TWI848196B - Tetraazaporphyrin compound, ink composition, film, optical material, optical film, display surface film and display device - Google Patents

Abstract

A tetraazaporphyrin compound represented by the following general formula (1):

Description

Porphyrin tetrazolyl compound, ink composition, film, optical material, optical film, display surface film, and display device

The present invention relates to a tetrazoporphyrin compound, and an ink composition, film, optical material, optical film, display surface film, and display device containing the tetrazoporphyrin compound.

In recent years, white LEDs (Light Emitting Diodes) have begun to be used extensively as light sources for lighting and display devices.

There are several types of white LED light sources, such as the following: a light source that combines three LEDs that emit single colors, R (red), G (green), and B (blue), and mixes colors; a light source based on a combination of blue light from a blue-emitting LED and a yellow-emitting fluorescent body; and a light source based on a combination of a blue-emitting LED and green and red-emitting fluorescent bodies.

Among them, when a method of obtaining white light by combining blue light from a blue-emitting LED and a yellow-emitting fluorescent body, or a combination of a blue-emitting LED and green and red-emitting fluorescent bodies is used, the light includes light that shows orange in the region around 590nm and cyan in the region around 490nm in the spectrum of the obtained white light. It is known that if the luminous intensity of the light in this region is higher, the color purity will decrease.

In order to improve the above-mentioned problems, for example, Patent Document 1 discloses a color correction filter containing a tetrazopyrin compound having an absorption maximum in the wavelength region around 570-620 nm.

Prior art literature Patent Literature

Patent document 1: Japanese Patent No. 5706097

The industry believes that in order to suppress light in unnecessary wavelength regions caused by light sources, optical components, or external light reflection, it is effective to use pigment compounds that selectively absorb light in unnecessary wavelength regions.

The tetrazo porphyrin compound described in Patent Document 1 has an absorption maximum near a wavelength of 570-620 nm, but has a side absorption at a wavelength shorter than the maximum absorption wavelength, thus causing a problem of reducing color reproducibility (color purity) or brightness.

The present invention is completed in view of the above-mentioned actual situation, and its purpose is to provide a tetrazopyrin compound that reduces the side absorption on the wavelength side shorter than the maximum absorption wavelength near 570-620nm (near 550nm), an ink composition containing the tetrazopyrin compound, a film, an optical material, an optical film, a display surface film, and a display device.

One embodiment of the present invention provides a tetrazo porphyrin compound represented by the following general formula (1).

[Chemistry 1]

[In the general formula (1), any one of the two substituents of ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 is independently a group selected from the following Group A, and the other substituent is independently a group selected from the following Group B, and M is a divalent metal atom or metal oxide.

Group A: Hydrogen atoms and aliphatic hydrocarbon groups with 1 to 12 carbon atoms

Group B: A base represented by the following general formula (2)

(In the general formula (2), Ar represents an (n+1)-valent aromatic hydrocarbon group, Q represents -OH, -SH, or -NH ₂ . n is an integer of 1 to 7, and * represents the bonding position with the tetrazoporphyrin skeleton)].

In one embodiment of the present invention, a tetraazaporphyrin compound is provided, wherein in the aromatic hydrocarbon group of the above general formula (2), Q is bonded to at least one carbon atom adjacent to the carbon atom bonded to the tetraazaporphyrin skeleton.

One embodiment of the present invention provides an ink composition, which contains the tetrazo porphyrin compound of one embodiment of the present invention and a binder component.

One embodiment of the present invention provides a film containing at least one of the ink composition of one embodiment of the present invention and its cured product.

One embodiment of the present invention provides an optical material, which contains the tetrazopyrin compound of one embodiment of the present invention.

One embodiment of the present invention provides an optical film containing the tetrazopyrin compound of one embodiment of the present invention.

One embodiment of the present invention provides a display device having the optical film of one embodiment of the present invention.

One embodiment of the present invention provides an ink composition for a display surface film, which contains the tetrazo porphyrin compound of one embodiment of the present invention and an adhesive component.

One embodiment of the present invention provides a display surface film, which contains the tetrazopyrin compound of one embodiment of the present invention.

One embodiment of the present invention provides a display device having a display surface film of one embodiment of the present invention.

According to the implementation method of the present invention, a tetrazopyrin compound that reduces the side absorption on the wavelength side shorter than the maximum absorption wavelength near 570-620nm, an ink composition containing the tetrazopyrin compound, a film, an optical material, an optical film, a display surface film and a display device can be provided.

1: Support body

2: Adhesive layer or bonding layer

10: Display panel

11,13,17,19: Protective film

12,18: Polarizing element

14,16,16': Translucent adhesive layer

15: Display components

20: Backlight device

30: Surface functional layer

40: Display surface film

100: Image display device

FIG1 is a schematic cross-sectional view of an example of a display surface film in one embodiment of the present invention.

FIG2 is a schematic cross-sectional view of an example of a display device according to an embodiment of the present invention.

FIG3 is a diagram illustrating an example of the tetrazo porphyrin compound of the present invention.

Hereinafter, the implementation mode and examples of the present invention will be described with reference to the attached drawings, etc. However, the present invention can be implemented in many different forms and is not limited to the description of the following implementation modes and examples. In addition, in order to explain more clearly, the attached drawings sometimes show the width, thickness, shape, etc. of each part in a schematic manner compared with the actual form, but it is ultimately an example and does not limit the explanation of the present invention. In addition, in this specification and each figure, the same symbols are attached to the same elements as those described in the figures shown, and sometimes the detailed description is appropriately omitted. In addition, for the convenience of explanation, there are cases where the words "above" or "below" are used for explanation, but the up and down directions can also be reversed.

"In this specification, when a component of a certain component or a certain region is located "above (or below)" another component or another region, unless otherwise specified, it includes not only the situation where it is located directly above (or directly below) other components, but also the situation where it is located above (or below) other components, that is, another component is contained in the space above (or below) other components.

