylic acid, and dicarboxylic acids in which the hydrogen atoms of these aromatic rings are replaced by methyl, ethyl, or phenyl groups)), 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), as well as polymers obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone monomers (e.g., polycaprolactone). Furthermore, as for polyester polymers, the definition of "polyester" as described in Japanese Patent Application Publication No. 2009-096971 can be appropriately referenced, and its content is directly incorporated into this specification.

[0336] (Cellulose acylated resin)

[0337] There are no particular restrictions on the cellulose acylate contained in the cellulose acylate resin, and commonly used cellulose acylates can be used appropriately. For example, the cellulose acylate described in paragraphs 0016 to 0021 of Japanese Patent Application Publication No. 2012-215689 is preferred, and the contents described in that paragraph are incorporated herein by reference directly as part of the description herein.

[0338] (Polycarbonate resin)

[0339] The polycarbonate contained in the polycarbonate resin is composed of the following polyphenolic compounds and carbonate compounds such as dialkyl carbonate, diaryl carbonate, and phosgene.

[0340] 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, and 2,2-bis(3=phenyl-4-hydroxyphenyl)propane. 2,2-bis(3-isopropyl-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 oxide, etc.

[0341] Among the above, the preferred polyphenol compounds are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, and bisphenol A.

[0342] Examples of carbonate compounds include phosgene, diphenyl carbonate, bis(chlorophenyl) carbonate, dinaphthalene carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate.

[0343] Among the above, the preferred carbonate compounds are phosgene, bis(diphenyl) carbonate, dimethyl carbonate, and diethyl carbonate.

[0344] In polycarbonates, preferred combinations of monomers and polymers include bisphenol A polycarbonates that use bisphenol A as a polyphenol compound and phosgene as a carbonate compound.

[0345] Commercially available products can be used as polycarbonates, such as Panlite (registered trademark) L-1250WP (trade name, aromatic polycarbonate resin powder, manufactured by TEIJIN LIMITED.), Panlite (registered trademark) SP-1516 (trade name, manufactured by TEIJIN LIMITED.), Iupizeta (registered trademark) EP-5000 (trade name, manufactured by MITSUBISHI GASCHEMICAL COMPANY, INC.), Iupizeta (registered trademark) EP-4000 (trade name, manufactured by MITSUBISHI GASCHEMICAL COMPANY, INC.), and CALIBUR301-30 (SD POLYCA301-30) (trade name, manufactured by Sumika Polycarbonate Ltd.), etc.

[0346] (Polyurethane resin)

[0347] Polyurethane resins are those containing urethane bonds (-NR). T Polymers of thiocarbamate bonds in which at least one oxygen atom in the -CO-O- group is replaced by a sulfur atom are acceptable; for example, polymers with -NR bonds are also acceptable. T -CS-O-、-NR T -CO-S- or -NR T -CS-S- polymers. Here, R T It represents a hydrogen atom or a substituent.

[0348] The glass transition temperature (Tg) of the resin used in the resin composition of the present invention is preferably -80 to 200°C, more preferably -30 to 180°C. If the resin composition contains a resin exhibiting a Tg within the above range, filters with appropriate softness and hardness can be manufactured. The glass transition temperature of the resin can be appropriately adjusted according to the composition of the resin (types or contents of constituent components). The glass transition temperature of the resin can be determined using a differential scanning calorimeter (DSC) and according to the methods described in the equipment analysis manual (publisher: Kagaku-Dojin Publishing Company, INC).

[0349] From the viewpoint of clarity of the absorbed waveform and lightfastness, the resin composition of the present invention preferably contains 50% by mass or more of adhesive resin in all solid components (specifically, components other than the organic solvents described later), more preferably 70% by mass or more, and particularly preferably 90% by mass or more.

[0350] The resin composition may contain two or more adhesive resins, and may also use adhesive resins with different component ratios and / or molecular weights together. In this case, the total content of each adhesive resin is within the range described above.

[0351] <Additives>

[0352] The resin composition of the present invention may contain additives within a range that does not impair the effects of the present invention. For example, it may contain additives that are generally compatible with plastic films, as needed. Examples of such additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, and fillers, the content of which can be selected within a range that does not impair the purpose of the present invention. Furthermore, examples of additives include known plasticizers, organic acids, polymers, delay modifiers, ultraviolet absorbers, antioxidants, or matting agents. For these, reference can be made to paragraphs

[0062] to

[0097] of Japanese Patent Application Publication No. 2012-155287, which are incorporated herein by reference. Furthermore, examples of additives include peel accelerators, organic acids, and polycarboxylic acid derivatives. For these, reference can be made to paragraphs

[0212] to

[0219] of International Publication No. 2015 / 005398, which are incorporated herein by reference. In addition, as additives, free radical scavengers, degradation inhibitors, etc., which will be described later can also be listed.

[0353] The content of additives (the total content of two or more additives when the resin composition contains two or more additives) is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 5 to 30 parts by weight, relative to 100 parts by weight of the adhesive resin.

[0354] (Antioxidants)

[0355] Antioxidants can also be listed as one of the preferred additives. For information on antioxidants, please refer to paragraphs

[0143] to

[0165] of International Publication No. 2015 / 005398, which are incorporated herein by reference.

[0356] (Free radical scavenger)

[0357] As one of the preferred additives, free radical scavengers can also be listed. Regarding free radical scavengers, reference can be made to paragraphs

[0166] to

[0199] of International Publication No. 2015 / 005398, which are incorporated herein by reference.

[0358] (Deterioration inhibitor)

[0359] As one of the preferred additives, degradation inhibitors can also be listed. For information on degradation inhibitors, please refer to the description in International Publication No. 2015 / 005398, paragraphs

[0205] to

[0206] , which are incorporated herein by reference.

[0360] (UV absorber)

[0361] In this invention, from the viewpoint of preventing degradation, an ultraviolet absorber can be added to the filter. As an ultraviolet absorber, from the viewpoint of excellent absorption of ultraviolet light with wavelengths below 370 nm and good liquid crystal display performance, an ultraviolet absorber with low absorption of visible light with wavelengths above 400 nm is preferred. Specific examples of ultraviolet absorbers preferred for use in this invention include hindered phenolic compounds, benzophenone compounds, benzotriazole compounds, salicylates, benzophenone, cyanoacrylates, and nickel complex salts.

[0362] Examples of hindered phenolic compounds include 2,6-di-tert-butyl-p-cresol, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate. Examples of benzotriazole compounds include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol), (2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, (2(2'-hydroxy-3',5'-di-tert-pentylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, etc.

[0363] The resin composition of the present invention can contain various additives, but when used as a forming material for a filter, it can be configured to be free of anti-fading agents. In the present invention, being free of anti-fading agents includes the following: the amount of anti-fading agent is less than that required to achieve the function of preventing the filter (the dye contained in the filter) from fading, for example, less than 1% by mass of 100% by mass of the total solids, preferably less than 0.5% by mass. There are no particular limitations on the anti-fading agent, and examples include commonly used anti-fading agents such as antioxidants described in paragraphs

[0143] to

[0165] of International Publication No. 2015 / 005398A1, free radical scavengers described in paragraphs

[0166] to

[0199] of International Publication No. 2015 / 005398A1, and degradation inhibitors described in paragraphs

[0205] to

[0206] of International Publication No. 2015 / 005398A1.

[0364] Furthermore, when the resin composition of the present invention is used as the forming material of the filter, it can be configured in a manner that does not contain copper compounds as described in Patent Document 2.

[0365] Solvent

[0366] The resin composition of the present invention may also contain a solvent. Particularly preferred are the resin compositions of the present invention used to form the coated dried product described later, which contain a solvent with a boiling point of 200°C or lower, and in which the aforementioned squaric acid compound and resin are dissolved. Here, regarding the dissolution of the squaric acid compound and resin, in addition to the case where all the squaric acid compound and resin are dissolved in the solvent, there is also the case where a portion is not dissolved, for example, where less than 0.5% by mass of the total 100% by mass of the squaric acid compound and resin is not dissolved and exists in a solid state.

[0367] The boiling point of the solvent can be appropriately determined based on the coating and drying conditions described later. From the perspective of avoiding excessive heating during drying and saving energy, it is preferably 180°C or lower, more preferably 160°C or lower. On the other hand, there is no particular limitation on the lower limit value, for example, it can be set to 60°C or higher. In addition, in this invention, the boiling point of the solvent is the standard boiling point or the ordinary boiling point, which refers to the boiling point at a pressure of 101325 Pa (atmospheric pressure).

[0368] The organic solvent and its content are the same as those in the "Method for Manufacturing Filters" below.

[0369] <Preparation of Resin Compositions>

[0370] The resin composition of the present invention can be prepared by conventional methods.

[0371] When the resin composition of the present invention is a simple mixture of squaric acid compound and resin, it can be prepared by dry mixing of squaric acid compound and resin using conventional methods.

[0372] When the resin composition of the present invention is a liquid composition, it can be prepared by wet mixing of the anhydride compound, resin and solvent using conventional methods.