In the present invention, (meth)acrylic acid represents acrylic acid or methacrylic acid, (meth)acrylate represents acrylic acid or methacrylate, and (meth)acryloyl represents acrylyl or methacryloyl.

In addition, in this manual, the terms "board", "sheet", and "film" are just different names and do not distinguish each other. "Film surface (board surface, sheet surface)" refers to the surface that is consistent with the plane direction of the film-like (plate-like, sheet-like) component as the object when observing the film-like (plate-like, sheet-like) component as a whole and in a big picture.

In addition, in this manual, "~" indicating a numerical range is used in the following meaning, that is, it includes the numerical values recorded before and after it as the lower limit and upper limit.

The following describes in detail the tetrazoporphyrin compound, ink composition, film, optical material, optical film, display surface film, and display device of the present invention.

A. Tetrazo porphyrin compounds

The tetrazoporphyrin compound of one embodiment of the present invention is a tetrazoporphyrin compound represented by the following general formula (1).

[In the general formula (1), any one of the two substituents of ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 is independently a group selected from the following Group A, and the other substituent is independently a group selected from the following Group B, and M is a divalent metal atom or metal oxide.

Group A: Hydrogen atoms and aliphatic hydrocarbon groups with 1 to 12 carbon atoms

Group B: A base represented by the following general formula (2)

(In the general formula (2), Ar represents an (n+1)-valent aromatic hydrocarbon group, Q represents -OH, -SH, or -NH ₂ . n is an integer of 1 to 7, and * represents the bonding position with the tetrazoporphyrin skeleton)].

The tetrazoporphyrin compound represented by the general formula (1) has four isomers. One of the two substituents of ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 independently represents a group selected from the above group A, and the other substituent independently represents a group selected from the above group B. Therefore, if the group selected from the above group A is represented by G _A and the group selected from the above group B is represented by G _B , there are four isomers represented by the following formulas (1)-a to (1)-d.

The above general formula (1) means all four isomers including the four isomers having different positional relationships between the two substituents ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 . The tetraazaporphyrin compound of one embodiment of the present invention may contain only one of the isomers or two or more of them as a mixture.

Furthermore, in the tetrazoporphyrin compounds represented by the above general formula (1) and the following formulas (1)-a to (1)-d, the groups selected from the above group A may be the same or different, and the groups selected from the above group B may be the same or different.

[Chemistry 5]

(In general formula (1)-a to formula (1)-d, _GA represents a group selected from the above group A, _BB represents a group selected from the above group B, and M represents a divalent metal atom or metal oxide).

The group selected from the above group A is selected from hydrogen atoms and aliphatic hydrocarbon groups having 1 to 12 carbon atoms. Examples of aliphatic hydrocarbon groups having 1 to 12 carbon atoms include straight chain, branched chain or cyclic saturated or unsaturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and may also be a combination of straight chain or branched chain aliphatic hydrocarbon groups and cyclic aliphatic hydrocarbon groups.

烷基、金剛烷基等直鏈、支鏈或環狀之烷基。作為不飽和脂肪族烴基，例如可例舉：伸乙基、伸丙基、伸丁基、己烯基、辛烯基、十二烯基、環己烯基、乙炔基、第三丁基乙炔基等。 Examples of the aliphatic alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, 1,2-dimethylpropyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methylpentyl, 4-methyl-2-pentyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 3-methylhexyl, 5-methylhexyl, 2,4 -dimethylpentyl, cyclohexylmethyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, 2,5-dimethylhexyl, 2,5,5-trimethylhexyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, 4-ethyloctyl, n-undecyl, 1-methyldecyl, n-dodecyl, 1,3,5,7-tetramethyloctyl, cyclopentyl, 2-methylcyclopentyl, cyclohexyl, 4-methylcyclohexyl, 2,6-dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, nordecyl

Alkyl, adamantyl and other linear, branched or cyclic alkyl groups. Examples of the unsaturated aliphatic hydrocarbon group include ethylene, propylene, butylene, hexenyl, octenyl, dodecenyl, cyclohexenyl, ethynyl and t-butylethynyl.

As the group selected from the above group A, in terms of the thermal stability of the compound, preferably, it is an aliphatic alkyl group with 1 to 10 carbon atoms, more preferably, it is an aliphatic alkyl group with 3 to 10 carbon atoms, and further preferably, it is tert-butyl or cyclohexyl.

The group selected from the above group B is selected from a valence group represented by the following general formula (2).

(In the general formula (2), Ar represents an (n+1)-valent aromatic hydrocarbon group, Q represents -OH, -SH, or -NH ₂ . n is an integer of 1 to 7, and * represents the bonding position with the tetrazoporphyrin skeleton)].

In the general formula (2), Ar represents an aromatic hydrocarbon group with a valence of (n+1). Examples of the aromatic hydrocarbon group include benzene, naphthalene, biphenyl, etc. In terms of solubility, benzene is preferred.

n is an integer of 1 to 7, and in terms of the stability of the compound, it is preferably an integer of 1 to 4, and more preferably an integer of 1 to 2.

Q represents -OH, -SH or -NH ₂ . When n is 2 or more, Q in the general formula (2) may be the same or different.

Among them, in order to form an intramolecular hydrogen bond, Q is preferably -OH or -SH, and more preferably -OH.

In the aromatic hydrocarbon group of the general formula (2), the position where Q is bonded is not particularly limited. In order to easily reduce the side absorption, it is preferred that Q is bonded to at least one carbon atom adjacent to the carbon atom bonded to the tetraazaporphyrin skeleton in the aromatic hydrocarbon group of the general formula (2). In this case, Q may be bonded to two carbon atoms adjacent to the carbon atom bonded to the tetraazaporphyrin skeleton on both sides, but if Q is bonded to one adjacent carbon atom, another Q may be bonded to a position that is para-equidistant from the carbon atom bonded to the tetraazaporphyrin skeleton.

In the aromatic hydrocarbon group of the general formula (2), the position where Q is bonded is not particularly limited.

Examples of the monovalent group represented by the general formula (2) include 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 3,5-dihydroxyphenyl, 3,4,5-trihydroxyphenyl, 2,3,5,6-tetrahydroxyphenyl, 2-butylphenyl, 3-butylphenyl, 4-butylphenyl, 2,4-dibutylphenyl, 2,6-dibutylphenyl, 3,5-dihydroxyphenyl, 3,4,5-trihydroxyphenyl, 2,3,5,6-tetrahydroxyphenyl, Alkylphenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2,4-diaminophenyl, 2,6-diaminophenyl, 3,5-diaminophenyl, 2-hydroxy-1-naphthyl, 2-hydroxy-2-naphthyl, 2-alkynyl-1-naphthyl, 2-alkynyl-2-naphthyl, 2-amino-1-naphthyl, 2-amino-2-naphthyl, 2,3-dihydroxy-1-naphthyl, 2-hydroxybiphenyl, 2-alkynylbiphenyl, 2-aminobiphenyl, etc.

M represents a divalent metal atom or metal oxide. Examples of M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, Sn, etc.

Examples of the metal oxide represented by M include VO, MnO, TiO, etc.

In general formula (1), in terms of the stability of the compound, M is preferably at least one selected from the group consisting of Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO, and TiO, and is further preferably at least one selected from the group consisting of Cu, Ni, Pd, and VO, and is particularly preferably Cu or VO.

As the tetraazaporphyrin compound represented by the general formula (1), for example, the following case can be cited, that is, in the tetraazaporphyrin compound represented by the formula (1)-a to the formula (1)-d, the group _GA selected from the above group A and the group _GB selected from the above group B are the following combinations, but are not limited thereto.

Furthermore, in the following compounds (C1) to (C33), M in the general formula (1)-a to (1)-d represents one selected from the group consisting of Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO, and TiO, and the preferred one is the same as above.

In Table 1, for example, compound (C7) represents the following situation: in the tetrazoporphyrin compounds represented by the above formula (1)-a to formula (1)-d, 4 _GAs in one molecule are tert-butyl groups, 2 _BBs in one molecule are 2-hydroxyphenyl groups, and 2 _BBs in one molecule are 2,4-dihydroxyphenyl groups.

The tetrazopyrin compound represented by the general formula (1) can be prepared by referring to known methods. Examples of known preparation methods include: Japanese Patent Publication No. 11-11015, Japanese Patent Publication No. 11-43619, Japanese Patent Publication No. 11-100520, Japanese Patent Publication No. 11-116574, Japanese Patent Publication No. 11-130971, Japanese Patent Publication No. 2002-129052, Japanese Patent Publication No. 2006-321925, etc.

The tetrazoporphyrin compound represented by the above general formula (1) can be prepared, for example, by reacting the compounds represented by the following general formulas (3a) to (3d) with a metal or a metal salt in the presence of a base as required.

Examples of the metal or metal salt include metal halides and metal carboxylates. Examples of the base include ammonium molybdate, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, trialkylamines, ammonia, and the like.

(In general formulae (3a) to (3d), R ¹ to R ⁸ have the same meanings as in general formula (1)).

The tetrazoporphyrin compound represented by the general formula (1) obtained by the cyclization reaction of the compounds represented by the general formulas (3a) to (3d) is usually a mixture of isomers having different positional relationships between the two substituents of ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 .

Regarding the tetrazopyrin compound represented by the above general formula (1), in order to improve the color purity of the display device in the visible light range, the maximum absorption wavelength (λmax) in the wavelength range of 380nm~750nm in the absorption spectrum, that is, the minimum transmission wavelength in the wavelength range of 380nm~750nm in the transmission spectrum is preferably 570nm~620nm, more preferably 580nm~610nm, and further preferably 585nm~605nm. The maximum absorption wavelength or minimum transmission wavelength of the tetrazopyrin compound in the wavelength range of 380nm~750nm can be appropriately changed by changing the central metal or substituent of the tetrazopyrin compound.

In addition, in order to cut off only the unnecessary light of the display device, the half-value width of the maximum absorption wavelength or the minimum transmission wavelength in the wavelength range of 380nm~750nm is preferably 60nm~20nm, and more preferably 50nm~20nm.

Furthermore, the tetrazo porphyrin compound represented by the general formula (1) is preferably one in which the side absorption is reduced in the short wavelength range of 530nm to 570nm as follows. The short wavelength side is the side shorter than the maximum absorption wavelength (λmax) in the wavelength range of 380nm to 750nm in the absorption spectrum, i.e., the minimum transmission wavelength in the wavelength range of 380nm to 750nm in the transmission spectrum, i.e., the transmittance at the minimum transmission wavelength in the wavelength range of 540nm to 560nm is preferably 78% or more, more preferably 80% or more.

Furthermore, the transmittance of the tetrazo porphyrin compound represented by the above general formula (1) at the minimum transmission wavelength in the wavelength range of 380nm~750nm and the minimum transmission wavelength in the wavelength range of 530nm~570nm in the above transmission spectrum can be measured by the following method.

Specifically, first, 79 parts by mass of pentaerythritol triacrylate (e.g., trade name M305, manufactured by Toagosei Co., Ltd.), 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (e.g., trade name Irgacure 184, manufactured by BASF) and 296 parts by mass of methyl ethyl ketone as a solvent are mixed with 1 part by mass of the tetrazopyrin compound represented by the general formula (1) to prepare a spectroscopic composition. Then, the spectroscopic composition is coated on a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., "OA-10G") having a thickness of 0.7 mm using a rotary coater. Thereafter, heat drying is performed on a hot plate at 80°C for 3 minutes to obtain a coating film. The coating was irradiated with ultraviolet light at 254nm, equivalent to 500mJ/ ^cm2 , using an ultra-high pressure mercury lamp to obtain a cured film. Furthermore, the film thickness was adjusted so that the transmittance of the minimum transmission wavelength in the wavelength range of 380nm~750nm in the transmission spectrum became 40%. The transmission spectrum of the cured film was measured using the "microspectroscopy measurement device OSPSP200" manufactured by Olympus.