[0373] When the resin composition of the present invention is a coated dry product, the above-mentioned liquid composition can be coated and dried onto a substrate to prepare the product. There are no particular limitations on the substrate; examples include resin substrates, glass substrates, metal substrates, vapor-deposited films, and the surface of components on which the filter described later is disposed. There are no particular limitations on the method of coating the liquid composition; examples include spraying, dipping, roller coating, flow coating (e.g., solution casting film formation method described later), rod coating, blade coating, spin coating, etc. There are no particular limitations on the coating conditions; they can be appropriately set considering the coating amount, viscosity of the liquid composition, and consequently, the shape and size of the coated dry product. There are no particular limitations on the drying method and conditions, as long as the solvent in the liquid composition can be removed down to below the aforementioned residual amount; they can be appropriately set. For example, examples of heating methods include heat drying and blow drying; heat drying is preferred. There are no particular restrictions on the heating temperature at this time. It can be set to a temperature above the boiling point of the solvent in the ambient pressure during drying, for example, it can be set to 50-200°C under normal pressure.

[0374] When the resin composition of the present invention is a molten mixture, it can be prepared by heating the squaric acid compound and the resin (including simple mixtures) while mixing to melt the resin, followed by cooling and solidification. The melting and mixing temperature is not particularly limited as long as it is above the temperature of the molten resin, and can be appropriately determined according to the type of resin, melting point, glass transition temperature, etc. For example, it can be set to 180°C or higher, preferably 200°C or higher. As an upper limit, it can be set to 400°C or lower, preferably 350°C or lower. The melting and mixing method and conditions can be appropriately determined, and various mixers are generally used.

[0375] In the preparation of coated dry materials and molten mixtures, it is possible to determine the preparation conditions, such as the coating amount and cooling method, so as to make them into shapes and sizes according to their uses, etc.

[0376] Furthermore, the prepared resin composition can be adjusted to the shape and size according to its intended use using conventional methods, such as molding and size adjustment methods. The molten mixture can also be subjected to the heat-melt molding method described later, which involves melt curing and molding.

[0377] [Filter]

[0378] The resin composition of the present invention is preferably used as a material for forming filters by appropriate molding or the like. Filters are usually molded into flat films or thin films, but in the present invention, they can also be molded into various shapes such as films or thin films with curved surface states depending on the surface shape of the component on which the filter is disposed, and further into powder, spheres, broken particles, blocky continuum, fibers, tubes, hollow fibers, granules, porous and so on.

[0379] The filter of the present invention is formed comprising the resin composition, coated dried material, or melt-mixed material of the present invention, and has a predetermined shape. Preferably, the filter of the present invention is formed by molding the resin composition, coated dried material, or melt-mixed material of the present invention into a film or thin film, more preferably a film-shaped or thin film-shaped form of the resin composition of the present invention. The content of each component (solid component excluding organic solvent) in the filter is the same as the content in the resin composition (solid component) of the present invention.

[0380] The filter of the present invention can be preferably used as a light-absorbing filter (film) that highly absorbs (blocks) light of a specific wavelength that is targeted at an unwanted wavelength in the incident light. Furthermore, in addition to exhibiting the aforementioned excellent characteristics and being able to highly absorb (block) near-infrared light in the aforementioned wavelength region, the filter of the present invention also exhibits excellent oblique incidence characteristics. Therefore, besides being a light-absorbing filter, it can also be preferably used as a near-infrared cutoff filter for visibility calibration of solid-state imaging elements that use silicon photodiodes that sense infrared light as light-receiving sections. When the filter of the present invention is used as a near-infrared cutoff filter, it can be used in a conventional manner (method of use, etc.), for example, referring to the description in Japanese Patent No. 6605039, the contents of which are directly incorporated into this specification.

[0381] <Filter Manufacturing Method>

[0382] The manufacturing method of the filter will be explained below.

[0383] The filter is not particularly limited except for using the resin composition, coated dried material, or melt-mixed compound of the present invention, and can be suitably manufactured by conventional manufacturing methods. For example, the method described in the preparation of the above-described resin composition can be applied.

[0384] (Solution casting film production method)

[0385] When the filter of the present invention is in the form of a film or thin film, it can be manufactured using the above-described coated dry material or molten mixture, but manufacturing by solution casting is one of the preferred forms. In the solution casting method, a thin film is manufactured using a solution (doped solution, a "liquid composition" as a form of the resin composition of the present invention) in which at least a squaric acid compound and a binder resin are dissolved in an organic solvent.

[0386] There are no particular limitations on organic solvents, as long as they can dissolve the squaric acid compound and the adhesive resin. For example, solvents selected from aliphatic hydrocarbon solvents with 6 to 12 carbon atoms, aromatic hydrocarbon solvents with 6 to 20 carbon atoms, alcohol solvents with 1 to 4 carbon atoms, ether solvents with 3 to 12 carbon atoms, ketone solvents with 3 to 12 carbon atoms, ester solvents with 3 to 12 carbon atoms, and halogenated hydrocarbon solvents with 1 to 6 carbon atoms, as well as mixtures thereof, can be used. As a mixture of solvents, for example, a mixture of aliphatic hydrocarbon solvents or ketone solvents with aromatic hydrocarbon solvents is preferred.

[0387] Aliphatic hydrocarbon solvents, ether solvents, ketone solvents, and ester solvents can have cyclic structures. Furthermore, compounds having two or more of the functional groups of the aforementioned ether solvents, ketone solvents, and ester solvents (i.e., -O-, -CO-, and -COO-) (e.g., alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, alkylene glycol monoalkyl ether acetates, alkylene glycol dialkyl ether acetates) can also be used as the aforementioned organic solvents. The aforementioned organic solvents may have other functional groups such as alcohol hydroxyl groups. In the case of organic solvents having two or more functional groups, the number of carbon atoms is preferably within the aforementioned preferred carbon atom number range for solvents having any one of the functional groups.

[0388] Organic solvents with boiling points below 200°C prevent excessively high drying temperatures after coating. The preferred boiling point range is as described above.

[0389] The content of the adhesive resin in the solution is preferably adjusted to 1-80% by mass, more preferably 10-75% by mass. Any of the above-mentioned additives may be added to the organic solvent (main solvent).

[0390] The total content of the total solids in the solution is set as the sum of the contents of the above-mentioned components of the squaric acid compound, the adhesive resin and the additives, preferably 1 to 80% by mass, more preferably 5 to 75% by mass, and even more preferably 10 to 65% by mass.

[0391] Regarding the drying method in solution casting film production, please refer to the specifications of U.S. Patent Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, 2,492,978, 2,607,704, 2,739,069, and 2,739,070; British Patent Nos. 640,731 and 736,892; and Japanese Patent Publications Nos. 45-4554, 49-5614, 60-176,834, 60-203,430, and 62-115,035. Drying on the annular belt can be carried out by blowing inert gases such as air or nitrogen.

[0392] The dopant solution is cast onto the ring, causing the solvent to evaporate and form a film. Regarding the adjustment of the dopant solution before casting, its concentration is preferably adjusted to ensure the solid content is in the range of 10–40% by mass. The surface of the ring is preferably finished to a mirror finish.

[0393] It is also possible to use the prepared solution (doped solution) to cast more than two layers to form a thin film.

[0394] When fabricating a thin film with two or more layers by casting multiple dopant solutions, such as cycloolefin resin solutions, the dopant solutions can be cast separately from multiple casting ports spaced apart along the travel direction of the support, and the thin films can be stacked simultaneously. This can be achieved, for example, by using the methods described in Japanese Patent Application Publications Nos. 61-158414, 1-122419, and 11-198285. Furthermore, it is also possible to form a thin film by casting the dopant solution from two casting ports. This can be achieved, for example, by using the methods described in Japanese Patent Application Publications Nos. 60-27562, 61-94724, 61-947245, 61-104813, 61-158413, and 6-134933. In addition, the resin film casting method described in Japanese Patent Application Publication No. 56-162617 can also be used, which uses a low-viscosity resin solution to encapsulate the flow of a high-viscosity resin solution and simultaneously extrudes the high / low viscosity resin solutions.

[0395] Furthermore, it is also possible to produce a film by using two casting openings, peeling off the film formed on the support through the first casting opening, and then performing a second casting on the side in contact with the support surface. For example, the method described in Japanese Patent Publication No. 44-20235 can be cited.

[0396] The casting solution can be the same or two or more different solutions. To impart multi-layer functionality, a solution corresponding to its function can be extruded from each casting port. Furthermore, solution casting can also be configured to cast simultaneously with other functional layers (e.g., adhesive layers, dye layers, antistatic layers, anti-halo layers, UV absorption layers, polarizing layers, etc.).

[0397] The addition of the compound (pigment) represented by general formula (1) to the above solution can, for example, be mixed with the binder resin into the organic solvent during the preparation of the dopant solution.

[0398] (Drying process)

[0399] The process from casting the dopant solution to post-drying can be performed in an air atmosphere or in an inert gas atmosphere such as nitrogen. The winding machine used to manufacture the filter of the present invention can be a conventional winding machine capable of winding using methods such as constant tension, constant torque, taper tension, or programmed tension control with constant internal stress. As for drying conditions, for example, the drying conditions used when making coated dried materials can be applied.

[0400] (Stretching treatment)

[0401] The above-mentioned filter can also be stretched. The stretching process can impart a desired delay to the filter. The stretching direction of the filter is preferably either the width direction or the long side direction.

[0402] Methods of stretching along the width direction are described, for example, in Japanese Patent Application Publication Nos. 62-115035, 4-152125, 4-284211, 4-298310, and 11-48271.