Regarding the tetraazaporphyrin compound represented by the general formula (1) of the present invention, any one of the substituents of ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 independently represents a group selected from a hydrogen atom and an aliphatic alkyl group having 1 to 12 carbon atoms, and the other substituent independently represents a monovalent group represented by the general formula (2) above, so that it has a maximum absorption wavelength near a wavelength of 570 to 620 nm, and the side absorption on the wavelength side shorter than the maximum absorption wavelength is reduced. Therefore, the tetraazaporphyrin compound represented by the general formula (1) of the present invention is a pigment compound that further selectively absorbs light in a desired wavelength region, that is, has a narrower absorption wavelength region and a higher wavelength selectivity. When the tetrazoporphyrin compound represented by the general formula (1) of the present invention is used, the decrease in color purity or brightness caused by the above-mentioned side absorption is suppressed, and the color purity or brightness is improved.

It is speculated that the side absorption at a wavelength shorter than the maximum absorption wavelength near 570-620nm is caused by the combination of tetrazoporphyrin compounds. In view of this, it is speculated that by making the tetrazoporphyrin compound represented by the general formula (1) of the present invention contain an aromatic hydrocarbon group having a polar group as one of the four substituents of ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 , the self-coalescence is suppressed due to its polarity and large volume, and the compatibility with the binder containing impurity atoms generally used for forming a coating film is improved, so that the compound is dispersed more uniformly, thereby reducing the side absorption near 550nm on the wavelength side shorter than the maximum absorption wavelength near 570~620nm.

Furthermore, when Q is bonded to at least one carbon atom adjacent to the carbon atom bonded to the tetraazaporphyrin skeleton in the aromatic hydrocarbon group of the general formula (2), a tendency to reduce the side absorption is particularly observed. The reason for this is presumably that the polar group such as the hydroxyl group substituted on the carbon atom adjacent to the carbon atom bonded to the tetraazaporphyrin skeleton in the aromatic hydrocarbon group interacts with the central metal M, thereby suppressing the vertical amplitude movement of the tetraazaporphyrin skeleton, which is a factor in the formation of the vibration energy level causing the side absorption (Figure 3). That is, it is speculated that the reason is that by substituting a polar group such as a hydroxyl group at the 2-position of the aromatic hydrocarbon ring, the configuration of the aromatic hydrocarbon ring is fixed in a form orthogonal to the plane of the tetraazaporphyrin skeleton, so that the polar group such as the hydroxyl group is located on the plane of the tetraazaporphyrin skeleton, thereby interacting with the central metal.

B. Ink composition

The ink composition of the present invention contains at least the tetrazoporphyrin compound of the present invention and a binder component.

The ink composition of the present invention can form a film or a molded body with reduced side absorption on the wavelength side shorter than the maximum absorption wavelength near 570-620nm and improved color purity or brightness by using the above-mentioned tetrazoporphyrin compound of the present invention in combination with a binder component.

The ink composition of the present invention contains at least the tetrazoporphyrin compound of the present invention and a binder component, and may also contain other components as needed.

Below, each component of the ink composition of the present invention is described in detail.

(Tetrazo porphyrin compound of the present invention)

The tetrazo porphyrin compound of the present invention contained in the ink composition of the present invention may be the same as that described above, and therefore, the description here is omitted.

The tetrazoporphyrin compound of the present invention can be used alone or in combination of two or more in the ink composition of the present invention. In addition, the tetrazoporphyrin compound of the present invention can be a single compound or a mixture of two or more positional isomers. The absorption peak positions of these positional isomers are usually not very different from each other, so even if they are a mixture, the peaks are relatively steep. If necessary, each positional isomer can be separated from the mixture of positional isomers, and one compound among the positional isomers can be used.

(Adhesive ingredients)

The ink composition of the present invention contains an adhesive component in order to impart film-forming properties, formability, and adhesion to the coated surface.

The adhesive component preferably contains at least a resin. The resin may be an adhesive or any one of a thermoplastic resin, a thermosetting resin, and a photocurable resin. The resin here is not limited to a macromolecular compound or a polymer, but may also be a low molecular compound or a monomer. In addition, it may also be particles of a synthetic resin such as a resin emulsion.

The adhesive component is preferably light-transmissive. When a film with a thickness of 3 μm is made using only the adhesive component, the transmittance in the visible light region is preferably 80% or more, and more preferably 84% or more. Furthermore, the above transmittance can be measured according to JIS K7361-1 (Test method for total light transmittance of plastic-transparent materials).

As adhesives, for example, there can be cited: acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives, ethylene-vinyl acetate adhesives, polyvinyl ethers, saturated amorphous polyesters, melamine resins and other adhesives.

In addition, examples of thermoplastic resins include acrylic resins such as poly(meth)acrylic acid, poly(meth)acrylate, polyacrylonitrile, and polyacrylamide; polystyrene resins; cellulose resins such as nitrocellulose, ethylcellulose, and triacetylcellulose; polyester resins such as polyethylene terephthalate; polycarbonate resins; thermoplastic urethane resins; modified olefin resins such as chlorinated polyethylene and chlorinated polypropylene; vinyl resins such as vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, and butyral resin, polyamide resins; polyimide resins; olefin resins such as cyclic polyolefins and polyolefins, etc.

In order to give sufficient hardness to the coating film, it is preferable to contain a curable adhesive component including a thermosetting resin or a light-curing resin. There is no particular limitation on the curable adhesive component, and previously known curable adhesive components can be appropriately used.

As the curable adhesive component, for example, a photocurable adhesive component or a thermosetting adhesive component can be used. The photocurable adhesive component includes a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, etc., and the thermosetting adhesive component includes a thermosetting resin that can be polymerized and cured by heating.

As a thermosetting adhesive, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst that can promote the thermosetting reaction may be further added. Examples of thermosetting functional groups include epoxy groups, cyclobutylene oxide, isocyanate groups, and ethylenic unsaturated bonds. As a thermosetting functional group, epoxy groups are preferably used. As specific examples of thermosetting adhesive components, for example, those described in International Publication No. 2012/144521 can be cited.

On the other hand, as a photocurable adhesive, a combination of a compound having one or more photocurable functional groups in one molecule and a photoinitiator is generally used. Such compounds and photoinitiators can be appropriately selected from previously known ones. As photocurable functional groups, free radical polymerizable groups containing ethylenic unsaturated bonds, cationic polymerizable epoxy groups, cyclobutylene oxides, etc. can be cited. As photocurable functional groups, groups containing ethylenic unsaturated bonds can be preferably used, and specifically, vinyl groups, (meth)acryloyl groups, etc. can be cited.

In order to increase the hardness, the number of photocurable functional groups in one molecule of the photocurable compound is preferably 2 or more, and more preferably 3 or more.

As the above-mentioned free radical polymerizable compound, in order to have a higher reactivity, a compound having a (meth)acryl group is preferred. It is preferred to use a compound having more than two (meth)acryl groups in one molecule, and oligomers having more than two (meth)acryl groups in the molecule such as (meth)acrylic acid urethane, polyester (meth)acrylate, (meth)acrylate epoxy, (meth)acrylate melamine, (meth)acrylate polyfluoroalkyl, silicone (meth)acrylate, etc., with a molecular weight of hundreds to thousands. In addition, it is also preferred to use a multifunctional (meth)acrylate polymer having more than two (meth)acryl groups on the side chain of an acrylate polymer. Among them, in order to improve the hardness, it is preferred to use a multifunctional (meth)acrylate monomer having more than two (meth)acryl groups in one molecule.

In addition, examples of resin emulsions include acrylic emulsions, styrene-acrylic emulsions, vinyl acetate emulsions, ethylene-vinyl acetate emulsions, etc.

Furthermore, when the film has a pattern and a photolithography step is used when forming the film, it is appropriate to use a photosensitive adhesive component with alkaline developability.

As the photosensitive adhesive component, there can be exemplified positive photosensitive adhesive components and negative photosensitive adhesive components. As the positive photosensitive adhesive component, there can be exemplified a system containing a compound containing an o-quinonediazide group as an alkali-soluble resin and a photosensitivity-imparting component, and as the alkali-soluble resin, there can be exemplified a polyimide precursor, etc.

As a negative photosensitive adhesive component, a system containing at least an alkali-soluble resin, a multifunctional monomer, and a photoinitiator is preferably used. Specific examples of the alkali-soluble resin, the multifunctional monomer, and the photoinitiator include those described in International Publication No. 2012/144521.

The tetraazaporphyrin compound of the present invention contains an aromatic hydrocarbon group having a polar group as one of the four substituents of ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 , thereby improving compatibility with a binder component containing a heteroatom, and can be suitably used in combination with a binder component containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. The tetraazaporphyrin compound of the present invention contains an aromatic hydrocarbon group having a polar group as the four substituents, and thus, even when combined with a radical polymerizable compound having two or more (meth)acryloyl groups in one molecule, the side absorption near 550 nm is suppressed, and therefore, a radical polymerizable compound having two or more (meth)acryloyl groups in one molecule can be suitably used as a binder component. In order to improve the hardness of the display surface, it is preferred that the ink composition for the display surface film described below contain a radical polymerizable compound having two or more (meth)acryl groups in one molecule as a binder component.

(Solvent)

The ink composition of the present invention may further contain a solvent. As the solvent used in the ink composition of the present invention, a solvent that can dissolve or disperse the above-mentioned tetrazoporphyrin compound of the present invention, the binder component and other components added as needed can be appropriately selected.

The solvent used in the ink composition of the present invention may be, for example: ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, ethyl acetate solvent; alcohol solvents such as methanol and ethanol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc., but are not limited thereto.

(Add any ingredients)

The ink composition of the present invention may also contain other light absorbing compounds and various additives as needed within the scope that does not harm the purpose of the present invention.

化合物、偶氮化合物、苯乙烯化合物、香豆素化合物、卟啉化合物、二苯并呋喃酮化合物、吡咯并吡咯二酮系化合物、若丹明化合物、

化合物、吡咯亞甲基化合物等。 As other light absorbing compounds, for example, compounds having the desired absorption in the visible light region can be cited, for example, squarylium compounds, anthraquinone compounds, phthalocyanine compounds, methine compounds, methine azo compounds,

Compounds, azo compounds, styrene compounds, coumarin compounds, porphyrin compounds, dibenzofuranone compounds, diketopyrrolopyrrole compounds, rhodamine compounds,

Compounds, pyrromethene compounds, etc.

The ink composition of the present invention may further include a compound having an absorption maximum in a wavelength region around 490 nm, for example.

Examples of additives include polymerization terminators, chain transfer agents, levelers, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, antistatic agents, fillers, etc. Additives may also include inorganic or organic microparticles for adjusting hardness and refractive index, antiglare agents, antifouling agents, flame retardants, antioxidants, light stabilizers, surface modifiers, etc.

(Ratio of ingredients in the composition)

In the ink composition of the present invention, the content of the tetrazoporphyrin compound of the present invention is not particularly limited, and can be appropriately selected according to the purpose. In order to improve the color purity of the display device by fully cutting off unnecessary light and allowing necessary light to pass, the content of the tetrazoporphyrin compound of the present invention is preferably in the range of 0.5-5 mass %, and further preferably in the range of 0.8-3 mass % relative to the total solid content of the composition. If the tetrazoporphyrin compound is too little, it may be difficult to obtain the required absorption of light in the unnecessary wavelength region. Furthermore, if the tetrazopyrin compound is too much, there is a risk that the coating properties such as adhesion to the support, surface roughness of the film, and coating hardness may become insufficient when the composition is applied to the support and dried, and then hardened. Furthermore, the solid components in the present invention are all components except the above-mentioned solvent, and also include multifunctional monomers that are liquid at 25°C.