[0403] The stretching of the membrane (filter before stretching) is performed under heating conditions. The membrane can be stretched during the drying process, which is particularly effective in the presence of solvent residue. In the case of stretching along the long side, for example, the membrane is stretched by adjusting the speed of the membrane on the conveyor rollers so that the winding speed is faster than the peeling speed. In the case of stretching along the width, the membrane can also be stretched by conveying it while maintaining its width using a tenter frame, and gradually expanding the width of the tenter frame. Stretching can also be performed using a stretching machine after the membrane has dried (preferably uniaxial stretching using a long stretching machine).

[0404] There are no particular limitations on the molding method of the filter; it can be manufactured as described above. Alternatively, either thermoforming or solution casting can be used. Thermoforming can be further categorized into extrusion molding, compression molding, expansion molding, injection molding, blow molding, and stretch molding. However, among these methods, extrusion molding, expansion molding, and compression molding are preferred for obtaining films with excellent mechanical strength and surface finish, with extrusion molding being the most preferred. Molding conditions can be appropriately selected based on the intended use and molding method. When using thermoforming, the roller temperature is appropriately set within the range of 150–400°C, preferably 200–350°C, and more preferably 230–330°C. If the polymer temperature is too low, the fluidity deteriorates, resulting in shrinkage marks or deformation in the film. If the polymer temperature is too high, it may cause porosity or silver streaks due to polymer thermal decomposition, or poor molding such as film yellowing.

[0405] (Physical properties or characteristics of the filter)

[0406] Preferred physical properties or characteristics of the filter of the present invention will be described.

[0407] As described above, the filter of the present invention exhibits small deviations in the state of the squaric acid compound and other properties, resulting in excellent surface appearance. Specifically, this is illustrated in the evaluation of surface appearance in the embodiments described later.

[0408] Considering the improved productivity resulting from reduced processability and drying time during lamination, the thickness of the filter typically ranges from 0.1 to 300 μm, preferably from 0.2 to 200 μm, and more preferably from 0.3 to 100 μm.

[0409] The wetting tension of the filter surface is preferably 40 mN / m or more, more preferably 50 mN / m or more, and even more preferably 55 mN / m or more. When the surface wetting tension is within the above range, the adhesion strength between the filter and the polarizer is improved. To adjust the surface wetting tension, methods such as corona discharge treatment, ozone blowing, ultraviolet irradiation, flame treatment, chemical treatment, and other known surface treatments can be implemented.

[0410] The phase difference (delay) of the filter of the present invention will be explained. The in-plane phase difference value Ro at 589 nm of the filter of the present invention is preferably 0 to 20 nm, more preferably 0 to 10 nm. Furthermore, the phase difference value Rth in the thickness direction is preferably -20 to 50 nm, more preferably -10 to 20 nm.

[0411] Typically, the delay can be controlled by the film's delay before stretching, the stretching ratio, the stretching temperature, and the thickness of the stretched oriented film. When the film thickness before stretching is constant, films with a higher stretching ratio tend to have a larger absolute value of delay. Therefore, by changing the stretching ratio, a stretched oriented film with the desired delay can be obtained.

[0412] When stretching the filter, the thickness of the filter before stretching is preferably about 50 to 500 μm. The smaller the thickness unevenness, the better. It is within ±8% over the entire surface, preferably within ±6%, and more preferably within ±4%.

[0413] The stretching ratio is preferably 1.1 to 10 times, more preferably 1.3 to 8 times, and the desired delay can be set within this range.

[0414] The resulting filter can be stretched to orient the molecules, giving them a delay of the desired size.

[0415] The smaller the delay deviation, the better. For the filter involved in this invention, the delay deviation of the wavelength 589nm for either the in-plane or thickness direction is generally within ±50nm, preferably less than ±30nm, and more preferably less than ±20nm.

[0416] For deviations in the in-plane and thickness directions of delay and uneven thickness of the filter, in addition to using these small pre-stretch films, it is also possible to reduce these deviations by applying stress evenly to the film during stretching. Therefore, stretching is preferably performed under a uniform temperature distribution, preferably within ±5°C, more preferably within ±2°C, and especially preferably within ±0.5°C.

[0417] [Image display device]

[0418] Examples of image display devices according to the present invention include liquid crystal display devices and organic electroluminescent display devices. For the image display device of the present invention, a preferred form of liquid crystal display device (also referred to as "the liquid crystal display device of the present invention") will be described as an example.

[0419] The liquid crystal display device of the present invention is characterized by including at least one filter of the present invention. The filter of the present invention, as described below, can be used as a polarizing protective film and / or an adhesive layer, and can also be included in the backlight unit of the liquid crystal display device.

[0420] A liquid crystal display device preferably includes a filter, a polarizer including a polarizer and a polarizing protective film, an adhesive layer, and a liquid crystal cell. The polarizer is preferably bonded to the liquid crystal cell via the adhesive layer. In this liquid crystal display device, the filter can also serve as either a polarizing protective film or an adhesive layer. That is, the liquid crystal display device can be categorized into two cases: one including a polarizer with a polarizer and a filter (polarizing protective film), an adhesive layer, and a liquid crystal cell; and the other including a polarizer with a polarizer and a polarizing protective film, a filter (adhesive layer), and a liquid crystal cell.

[0421] Figure 1 This is a schematic diagram illustrating an example of the liquid crystal display device of the present invention. Figure 1 The liquid crystal display device 10 includes a liquid crystal cell having a liquid crystal layer 5 and a liquid crystal cell upper electrode substrate 3 and a liquid crystal cell lower electrode substrate 6 disposed above and below the liquid crystal layer 5, and an upper polarizer 1 and a lower polarizer 8 disposed on both sides of the liquid crystal cell (the direction of each absorption axis is indicated by arrows with additional symbols 2 or 9). A color filter layer may be stacked on the liquid crystal cell upper electrode substrate 3 or the liquid crystal cell lower electrode substrate 6 (each orientation control is indicated by arrows with additional symbols 4 or 7). A backlight unit B is disposed on the back side of the liquid crystal display device 10. The light source of the backlight unit B is not particularly limited. For example, a light-emitting device using white LEDs can be used.

[0422] The upper polarizer 1 and the lower polarizer 8 each have a structure in which the polarizer is sandwiched between two polarizer protective films. In the liquid crystal display device 10 of the present invention, at least one polarizer is preferably a polarizer including the filter (not shown) of the present invention.

[0423] Furthermore, in the liquid crystal display device 10 of the present invention, the liquid crystal cell and the polarizer (upper polarizer 1 and / or lower polarizer 8) can be bonded via an adhesive layer (not shown). In this case, the filter of the present invention can also serve as the adhesive layer.

[0424] The liquid crystal display device 10 includes image direct viewing type, image projection type, and light modulation type. In this invention, active matrix liquid crystal display devices using 3-terminal or 2-terminal semiconductor elements such as TFTs or MIMs are effective. Of course, passive matrix liquid crystal display devices, represented by the STN mode known as time-division driving, are also effective.

[0425] When the filter of the present invention is included in the backlight unit B, the polarizer of the liquid crystal display device can be a conventional polarizer (excluding the polarizer of the filter of the present invention) or a polarizer including the filter of the present invention. Furthermore, the adhesive layer can be a conventional adhesive layer (not the filter of the present invention) or an adhesive layer based on the filter of the present invention.

[0426] The IPS-mode liquid crystal display device described in paragraphs 128 to 136 of Japanese Patent Application Publication No. 2010-102296 is preferably the liquid crystal display device of the present invention.

[0427] <Polarizing plate>

[0428] The polarizer used in this invention includes a polarizer and at least one polarizer protective film.

[0429] The polarizer used in this invention preferably has a polarizer and polarizer protective films on both sides of the polarizer, and preferably includes the filter of this invention as a polarizer protective film on at least one side. A conventional polarizer protective film may be present on the side of the polarizer opposite to the side having the filter (polarizer protective film) of this invention.

[0430] The polarizer protective film used in this invention has a thickness of 5 μm or more and 120 μm or less, more preferably 10 μm or more and 100 μm or less. A thinner film is less likely to cause display unevenness after high temperature and humidity time when mounted in a liquid crystal display device, and is therefore preferred. On the other hand, if it is too thin, it is difficult to maintain stable transport during film manufacturing and polarizer fabrication. The thickness of the filter constituting the polarizer protective film preferably meets the above-mentioned range.

[0431] -Shape, Composition-

[0432] The polarizers used in this invention include not only polarizers cut into films that can be directly mounted on liquid crystal display devices, but also polarizers manufactured in a continuous process, formed into elongated shapes, and wound into rollers (e.g., rollers with a length of 2500 mm or more, or 3900 mm or more). For use in large-screen liquid crystal display devices, the width of the polarizer is preferably 1470 mm or more.

[0433] The polarizer used in this invention consists of a polarizer and at least one polarizer protective film, and preferably a separation film is further bonded to the surface of one side of the polarizer.

[0434] Separation films are used to protect polarizers during shipping and product inspection. They are used to cover the adhesive layer bonded to the LCD panel and to bond the polarizer to the side of the LCD panel.

[0435] (Polarizer)

[0436] The polarizer used in the polarizer of the present invention will be described.