The total content of the binder components is not particularly limited, and can be appropriately selected according to any added components. The total content of the binder components relative to the total solid content of the composition is preferably 80% by mass or more, more preferably 85% by mass or more, and can also be 95% by mass or more, and can also be 97% by mass or more. On the other hand, the upper limit is preferably 99.5% by mass or less, and more preferably 99.2% by mass or less.

Furthermore, when a solvent is contained in the composition, its content can be appropriately adjusted in terms of the dispersibility of the tetrazoporphyrin compound and the coating properties of the composition. The amount of the solvent relative to the total amount of the composition containing the solvent is usually preferably in the range of 65-95% by mass, and more preferably in the range of 75-88% by mass.

Furthermore, when the composition contains additives, the content is not particularly limited and can be appropriately selected according to the purpose.

When other light absorbing compounds are contained in the composition, their content is not particularly limited, as long as it is appropriately selected according to the purpose. Regarding the content of other light absorbing compounds, for example, it can be exemplified as: 0.5~5 mass % relative to the total solid content of the composition, and further in the range of 0.8~3 mass %.

(Manufacturing of the composition)

The method for preparing the composition is not particularly limited.

When using adhesives or thermoplastic resins as adhesive components, the tetrazoporphyrin compound of the present invention can be added to the adhesives or thermoplastic resins and mixed before use.

Alternatively, the following method can be cited: after adding a binder component and various additive components as needed to a solvent and mixing them, the tetrazo porphyrin compound of the present invention is added thereto and mixed.

C. Membrane

The membrane of one embodiment of the present invention contains at least one of the ink composition of one embodiment of the present invention and its cured product.

The film of one embodiment of the present invention contains at least one of the ink composition of one embodiment of the present invention and its cured product, and can selectively absorb wavelengths around 570-620nm, and the side absorption on the wavelength side shorter than the maximum absorption wavelength is reduced, and the color purity or brightness is improved.

The film of the present invention may have a pattern or may be a film without a pattern (flat film). In addition, the film of the present invention may be used in a state of being layered on a support or may be used after being peeled off from the support.

The film of the present invention can also be called a sheet or plate, and the film thickness can be appropriately adjusted according to the purpose. The film thickness can be less than 200μm, and further can be less than 150μm. Among them, in order to ensure the total light transmittance, the film of the present invention is preferably less than 100μm, more preferably less than 80μm, and further preferably less than 50μm. The lower limit of the film thickness is preferably more than 0.1μm, more preferably more than 0.2μm, and further preferably more than 0.3μm.

The film of the present invention contains the tetrazo porphyrin compound of the present invention, so when the film thickness is 3μm, the transmittance at a wavelength of 590nm is preferably less than 40%, more preferably less than 30%, and further preferably less than 20%.

Furthermore, regarding the transmittance of different thicknesses, the Lambert-Beer law can be used to calculate the conversion value based on the measured transmittance value at a certain thickness, and the calculated conversion value can be used as the transmittance of different thicknesses.

Specifically, according to the Lambert-Beer law, the transmittance T is Log ₁₀ (1/T) = kcb

(k=constant inherent to the substance, c=concentration, b=optical path length)

In the case of the transmittance of the membrane, if we assume that the density remains constant even if the membrane thickness changes, then c is also a constant. Therefore, the above formula can be expressed using the constant f as Log ₁₀ (1/T) = fb

(f=kc). Here, if the transmittance at a certain film thickness is known, the intrinsic constant f of each substance can be calculated. Therefore, if the formula T=1/10 ^{f. b} is used, and the intrinsic constant is substituted into f and the target film thickness is substituted into b, the transmittance at the required film thickness can be calculated.

Furthermore, the film of the present invention reduces the side absorption at the wavelength side shorter than the maximum absorption wavelength near 570-620nm (near 550nm) by containing the tetrazopyrin compound of the present invention. Specifically, for example, the ratio of transmittance _T2 (%) to transmittance _T1 (%) ( _T2 / _T1 ) is preferably 1.95 or more, more preferably 2.00 or more, the transmittance _T2 (%) is the transmittance at the minimum transmission wavelength in the range of 530nm-570nm, and the transmittance _T1 (%) is the transmittance at the minimum transmission wavelength in the range of 380nm-750nm in the transmission spectrum.

As a method for manufacturing a film according to one embodiment of the present invention, for example, a method including the following steps can be cited: using the ink composition according to one embodiment of the present invention to form a composition layer on a support; and further hardening the composition layer as needed.

The support is not particularly limited. In addition to supports made of materials such as glass, silicon, polycarbonate, polyester, polyacrylic acid, aromatic polyamide, polyamide imide, polyimide, cycloolefin polymer, and acylated cellulose, it can also be other optical components used in display devices.

As a method for applying the ink composition to the support, a known method can be appropriately selected and used. For example, there can be cited: gravure coating, reverse coating, doctor blade coating, dip coating, spray coating, air knife coating, rotary coating, roller coating, printing, dip-pull coating, curtain coating, die-mouth coating, casting, rod coating, extrusion coating, E-type coating and other coating methods, inkjet, nozzle jet and other jet-type printing, soft printing, screen printing, gravure printing, reverse offset printing, metal mask printing and other various printing methods, transfer methods using molds, etc., nano-imprinting methods, etc.

The composition layer applied on the support can be formed into a film by removing the solvent (drying) as needed.

As a step for hardening the above-mentioned composition layer, it is sufficient to select a known method such as applying at least one of heating and light irradiation to harden the adhesive component according to the curability of the adhesive component contained in the composition.

In addition, the support can be removed after the membrane is manufactured.

As one embodiment of the present invention, the method for manufacturing a film having a pattern may include the following steps: forming a pattern on the composition layer by photolithography or dry etching.

There is no particular limitation on photolithography or dry etching, and a known method can be appropriately selected and applied depending on the adhesive components contained in the composition.

As another method for manufacturing the film of one embodiment of the present invention, for example, a method of using the ink composition of one embodiment of the present invention and forming it can be cited. As a forming method, a known method can be appropriately selected and applied depending on the binder component contained in the ink composition.

In addition to being used in image display devices, the film of one embodiment of the present invention can also be used in various devices such as solid-state imaging devices such as CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor). In addition, the film of one embodiment of the present invention is suitable for use as an optical film for the purpose of transmitting or reflecting absorbed light to impart various effects, and can also be used for recording media that utilize selective wavelength absorption of heat, etc.

The film of one embodiment of the present invention is particularly suitable for the following display surface film because it can selectively absorb wavelengths near 570-620nm, and the side absorption on the wavelength side shorter than the maximum absorption wavelength near 570-620nm is reduced, and the color purity or brightness is improved.

D. Optical materials, optical films, optical filters and display surface films

The optical material of one embodiment of the present invention contains the tetrazopyrin compound of the present invention.

In addition, an optical film of one embodiment of the present invention contains the tetrazopyrin compound of the present invention.

In addition, an optical filter in one embodiment of the present invention contains the tetrazo porphyrin compound of the present invention.

In addition, the display surface film of one embodiment of the present invention contains the tetrazo porphyrin compound of the present invention.

The optical material of one embodiment of the present invention is a material that transmits or reflects or absorbs light to impart various effects.

As the optical material of the present invention, for example, a lens can be cited. As the lens, for example: plastic eyeglass lenses, sunglasses lenses, goggles, etc. can be cited.

Furthermore, as an optical material of the present invention, for example, an optical film can be cited, which is a film that transmits or reflects or absorbs light to impart various effects.

As optical films, specifically, for example, anti-reflection films, alignment films, etc. can be cited. In addition, the optical film includes, for example, an optical filter, which transmits only light with specified properties (for example, light in a specific wavelength range) in the incident light, and does not transmit other light. As the optical filter, for example, a specific wavelength absorption filter that selectively absorbs light in an unnecessary wavelength range, a color correction filter that adjusts the color tone, an ultraviolet cut-off filter, an infrared cut-off filter, etc. can be cited.

As an optical filter, it is used in display devices, lighting devices, window materials, etc.

The optical material of one embodiment of the present invention can be manufactured, for example, by forming the ink composition of one embodiment of the present invention, or can be manufactured in the same manner as the film of one embodiment of the present invention.

Furthermore, the optical film of one embodiment of the present invention including the optical filter of one embodiment of the present invention is preferably a film containing the above-mentioned one embodiment of the present invention.

The optical film of one embodiment of the present invention may be the same as the film of one embodiment of the present invention described above, and may include a support, and may further be laminated with an adhesive layer and a peelable peelable film. As the support, adhesive layer, and peelable peelable film, previously known structures may be appropriately selected and applied. As specific examples of adhesive layers and peelable peelable films, for example, those described in Japanese Patent Publication No. 2009-251511 may be cited.

The optical film of one embodiment of the present invention may also have other functional layers.

As other functional layers, for example, polarizing elements, protective films, anti-reflective layers, anti-glare layers, anti-fouling layers, anti-static layers, hard coating layers, adhesive layers, and bonding layers can be cited. As polarizing elements, protective films, anti-reflective layers, anti-glare layers, anti-fouling layers, anti-static layers, hard coating layers, adhesive layers, and bonding layers, previously known structures can be used.

Furthermore, in an optical film of one embodiment of the present invention, the film containing the tetrazoporphyrin compound of the present invention can be further endowed with other functions in addition to the function of selectively absorbing wavelengths around 570-620 nm. As other functions, for example, functions possessed by one or more layers selected from the group consisting of a protective film, an anti-reflection layer, an anti-glare layer, an anti-fouling layer, an anti-static layer, a hard coating layer, an adhesive layer, and a bonding layer can be cited.

The optical film of one embodiment of the present invention may also be a previously known optical film that contains the above-mentioned tetrazopyrin compound of the present invention. For example, an optical film in which at least one functional layer contains the above-mentioned tetrazopyrin compound of one embodiment of the present invention can be cited.

The optical film of one embodiment of the present invention may also be a display surface film for the observer-side surface of a display panel disposed in a display device.

The display surface film of one embodiment of the present invention contains the above-mentioned tetrazo porphyrin compound of the present invention, and usually has a required surface functional layer on the display surface, and further has an adhesive layer or a bonding layer on the support of the surface functional layer and the surface of the support opposite to the surface functional layer. As the surface functional layer, for example, at least one of a hard coating layer, an anti-reflection layer, an anti-glare layer, an anti-fouling layer, and an anti-static layer can be cited.

As a surface functional layer, if the surface hardness of the display surface film is to be improved and a coating film can be formed by a solution process, a layer having the function of a hard coating layer is preferred, and a layer having at least the functions of a hard coating layer and an anti-reflection layer is more preferred.

The hard coating layer is usually a layer that has a higher hardness than the protective film and at least imparts scratch resistance. The hard coating layer preferably has a hardness of "H" or above in the pencil hardness test (4.9N load) specified in JIS K5600-5-4 (1999).

The hard coating layer preferably has anti-reflection and anti-glare functions to improve visibility, and may also have anti-fouling and anti-static functions.

The hard coating layer may be appropriately selected from the hard coating layers used in the optical filters or optical films of the previously known display devices. As the hard coating layer, for example, reference may be made to the hard coating layers described in International Publication No. 2012/018087, International Publication No. 2011/065531, and Japanese Patent Publication No. 2018-51918, etc., and although the contents are incorporated into this specification, they are not limited thereto.