[0437] As a polarizer that can be used in the present invention, it is preferably composed of polyvinyl alcohol (PVA) and dichroic molecules, as described in Japanese Patent Application Publication No. 11-248937. A polyethylene strut polarizer that generates a polyene structure and orients it by dehydrating and dechlorinating PVA and polyvinyl chloride is also possible.

[0438] -Polarizer film thickness-

[0439] The film thickness before stretching by the polarizer is not particularly limited, but from the viewpoint of maintaining film stability and stretching uniformity, it is preferably 1 μm to 1 mm, and more preferably 5 to 200 μm. Furthermore, as described in Japanese Patent Application Publication No. 2002-236212, a thin PVA film with a stress of less than 10 N generated when stretched 4 to 6 times in water can be used.

[0440] - Manufacturing method of polarizer-

[0441] There are no particular limitations on the manufacturing method of the polarizer. For example, it is preferable to form the above-mentioned PVA film and then introduce dichroic molecules to construct the polarizer. The manufacturing of the PVA film can be carried out with reference to the methods described in Japanese Patent Application Publication No. 2007-86748 (0213) to (0237), Japanese Patent No. 3342516, Japanese Patent Application Publication No. 09-328593, Japanese Patent Application Publication No. 2001-302817, and Japanese Patent Application Publication No. 2002-144401.

[0442] (Layering method of polarizer and polarizer protective film)

[0443] The polarizer used in this invention is manufactured by bonding (laminating) at least one polarizer protective film (preferably the filter of this invention) to at least one side of the polarizer.

[0444] Preferably, the polarizer is manufactured by laminating both sides of the polarizer, which is made by alkali treatment of the polarizer protective film and stretching the polyvinyl alcohol film by immersing it in an iodine solution, using a fully saponified aqueous solution of polyvinyl alcohol.

[0445] As an adhesive used to bond the aforementioned polarizer protective film to the processing surface and the polarizer, examples include polyvinyl alcohol-based adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl-based latexes such as acrylic resin.

[0446] Regarding the method of attaching the polarizer protective film of the polarizer used in the present invention to the polarizer, it is preferable to attach the polarizer in a manner in which the transmission axis of the polarizer is substantially parallel, orthogonal, or at 45° to the slow axis of the polarizer protective film.

[0447] The slow axis can be measured using various known methods, such as a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments Co., Ltd.).

[0448] Here, "paired" essentially means that the direction of the principal refractive index nx of the polarizer protective film and the direction of the polarizer's transmission axis intersect at an angle within ±5°, preferably within ±1°, and more preferably within ±0.5°. If the angle of intersection is within 1°, the polarization performance of the polarizer under orthogonal Nicol is less likely to decrease, and light leakage is less likely to occur, which is therefore preferred.

[0449] The fact that the direction of the principal refractive index nx is orthogonal to or at 45° to the direction of the transmission axis means that the angle at which the direction of the principal refractive index nx intersects the direction of the transmission axis is within the range of ±5° from a strict angle related to orthogonality and 45°. The error from the strict angle is preferably within the range of ±1°, and more preferably within the range of ±0.5°.

[0450] (Functionalization of Polarizing Films)

[0451] The polarizer used in this invention is also preferably used as a functionalized polarizer composited with an optical film having functional layers such as an anti-reflective film, a brightness enhancement film, a hard coating, a forward scattering layer, an anti-glare (anti-fouling) layer, an anti-fouling layer, and an antistatic layer for improving the visibility of a display. The functionalized anti-reflective film, brightness enhancement film, other functional optical films, hard coating, forward scattering layer, and anti-glare layer are described in paragraphs

[0257] to

[0276] of Japanese Patent Application Publication No. 2007-86748, and functionalized polarizers can be manufactured based on these descriptions.

[0452] (Adhesive layer)

[0453] In the liquid crystal display device of the present invention, the polarizer is preferably bonded to the liquid crystal cell via an adhesive layer. The filter of the present invention can also serve as the aforementioned adhesive layer. When the filter of the present invention does not serve as an adhesive layer, a conventional adhesive layer can be used.

[0454] As an adhesive layer, there are no particular limitations as long as it can adhere to the polarizer and the liquid crystal cell. For example, acrylic, urethane, and polyisobutylene are preferred.

[0455] When the filter of the present invention is also used as an adhesive layer, the adhesive layer contains the above-mentioned pigment and the above-mentioned adhesive, and further contains crosslinking agents, coupling agents, etc. to impart adhesion.

[0456] When the filter also serves as an adhesive layer, the adhesive layer preferably contains 90-100% by mass of the above-described adhesive, more preferably 95-100% by mass of the above-described adhesive. The pigment content is as described above.

[0457] The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 50 μm, and more preferably 3 to 30 μm.

[0458] (Liquid Crystal Unit)

[0459] There are no particular limitations on the liquid crystal cell; a standard liquid crystal cell can be used.

[0460] [Solid-state camera element]

[0461] The solid-state imaging element of the present invention includes the filter of the present invention described above. As for the configuration of the solid-state imaging element of the present invention, there are no particular limitations as long as it includes the filter of the present invention and functions as a solid-state imaging element. The solid-state imaging element of the present invention includes the filter (color filter) of the present invention, which has excellent weather resistance and contrast, and therefore exhibits excellent tonal and color reproduction of images even after long-term use.

[0462] There are no particular limitations on the configuration of a solid-state imaging element, as long as it incorporates the color filter of the present invention and functions as a solid-state imaging element. For example, a configuration can be described as follows: a support having a plurality of photodiodes constituting a light-receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a light-receiving element including polysilicon, etc., and the color filter of the present invention is provided on the side of the support on which the light-receiving element is formed (e.g., the part other than the light-receiving portion and the pixel portion for color adjustment, etc.) or on the side opposite to the forming surface.

[0463] Example

[0464] The following examples further illustrate the present invention in detail. The materials, reagents, quantities, proportions, operations, etc., shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the invention is not limited to the following specific examples.

[0465] In this invention, "room temperature" refers to 25°C.

[0466] [Example A] Synthesis and Evaluation of Squamous Acid Compounds

[0467] [Synthetic Example 1] Synthesis of Compound B-12

[0468] [Chemical Formula 29]

[0469]

[0470] 0.91 g of 4-butylaniline, 1.00 g of 3-bromonitrobenzene, 1.85 g of potassium carbonate, and 30 mL of isopropanol were mixed and stirred at room temperature for 1 hour under nitrogen bubbling. Then, 0.16 g of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (xPhos) and 0.061 g of tris(benzylacetone)dipalladium (Pd2bda3) were added, and the mixture was heated and stirred at 110 °C for 8 hours. After the reaction was complete, the reaction mixture was cooled to room temperature and then ice-cooled. 30 mL of water containing 2.15 g of ammonium chloride was slowly added dropwise, and the mixture was stirred for another hour. The obtained crystals were filtered, and the filtrate (crystals) was purified by silica gel column chromatography to obtain 0.65 g (54%) of intermediate 1.

[0471] 4.5 g of intermediate and 40 mL of 1, dimethylacetamide were added, and 0.7 g of sodium hydride was slowly added while stirring under ice-cold conditions for 30 minutes. Then, 4.25 g of 2-ethylhexyl bromide was added dropwise, and the mixture was heated and stirred at room temperature for 6 hours, followed by heating and stirring at an internal temperature of 45°C for another 6 hours. After the reaction was complete, the reaction mixture was cooled and 100 mL of water was added dropwise. Then, 100 mL of ethyl acetate and 100 mL of hexane were added, and the organic layer was extracted. The organic layer was washed with water and saturated brine, dried with magnesium sulfate, concentrated, and then purified by silica gel column chromatography (hexane / ethyl acetate = 4 / 1) to obtain 2.0 g (31%) of intermediate 2.

[0472] After adding 2.0 g of intermediate 2 and 20 mL of tetrahydrofuran and stirring, 1.0 g of palladium hydroxide was added. The flask was then completely purged with hydrogen, and the reaction was allowed to proceed at room temperature for 5 hours. After the reaction was complete, the reaction mixture was concentrated, filtered through silica gel, and purified by silica gel column chromatography (hexane / ethyl acetate = 4 / 1) to obtain 1.8 g (61%) of intermediate 3.

[0473] 1.1 g of intermediate 3 and 15 mL of dimethylacetamide were added, followed by 0.42 g of dimethylaminopyridine and 0.72 g of ferrocene carboxylic acid. The mixture was stirred at room temperature for 30 minutes. Then, 0.66 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added to the resulting mixture, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, 50 mL of hexane, ethyl acetate, and 100 mL of 1N hydrochloric acid were added to the reaction mixture, and the organic layer was extracted. The organic layer was washed with water and saturated brine, dried over magnesium sulfate, concentrated, and then purified by silica gel column chromatography (hexane / ethyl acetate = 4 / 1) to obtain 1.8 g (88%) of intermediate 4.

[0474] 0.80 g of intermediate 4, 0.08 g of squaric acid, 10 mL of toluene, and 10 mL of n-butanol were added to a flask fitted with a Dean-Stark tube and mixed. The mixture was heated under reflux for 4 hours. After the reaction was complete, the reaction mixture was cooled to 0°C, and the resulting crystals were filtered off. The filtrate (crystals) was then washed with methanol. 10 mL of methanol was added to the crude crystals, and the mixture was heated under reflux for 1 hour. The filtrate (crystals) was then washed off with methanol. This yielded 0.69 g (80%) of squaric acid compound B-12.

[0475] Through nuclear magnetic resonance spectroscopy ( 1 The squaric acid compound B-12 was identified by 1H-NMR.

[0476] 1 H-NMR (CDCl3): δ11.77~11.33 (m, 2H), 8.50~8.22 (m, 4H), 7.28~7.26 (m, 4H), 7.1 5~7.13 (m, 4H), 6.36~6.33 (m, 2H), 5.32~5.20 (m, 4H), 4.44~4.34 (m, 4H), 4.23~4 .15(m, 10H), 3.84~3.74(m, 4H), 2.69~2.65(m, 4H), 1.85~1.80(m, 2H), 1.69~1.6 2(m, 4H), 1.51~1.36(m, 12H), 1.24~1.22(m, 8H), 0.97(t, 6H), 0.87~0.83(m, 12H)

[0477] [Experimental Example 1] Determination of the maximum absorption wavelength of squaric acid compounds

[0478] The obtained squaric acid compound B-12 was dissolved in chloroform (concentration 1×10⁻⁶). -6 The maximum absorption wavelength λmax of squaric acid compound B-12 was determined using a cell with an optical path length of 10 mm and a UV-1800PC spectrophotometer (manufactured by Shimadzu Corporation). The results of the determination of the maximum absorption wavelength λmax of compound B-12 are shown in Table 1 below.

[0479] [Experimental Example 2] Evaluation of the solubility of squaric acid compounds

[0480] The solubility of the obtained squaric acid compound B-12 in a toluene / cyclohexanone mixed solvent (toluene / cyclohexanone = 90 / 10 (vol%)) was confirmed. Specifically, the amount of squaric acid compound B-12 dissolved relative to 100 parts by mass of the toluene / cyclohexanone mixed solvent was determined (mass%).

[0481] Solubility was evaluated by applying the obtained solubility to the following criteria.

[0482] - Evaluation Criteria for Solubility -

[0483] A: 0.1% by mass or more

[0484] B: ≥0.01% by mass and <0.1% by mass

[0485] C: less than 0.01% by mass

[0486] Based on the above [Synthesis Example 1], the squaric acid compounds shown in Table 1 below and the comparative compounds C-1 to C-6 below were synthesized respectively.

[0487] The following shows the specific synthetic methods for compounds A-19, A-28 and A-4.

[0488] [Synthetic Example 2] Synthesis of Compound A-19

[0489] Compound A-19 was synthesized according to the following scheme.

[0490] [Chemical Formula 30]

[0491]

[0492] 2.1 g of intermediate 3 obtained in [Synthetic Example 1] and 13 mL of dimethylacetamide were added and stirred under ice. Then, 0.92 g of 2,2-dimethylacetamide was added dropwise. After the addition was complete, the mixture was returned to room temperature and stirred for 4 hours. After the reaction was complete, it was cooled again, and 40 mL of water was added dropwise. A 5% NaOH aqueous solution was then added until the reaction solution reached pH 8. Then, 60 mL of ethyl acetate was added and the organic layer was extracted. The organic layer was washed with water and saturated brine, dried with magnesium sulfate, concentrated, and then purified by silica gel column chromatography (hexane / ethyl acetate = 8 / 1) to obtain 2.4 g (86%) of intermediate 5.

[0493] 2.2 g of intermediate 5, 0.42 g of squaric acid, 10 mL of toluene, and 10 mL of n-butanol were added to a flask fitted with a Dean-Stark tube and mixed. The mixture was heated under reflux for 10 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, and 30 mL of methanol was added. The mixture was stirred at room temperature for 2 hours. The resulting crystals were filtered, and the filtrate (crystals) was washed with methanol. Thus, 2.0 g (85%) of squaric acid compound A-19 was obtained.

[0494] Through nuclear magnetic resonance spectroscopy ( 1 The squaric acid compound A-19 was identified by 1H-NMR.

[0495] 1 H-NMR (CDCl3): δ11.37~11.05 (m, 2H), 8.48~8.41 (m, 4H), 7.26~7.24 (d, 4H), 7.11~7.09 (d, 4H), 6.26~6.24 (d, 2H), 3.76~3.74 (m, 4H), 2.67~2.63(m, 4H), 1.83~1.74(m, 6H), 1.67~1.60(m, 4H), 1.41~1.33(m, 24H), 1.25~1.21(m, 8H), 0.97-0.93(m, 6H), 0.89~0.81(m, 18H)

[0496] [Synthetic Example 3] Synthesis of Compound A-28

[0497] Compound A-28 was synthesized according to the following scheme.

[0498] [Chemical Formula 31]

[0499]

[0500] 2.2 g of intermediate 6, 0.42 g of squaric acid, 10 mL of toluene, and 10 mL of n-butanol were added to a flask fitted with a Dean-Stark tube and mixed. The mixture was heated under reflux for 10 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, and 30 mL of methanol was added. The mixture was stirred at room temperature for 2 hours. The resulting crystals were filtered, and the filtrate (crystals) was washed with methanol. The crude crystals were further purified by silica gel column chromatography (hexane / ethyl acetate = 6 / 1) and then dried. Thus, 1.6 g (67%) of squaric acid compound A-28 was obtained.

[0501] In addition, intermediate 6 is synthesized by referring to the synthesis method of intermediate 5 in [Synthesis Example 2].

[0502] Through nuclear magnetic resonance spectroscopy ( 1 The squaric acid compound A-28 was identified by 1H-NMR.

[0503] 1H-NMR (CDCl3): δ12.40~12.03(m, 2H), 8.44~8.34(m, 4H), 8.12~7.90(m, 4H), 7.65~7.39(m, 4H), 7.37~7.27(m, 5H), 7.13~7.03(m, 5H), 6.35~6.32(m, 2H), 3.85~3.75(m, 4H), 2.68~2.64(m, 4H), 1.85~1.79(m, 2H), 1.68~1.61(m, 4H), 1.51~1.33(m, 12H), 1.25~1.21(m, 8H), 0.98~0.94(m, 6H), 0.87~0.81(m, 12H)

[0504] [Synthetic Example 4] Synthesis of Compound A-4

[0505] Compound A-4 was synthesized according to the following scheme.

[0506] [Chemical Formula 32]

[0507]

[0508] After adding 5.7 g of intermediate 7, 2.0 g of aromatic acyl chloride, and 50 mL of toluene, the mixture was heated to reflux for 8 hours. After the reaction was complete, 100 mL of water was added dropwise to the reaction mixture, which had been cooled to room temperature, and the mixture was stirred for 1 hour. Then, 50 mL of toluene was added to extract the organic layer. The organic layer was repeatedly washed with water and then concentrated under reduced pressure. Next, 50 mL of acetic acid, 50 mL of water, and 4 mL of hydrochloric acid solution of a specified concentration were added to the concentrated residue, and the mixture was heated to reflux for 8 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, and the reaction solvent was concentrated under reduced pressure. Then, 10 mL of methanol was added. After stirring at room temperature for 1 hour, the obtained crystals were filtered, and the filtrate (crystals) was washed with water and methanol and then dried. Thus, 3.1 g (45%) of the target intermediate 8 was obtained.

[0509] 1.0 g of intermediate 8, 0.73 g of intermediate 9, 10 mL of toluene, and 10 mL of n-butanol were added to a flask fitted with a Dean-Stark tube and mixed. The mixture was heated to reflux for 2 hours. After the reaction was complete, the reaction mixture was cooled to 0°C, and the resulting crystals were filtered off. The filtrate (crystals) was washed with methanol. The crude crystals were further purified by silica gel column chromatography (hexane / ethyl acetate = 2 / 1) and then dried. Thus, 1.1 g (68%) of the target compound A-4 was obtained.

[0510] In addition, intermediates 7 and 9 were synthesized by referring to the synthesis method of intermediate 5 in [Synthesis Example 2].

[0511] The obtained squaric acid compound A-4 was identified by matrix-assisted laser ionization mass spectrometry (MALDI-MS).

[0512] MS: m / z = 895.6([M+H]) + )

[0513] For each synthesized compound, the maximum absorption wavelength λmax and solubility were measured and evaluated in the same manner as in Experimental Examples 1 and 2 above, and the results are shown in Table 1. In addition, the measured solubility of comparative compounds C-1 to C-3, C-5 and C-6 is also recorded.

[0514] In Table 1, the numbers attached to each of the acid compounds correspond to the example compound numbers of the acid compounds described above (the same applies to Tables 2 to 5).

[0515] [Chemical Formula 33]

[0516]

[0517] [Table 1]

[0518] Squamous acid compounds λmax(nm) Solubility A-1 688 A A-2 690 A A-4 699 A A-5 681 A A-8 693 A A-10 691 A A-12 687 A A-14 693 A A-16 688 A A-19 687 A A-20 696 A A-21 688 A A-22 688 A A-24 684 A A-26 688 A A-28 695 A A-29 695 A A-30 697 A B-1 700 B B-2 691 A B-3 684 A B-4 714 A B-5 693 B B-7 694 A B-11 697 A B-12 696 A B-15 691 B B-20 701 A C-1 680 C (<0.005% by mass) C-2 737 C (<0.005% by mass) C-3 658 C (<0.005% by mass) C-4 685 B C-5 682 C (<0.005% by mass) C-6 681 C (<0.01% by mass)

[0519] [Example B] Preparation of resin composition and fabrication and evaluation of filter

[0520] The resin composition (liquid composition) of the present invention was prepared using the squaric acid compound synthesized in Example A, and then a filter was made to evaluate its lightfastness and surface properties.

[0521] The materials used in this embodiment are shown below.

[0522] (Resin 1)

[0523] Commercially available polystyrene (manufactured by PS Japan Corporation, SGP-10, Tg: 100°C) is heated at 110°C and then returned to room temperature (23°C) before use.

[0524] (Resin 2)

[0525] Heating commercially available ARTON (manufactured by JSR Corporation, RX4500, Tg140℃, cyclic polyolefin) at 110℃ and then allowing it to return to room temperature before use.

[0526] (Substrate film 1)

[0527] Commercially available polyethylene terephthalate film and Lumirror(R)S105 (film thickness 38μm, manufactured by TORAYINDUSTRIES, INC.) were used as substrate 1.

[0528] <Example 28>

[0529] (Preparation of the resin composition)

[0530] A resin solution S-1, which is one embodiment of the resin composition of the present invention, was prepared by mixing the components shown below (dissolved in a toluene / cyclohexanone mixed solvent).

[0531]

[0532] Next, the obtained resin solution S-1 was filtered with filter paper (#63, manufactured by Toyo Roshi Kaisha, Ltd.) with an absolute filtration accuracy of 10 μm, and then filtered with a sintered metal filter (FH025, manufactured by NIHON PALLLTD.) with an absolute filtration accuracy of 2.5 μm.

[0533] (Filter fabrication)

[0534] The resin solution S-1 after filtration was coated onto the substrate film 1 using a rod coater to achieve a thickness of 5.0 μm after drying, and then dried at 100°C to produce a filter (resin film) 101 as the coated and dried material.

[0535] <Experimental Example 3> Evaluation of the lightfastness of filters

[0536] The lightfastness of the filter 101 fabricated in Example 28 was evaluated by the rate of change of absorbance (%).

[0537] Specifically, using a Super Xenon Lamp Weathering Tester SX75 (trade name, manufactured by Suga Test Instruments Co., Ltd.), filter 101 was irradiated with 100,000 lux of light for 90 hours at 50°C and 50% relative humidity. The absorbance difference at the wavelength of maximum absorption was measured, and the absorbance change rate was calculated using the following formula. The results are shown in Table 2.

[0538] (Absorbance change rate) (%) = [(Absorbance difference after 90 hours of irradiation) / (Absorbance difference before 90 hours of irradiation)] × 100

[0539] Here, the absorbance difference at the wavelength of maximum absorption of the filter is determined as follows.

[0540] For a filter (blank culture medium) prepared in the same manner as filter 101, except that it was made using a UV3600 spectrophotometer (manufactured by Shimadzu Corporation) and did not contain filter 101 or squaric acid compound B-12, the absorbance per 1 nm in the wavelength range of 400–800 nm was measured. The absorbance difference between the absorbance of filter 101 at each wavelength and the absorbance of the filter (blank culture medium) was calculated, and the wavelength with the largest absorbance difference was defined as the absorption maximum wavelength. That is, the largest absorbance difference was set as the absorbance difference at the absorption maximum wavelength of filter 101.

[0541] <Experimental Example 4> Evaluation of the surface shape of the filter

[0542] The surface appearance of the filter 101 fabricated in Example 28 was evaluated by visual observation using an optical microscope. Specifically, ten random points on the filter 101 were observed at 200x magnification using an optical microscope MX-61L (trade name, manufactured by Olympus Corporation). At each observation point, the presence or absence of inhomogeneities in the resin film was confirmed (such as linear scratches, protrusions, or unevenness on the surface, or the presence or aggregation of squaric acid compounds within or on the film surface). Specifically, inhomogeneities were defined as those that could be visually identified by linear scratches on the surface, unevenness originating from repulsion, or scattering or turbidity of the resin film due to precipitates caused by the presence or aggregation of squaric acid compounds.

[0543] The total number of observation points (out of all 10 observation points) was used to evaluate the isomorphism based on the following evaluation criteria. The results are shown in Table 2.

[0544] -Evaluation Criteria for Areas-

[0545] A: The total number of observation points is 9 or more.

[0546] B: The total number of observation points is more than 6 and less than 8.

[0547] C: The total number of observation points is less than 6.

[0548] <Examples 1-15, 21-27, 29-34 and Comparative Examples 1-6>

[0549] The resin used in Example 28, as well as the squaric acid compound and its content, were changed to those shown in Table 2. Otherwise, the resin compositions and filters of Examples 1-15, 21-27, 29-34, and Comparative Examples 1-6 were prepared or manufactured in the same manner as in Example 28. The thickness of each filter was also the same as that of filter 101 in Example 28.

[0550] In addition, in Examples 11-13, 15 and 31-34 using resin 2, the toluene / cyclohexanone mixed solvent was changed to a mixed solvent of 1427 parts by mass of cyclohexane and 250 parts by mass of ethyl acetate in the preparation of the resin composition, and the substrate film 1 was changed to a triacetyl cellulose film ZRD40SL (trade name, manufactured by FUJIFILM Corporation) in the fabrication of the filter.

[0551] Furthermore, since compounds C-1 to C-6 were not completely soluble in the toluene / cyclohexanone mixed solvent at the following concentrations, filters were made using resin solutions obtained by filtering out the insoluble matter.

[0552] For each filter fabricated, the lightfastness and surface properties were evaluated in the same manner as in Experimental Examples 3 and 4 above, and the results are shown in Table 2.

[0553] [Table 2]

[0554]

[0555] In Table 2, the "content*" of the squaric acid compound is the mass ratio (parts by mass) relative to 100 parts by mass of the resin.

[0556] In Examples 1-15, 21-27, 29-34 and Comparative Examples 1-6, the content of the squaric acid compound was changed to 1.49 parts by mass, the same as in Example 28 (resin solution S-1). Otherwise, the resin compositions were prepared in the same manner as in each example or comparative example, and filters were made accordingly.

[0557] As a result, the lightfastness test results of Examples 1-15, 21-27, 29-34 and Comparative Examples 1-6 showed slight variations compared to the values ​​recorded in Table 2, but were generally equal to the values ​​recorded in Table 2, and the same improvement trend in lightfastness was confirmed. Furthermore, the surface area of ​​the filter yielded the same results as shown in Table 2. Therefore, it can be seen that even with appropriate changes in the resin composition and the content of the squaric acid compound in the filter within the range specified in this invention, the same effect can be obtained.

[0558] [Example C] Preparation of resin composition and fabrication and evaluation of filter

[0559] The resin composition (liquid composition) of the present invention, prepared using the squaric acid compound synthesized in Example A and the poly(meth)acrylic acid resin as resin 3, was coated and dried to produce a filter as the coated and dried product. The lightfastness and surface appearance of the obtained filter were evaluated.

[0560] <Example 107>

[0561] A liquid resin composition was prepared by mixing 0.07 parts by mass of squaric acid compound B-12, 14 parts by mass of a propylene glycol monomethyl ether acetate solution containing 40% by mass of resin 3: benzyl methacrylate / methacrylic acid copolymer (molar ratio = 70 / 30, Tg = 80-90℃), and 30 parts by mass of tetrahydrofuran to dissolve the squaric acid compound and resin 3. The obtained resin composition was spin-coated (500 rpm, 30 seconds) onto a glass substrate to form a coating film. The obtained coating film was dried at 110℃ for 2 minutes to prepare a 10 μm thick coated dried product (resin film).

[0562] <Experimental Example 5> Evaluation of the lightfastness of coated dried products

[0563] For the coated dried material prepared above, the retention rate of absorbance at the maximum absorption wavelength (λmax) was calculated using the following (condition 1) to evaluate its lightfastness. Specifically, after measuring the absorbance at the maximum absorption wavelength (λmax) of the coated dried material, a lightfastness test was conducted after irradiating the coated dried material for 50 hours using the following (condition 2), and the absorbance at the maximum absorption wavelength (λmax) of the coated dried material after the lightfastness test was measured. The rate of change of absorbance at the maximum absorption wavelength (λmax) was calculated using the following formula. The results are shown in Table 3.

[0564] Absorbance change rate (%) = [(Absorbance at λmax after 50 hours of irradiation) / (Absorbance at λmax before 50 hours of irradiation)] × 100

[0565] (Condition 1)

[0566] For glass substrates with coated films, absorbance was measured using a UV1900 spectrophotometer (Shimadzu Corporation) at 1 nm wavelength intervals within the wavelength range of 300–1000 nm.

[0567] (Condition 2)

[0568] Apparatus: Xenon lamp weathering tester (Suga Test Instruments Co., Ltd.: XL75)

[0569] Illuminance: 10klx (40w / m²) 2 )

[0570] Test duration: 50 hours

[0571] Environment: 23℃, relative humidity 50%

[0572] <Experimental Example 6> Evaluation of the surface appearance of the coated dried product

[0573] The evaluation of the surface appearance of the coated dried material was conducted in the same manner as in <Experimental Example 4> above. The results are shown in Table 3.

[0574] <Examples 101-106 and 108>

[0575] The squaric acid compound and its content (parts by mass) used in Example 107 were changed to those shown in Table 3. Otherwise, the coated dried products of Examples 101-106 and 108 were prepared in the same manner as in Example 107. The thickness of each coated dried product was also the same as that of the coated dried product in Example 107.

[0576] The lightfastness and surface texture of each coated dried product were evaluated in the same manner as in Experimental Examples 5 and 6 above, and the results are shown in Table 3.

[0577] [Table 3]

[0578]

[0579] [Example D] Preparation of resin composition and fabrication and evaluation of filter

[0580] The resin composition (melt mixture) of the present invention was prepared using the squaric acid compound synthesized in Example A and the polycarbonate resin as resin 4. A filter was fabricated, and the presence of squaric acid compound precipitates in the obtained filter was evaluated.

[0581] <Examples 201-208>

[0582] In a stainless steel drum, 1 kg of polycarbonate resin (SD POLYCA301-30 (trade name), glass transition temperature 145–150 °C, manufactured by Sumika Polycarbonate) and 0.4 g of the squaric acid compound shown in Table 4 below were stirred for 1 hour to obtain a mixture. The obtained mixture was melt-kneaded for 1 minute at 280–320 °C using a biaxial compounding extruder (KZW15TW-45 / 60MG-NH (trade name), manufactured by Technobell) to obtain granular melt-kneaded material. After drying the obtained granular melt-kneaded material at 80 °C for 3 hours, it was molded using a press to produce molded sheets with a thickness of 0.15 mm.

[0583] <Experimental Example 7>

[0584] For each molded plate (polycarbonate film) produced, the presence or absence of precipitates of succinic acid compounds was visually observed.

[0585] -Evaluation Criteria-

[0586] A: No precipitates were found.

[0587] B: There is precipitate

[0588] [Table 4]

[0589] Squamous acid compounds Precipitation Example 201 A-4 A Example 202 A-12 A Example 203 A-19 A Example 204 A-28 A Example 205 B-2 A Example 206 B-11 A Example 207 B-12 A Example 208 B-20 A

[0590] [Example E] Preparation of resin composition and fabrication and evaluation of filter

[0591] The resin composition (melt mixture) of the present invention was prepared using the squaric acid compound synthesized in Example A and polyethylene terephthalate resin as resin 5. A filter was fabricated, and the presence of squaric acid compound precipitates in the obtained filter was evaluated.

[0592] <Examples 301-308>

[0593] A mixture was obtained by stirring 500g of polyethylene terephthalate (TRN-8550F (trade name), melting point 252℃, manufactured by TEIJIN LIMITED.) and 0.4g of the squaric acid compound shown in Table 5 below in a stainless steel rotary drum for 1 hour. The obtained mixture was melt-kneaded at 270℃ to obtain granular melt-knead. After drying the obtained granular melt-knead at 80℃ for 3 hours, it was molded using a press to produce molded plates with a thickness of 0.15mm.

[0594] <Experimental Example 8>

[0595] For each molded sheet (PET film) produced, the presence or absence of precipitates of succinic acid compounds was visually observed.

[0596] -Evaluation Criteria-

[0597] A: No precipitates were found.

[0598] B: There is precipitate

[0599] [Table 5]

[0600] Squamous acid compounds Precipitation Example 301 A-4 A Example 302 A-12 A Example 303 A-19 A Example 304 A-28 A Example 305 B-2 A Example 306 B-11 A Example 307 B-12 A Example 308 B-20 A

[0601] The following information can be obtained from the results in Tables 1 to 5.

[0602] It is known that comparative compounds C-1 to C-3, C-5, and C-6 do not exhibit solubility in organic solvents, while comparative compound C-4 does exhibit solubility in organic solvents. However, filters containing these comparative compounds do not possess both lightfastness and surface properties. This is believed to be because comparative compounds C-1 and C-4, although satisfying the requirement of being able to function as R in formula (1), 1 ~R 4The group contains no branched alkyl groups with more than 4 carbon atoms. Furthermore, it is believed that this is because the R group in formula (1) of compound C-2 is compared to the group containing the group. 1 ~R 4 All are phenyl groups, and none contain branched alkyl groups with more than four carbon atoms. This is believed to be because, although compound C-3 satisfies the condition of being able to function as R in formula (1),... 1 ~R 4 The group, but there are no branched alkyl groups with more than 4 carbon atoms, and in addition, there is a hydroxyl group as R. 5 and R 6 This is believed to be because, in the comparative compound C-5, even with an intramolecular metallocene structure, due to R in formula (4) 1 ~R 4 All are methyl groups and lack branched alkyl groups with more than 4 carbon atoms, resulting in poor solubility. This is believed to be because, comparing compounds C-6, the R in formulas (1) and (2)... 2 R 4 All are alkyl groups with 4 carbon atoms, but they are straight chains, not branched chains. In particular, among the C-1 to C-3 and C-5 compounds, they have low solubility and readily form associative compounds, resulting in very poor surface properties of the filters.

[0603] In contrast, the squaric acid compounds of the present invention, represented by formula (1) or (3) above, exhibit both extremely high absorption wavelengths in the 670–740 nm wavelength range and sufficient solubility in organic solvents. Furthermore, the filters of the present invention containing these squaric acid compounds exhibit excellent surface properties (with minimal deviations during film formation) regardless of their manufacturing method, becoming uniform membrane filters. Therefore, filters containing these squaric acid compounds can prevent incident light from reflecting into the filter, specifically absorb and block light in a particular wavelength range as unwanted wavelengths, and exhibit a higher absorbance variation rate (lightfastness) than the filters of the comparative examples. Additionally, it has been shown that even with high concentrations of the squaric acid compounds of the present invention, it is possible to achieve resin compositions free from precipitates, exudates, etc., caused by the aggregation (association) of the squaric acid compounds, and thus to create filters that specifically absorb and block light in a particular wavelength range.

[0604] Therefore, image display devices equipped with the filters of the present invention are expected to exhibit excellent lightfastness and spectral characteristics close to the relative visibility curve over a wide color reproduction range and especially at longer wavelengths. Furthermore, solid-state imaging elements incorporating the filters of the present invention exhibit excellent lightfastness and excellent color reproduction. Moreover, the filters of the present invention exhibit excellent transmittance in the 400–600 nm range and excellent oblique incidence characteristics without incident angle dependence, thus they are also preferably used as high-lightfast near-infrared cutoff filters.

[0605] The invention has been described in conjunction with its embodiments, but unless otherwise stated, we do not intend to limit the invention to any of the details described, and it is to be interpreted broadly without departing from the spirit and scope of the invention as shown in the appended claims.

[0606] This application claims priority based on Japanese Patent Application 2020-217497 filed on December 25, 2020, and Japanese Patent Application 2021-196123 filed on December 2, 2021, which are incorporated herein by reference as part of the description herein.

[0607] Symbol Explanation

[0608] 1-Upper polarizer, 2-Direction of absorption axis of upper polarizer, 3-Upper electrode substrate of liquid crystal unit, 4-Orientation control direction of upper electrode substrate of liquid crystal unit, 5-Liquid crystal layer, 6-Lower electrode substrate of liquid crystal unit, 7-Orientation control direction of lower electrode substrate of liquid crystal unit, 8-Lower polarizer, 9-Direction of absorption axis of lower polarizer, B-Backlight unit, 10-Liquid crystal display device.

Claims

1. A resin composition comprising a squarylium compound and a resin, the squarylium compound comprises at least one selected from a squarylium compound represented by formula (1) and a squarylium compound represented by formula (3), In the formula (1), R 1 ~R 4 represents an alkyl group having 1 to 40 carbon atoms optionally having an alkyl group, an acyl group, an alkoxy group, an amido group, or a sulfonamido group as a substituent, or an aryl group having 6 to 30 carbon atoms optionally having an alkyl group, an aryl group, an acyl group, an alkoxy group, an amido group, or a sulfonamido group as a substituent, and R 1 ~R 4 at least one of R 1 ~R 4 is an alkyl group, R 5 and R 6 represent -NR 9 R 10 , R 9 and R 10 represent a hydrogen atom, -COR N , -COOR N , -CON(R N )2 or -SO2R N , R N represents a hydrogen atom, or an alkyl group having 1 to 40 carbon atoms optionally having a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group as a substituent, or an aryl group having 6 to 30 carbon atoms optionally having a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group as a substituent, R 7 and R 8 represent an alkenyl group, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amido group, a sulfonamido group or a hydroxyl group as a substituent, in the case where a plurality of R 7 and R 8 are present, a plurality of R 7 or a plurality of R 8 may optionally be bonded to each other to form a condensed ring together with the benzene ring in the formula (1), m and n are integers of 0 to 3, wherein the squarylium compound represented by the formula (1) has at least one branched alkyl group having 4 or more carbon atoms, In the formula (3), Dye represents a structural portion in which n1 hydrogen atoms are removed from a squarylium compound represented by the following formula (4), Q 1 represents a group represented by the following formula (4M), n1 is an integer of 1 to 6, In the formula (4), R 1 ~R 4 represents an alkyl group having 1 to 40 carbon atoms optionally having an alkyl group, an acyl group, an alkoxy group, an amido group or a sulfonamido group as a substituent, or an aryl group having 6 to 30 carbon atoms optionally having an alkyl group, an aryl group, an acyl group, an alkoxy group, an amido group or a sulfonamido group as a substituent, wherein at least one of R 1 ~R 4 is an aryl group, at least one of R 1 ~R 4 is an alkyl group, R 5 and R 6 represent -NR 9 R 10 , R 9 and R 10 represent a hydrogen atom, -COR N , -COOR N , -CON(R N )2 or -SO2R N , R N represents a hydrogen atom, or an alkyl group having 1 to 40 carbon atoms optionally having a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group as a substituent, or an aryl group having 6 to 30 carbon atoms optionally having a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group as a substituent, R 7 and R 8 represent an alkenyl group, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amido group, a sulfonamido group or a hydroxyl group as a substituent, in the case of having a plurality of R 7 and R 8 , respectively, the plurality of R 7 or the plurality of R 8 may optionally be bonded to each other to form a condensed ring together with the benzene ring in the formula (1), and m and n are integers of 0 to 3. In the formula (4M), L represents a single bond or a divalent linking group not conjugated with Dye, R 1m ~R 9m represents a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amino group, or an amido group, M represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V, or Pt, represents a bonding portion to Dye.

2. The resin composition according to claim 1, wherein the squarylium compound represented by the formula (1) is represented by the following formula (2), In the formula (2), R 2 and R 4 represent an alkyl group, R 11 and R 12 represent an alkyl group, an aryl group, an acyl group, an alkoxy group, an amido group or a sulfonamido group, p and q are integers of 0 to 5, R 5 to R 8 , m and n have the same meanings as R 5 to R 8 , m and n of the formula (1), wherein the squarylium compound represented by the formula (2) has at least one branched alkyl group having 4 or more carbon atoms.

3. The resin composition according to claim 1 or 2, wherein R 2 , R 4 , R 9 , and at least one of R 10 comprises a branched alkyl group having 4 or more carbon atoms.

4. The resin composition according to claim 1, wherein the squarylium compound represented by the formula (4) is represented by the following formula (5), In the formula (5), R 2 and R 4 represent an alkyl group, R 11 and R 12 represent an alkyl group, an aryl group, an acyl group, an alkoxy group, an amido group or a sulfonamido group, p and q are integers of 0 to 5, R 5 to R 8 , m and n have the same meanings as R 5 to R 8 , m and n in the formula (4).

5. The resin composition according to claim 1 or 4, wherein the squarylium compound represented by the formula (4) or the squarylium compound represented by the formula (5) has at least one branched alkyl group having 4 or more carbon atoms.

6. The resin composition according to claim 1 or 4, wherein M of the formula (4M) is Fe.

7. The resin composition according to claim 1 or 2, wherein the glass transition temperature of the resin is -80°C to 200°C.

8. The resin composition according to claim 1 or 2, wherein the resin is at least one selected from polystyrene resin, cellulose acylate resin, poly(meth)acrylic acid-based resin, polyester resin, cyclic olefin resin, and polycarbonate resin.

9. The resin composition according to claim 1 or 2, comprising a solvent having a boiling point of 200°C or lower, in which the resin and the squarylium compound are dissolved.

10. A coated dried article obtained by coating and drying the resin composition according to claim 9 on a substrate.

11. A melt-kneaded product of the resin composition according to any one of claims 1 to 8.

12. An optical filter comprising the resin composition according to any one of claims 1 to 7, the coated dried article according to claim 10, or the melt-kneaded product according to claim 11.

13. The optical filter according to claim 12, which is in a film shape.

14. An image display device comprising the optical filter according to claim 12 or 13.

15. A solid-state imaging element comprising the optical filter according to claim 12 or 13.

16. A squarylium compound represented by the following formula (1) or the following formula (3), In the formula (1), R 1 ~R 4 represents an alkyl group having 1 to 40 carbon atoms optionally having an alkyl group, an acyl group, an alkoxy group, an amido group, or a sulfonamido group as a substituent, or an aryl group having 6 to 30 carbon atoms optionally having an alkyl group, an aryl group, an acyl group, an alkoxy group, an amido group, or a sulfonamido group as a substituent, and R 1 at least one of R 4 at least one of R 1 at least one of R 4 at least one of R 5 and R 6 represents -NR 9 R 10 , R 9 and R 10 represent a hydrogen atom, -COR N , -COOR N , -CON(R N )2 or -SO2R N , R N represents a hydrogen atom, or an alkyl group having 1 to 40 carbon atoms optionally having a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group as a substituent, or an aryl group having 6 to 30 carbon atoms optionally having a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group as a substituent, R 7 and R 8 represent an alkenyl group, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amido group, a sulfonamido group or a hydroxyl group as a substituent, and in the case where a plurality of R 7 and R 8 are present, a plurality of R 7 or a plurality of R 8 may optionally be bonded to each other to form a condensed ring together with the benzene ring in the formula (1), m and n are integers of 0 to 3, wherein the squarylium compound represented by the formula (1) has at least one branched alkyl group having 4 or more carbon atoms, In the formula (3), Dye represents a structural portion in which n1 hydrogen atoms are removed from a squarylium compound represented by the following formula (4), Q 1 represents a group represented by the following formula (4M), n1 is an integer of 1 to 6, In equation (4), R 1 ~R 4 R represents an alkyl group having 1 to 40 carbon atoms, optionally having an alkyl, acyl, alkoxy, amide, or sulfonamide as a substituent, or an aryl group having 6 to 30 carbon atoms, optionally having an alkyl, aryl, acyl, alkoxy, amide, or sulfonamide as a substituent, wherein R 1 ~R 4 At least one of them is aryl, R 1 ~R 4 At least one of them is an alkyl group, R 5 and R 6 Indicates -NR 9 R 10 R 9 and R 10 Represents hydrogen atom, -COR N -COOR N -CON(R) N )2 or -SO2R N R N R represents an alkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 30 carbon atoms, optionally having a halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, or acyl group as substituents, wherein the alkyl group has a hydrogen atom, or optionally has a halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, or acyl group as substituents. 7 and R 8 This refers to the alkenyl, halogen, alkyl, acyl, alkoxy, amide, sulfonamide, or hydroxyl groups that are substituents, each having multiple R groups. 7 and R 8 In the case of multiple R 7 or multiple R 8 The elements can be arbitrarily bonded together to form a fused ring with the benzene ring in formula (1), where m and n are integers from 0 to 3. In the formula (4M), L represents a single bond or a divalent linking group not conjugated with Dye, R 1m ~R 9m represents a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amino group, or an amido group, M represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, V, or Pt, represents a bonding portion to Dye.

17. The squarylium compound according to claim 16, wherein the squarylium compound represented by the formula (1) is represented by the following formula (2), In the formula (2), R 2 and R 4 represent an alkyl group, R 11 and R 12 represent an alkyl group, an aryl group, an acyl group, an alkoxy group, an amido group, or a sulfonamido group, p and q are integers of 0 to 5, R 5 to R 8 , m, and n have the same meanings as R 5 to R 8 , m, and n of the formula (1), wherein the squarylium compound represented by the formula (2) has at least one branched alkyl group having 4 or more carbon atoms.

18. The squarylium compound according to claim 16, wherein the squarylium compound represented by the formula (4) is represented by the following formula (5), In the formula (5), R 2 and R 4 represent an alkyl group, R 11 and R 12 represent an alkyl group, an aryl group, an acyl group, an alkoxy group, an amido group, or a sulfonamido group, p and q are integers of 0 to 5, R 5 to R 8 , m, and n have the same meanings as R 5 to R 8 , m, and n of the formula (4).

19. A method for producing a squaric acid compound, which produces a squaric acid compound represented by the following formula (1) by reacting a compound represented by the following formula (A) with squaric acid or a compound represented by the following formula (B), In the formula (A), the formula (B) and the formula (1), R 1 ~R 4 represents an alkyl group having 1 to 40 carbon atoms optionally having an alkyl group, an acyl group, an alkoxy group, an amido group or a sulfonamido group as a substituent, or an aryl group having 6 to 30 carbon atoms optionally having an alkyl group, an aryl group, an acyl group, an alkoxy group, an amido group or a sulfonamido group as a substituent, R 5 and R 6 represent -NR 9 R 10 , R 9 and R 10 represent a hydrogen atom, -COR N , -COOR N , -CON(R N )2 or -SO2R N , R N represents a hydrogen atom, or an alkyl group having 1 to 40 carbon atoms optionally having a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group as a substituent, or an aryl group having 6 to 30 carbon atoms optionally having a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group as a substituent, R 7 and R 8 represent an alkenyl group, a halogen atom, an alkyl group, an acyl group, an alkoxy group, an amido group, a sulfonamido group or a hydroxyl group as a substituent, in the case of having a plurality of R 7 and R 8 , a plurality of R 7 or a plurality of R 8 may optionally be bonded to each other to form a condensed ring together with the benzene ring in the formula (1), and m and n are integers of 0 to 3, wherein, In the compound represented by the formula (A) which reacts with the squarylium compound, at least one of R 1 and R 2 is an aryl group, and at least one of R 1 and R 2 is an alkyl group, a branched alkyl group having 4 or more carbon atoms, In the compounds represented by the formula (A) or the formula (B) which are allowed to react with each other, at least one of R 1 ~R 4 is an aryl group, and at least one of R 1 ~R 4 is an alkyl group, a branched alkyl group having a carbon atom number of 4 or more, The squaric acid compound represented by the formula (1) has at least one branched alkyl group having 4 or more carbon atoms.

Images