The anti-reflection layer, anti-glare layer, anti-fouling layer, and anti-static layer used as the surface functional layer may also be appropriately selected from previously known structures, such as Japanese Patent No. 6070195, Japanese Patent No. 6040936, Japanese Patent Unexamined No. 2017-21293, Japanese Patent Unexamined No. 2013-142817, Japanese Patent Unexamined No. 2011-90301, etc.

FIG1 is a schematic cross-sectional view showing an example of a display surface film of the present invention. As shown in FIG1 , the display surface film 40 can be exemplified as a laminate having a surface functional layer 30 on one side of a support 1 and an adhesive layer or bonding layer 2 on the other side of the support 1.

The display surface film of the present invention may also only include a film equivalent to the surface functional layer 30.

However, the surface functional layer 30 may be a single layer or a laminate including two or more layers. When the surface functional layer 30 is a laminate, for example, a hard coating layer and an anti-reflection layer including a low refractive index layer and a high refractive index layer are sequentially laminated.

The display surface film of the present invention may contain the tetrazoporphyrin compound of the present invention in any of the surface functional layer 30, the support 1, and the adhesive layer or the bonding layer 2, and may also contain the tetrazoporphyrin compound of the present invention in more than two layers.

The surface functional layer 30 containing the tetrazoporphyrin compound of the present invention, the support 1, and the adhesive layer or the bonding layer 2 can be manufactured in the same manner as the method for manufacturing the film of one embodiment of the present invention described above, by appropriately selecting the adhesive component and other further required components as needed.

The material of the support 1 is preferably selected from the thermoplastic resin in the binder component of the ink composition of one embodiment of the present invention, and can be the same as the support of the film of one embodiment of the present invention. As the support 1, triacetyl cellulose film (TAC film), cycloolefin polymer film, etc. are preferably used in terms of optical properties.

Furthermore, as the material of the adhesive layer or the bonding layer 2, it is sufficient to appropriately select and use an adhesive component with a higher transmittance in the visible light region from the adhesive component or the curable adhesive component in the adhesive component of the ink composition of one embodiment of the present invention.

In terms of being able to use existing manufacturing steps of the display device, the tetrazopyrin compound of the present invention is preferably contained in the surface functional layer 30.

The tetrazoporphyrin compound of the present invention can suppress the side absorption near 550nm even when combined with a radical polymerizable compound having two or more (meth)acryl groups in one molecule, and is suitable for use. Therefore, the display surface film of the present invention may include a layer or film containing the tetrazoporphyrin compound of the present invention and a cured product of a radical polymerizable compound having two or more (meth)acryl groups in one molecule, which can selectively absorb wavelengths near 570~620nm, and the side absorption on the wavelength side shorter than the maximum absorption wavelength near 570~620nm can be reduced, and the hardness of the display surface can be increased, and the scratch resistance can be improved.

In the display surface film of the present invention, the total thickness of the surface functional layer can be appropriately selected, for example, 10~150μm, but usually set to 20~100μm.

In the display surface film of the present invention, the thickness of the support body when it has a support body can be appropriately selected, for example, 10~150μm can be cited, but it is usually set to 20~100μm.

In the display surface film of the present invention, when there is an adhesive layer or a bonding layer, the thickness of the adhesive layer or the bonding layer can be appropriately selected, for example, 10~150μm, but usually set to 20~100μm.

Regarding the display surface film of the present invention, the transmittance in the visible light region (380nm~750nm) measured according to JISK7361-1 is preferably 80% or more, and more preferably 90% or more.

E. Display device

A display device according to one embodiment of the present invention is a display device having an optical film according to one embodiment of the present invention.

The optical film of the present invention can be used as long as it is assembled into a display device, and the assembly method is not particularly limited. It can be used as a display device without any particular limitation.

Examples of display elements constituting a display device include: a liquid crystal display element, an EL (inorganic EL, organic EL) display element, a plasma display element, an electronic paper display element, an LED display element (micro LED, etc.), and a display element using a quantum dot light emitting diode (QLED). That is, examples of display devices include: a liquid crystal display device, an EL (inorganic EL, organic EL) display device, a plasma display device, an electronic paper display device, an LED display device (micro LED, etc.), and a display device using a quantum dot light emitting diode (QLED).

Furthermore, in the case of a liquid crystal display device, a backlight needs to be arranged on the side opposite to the molded body of the display element.

Among them, in order to display colors with higher color purity, the display device of one embodiment of the present invention is preferably equipped with a display surface film containing the tetrazopyrin compound of the present invention.

An example of a display device according to one embodiment of the present invention is described using the attached diagram.

As shown in FIG. 2 , the image display device 100 mainly includes: a display panel 10 for displaying images, and a backlight device 20 disposed on the back side of the display panel 10. In this embodiment, the display panel 10 is a liquid crystal display panel, so the image display device 100 has the backlight device 20, but depending on the type of display panel (display element), it may not have the backlight device 20.

(Show Panel)

As shown in FIG2 , the display panel 10 has a structure in which a protective film 11, a polarizing element 12, a protective film 13, a light-transmitting adhesive layer 14, a display element 15, a light-transmitting adhesive layer 16, a protective film 17, a polarizing element 18, a light-transmitting adhesive layer 16', a protective film 19, and a surface functional layer 30 are sequentially stacked from the backlight device 20 side to the observer side. In FIG2 , the stack of the light-transmitting adhesive layer 16', the protective film 19, and the surface functional layer 30 is equivalent to the display surface film 40.

Furthermore, the display panel 10 only needs to have the display element 15 and does not need to have the protective film 11, etc.

The display element 15 in FIG. 2 is a liquid crystal display element. However, the display element 15 is not limited to a liquid crystal display element, and may be, for example, a display element as described above. The liquid crystal display element is provided with a liquid crystal layer, an alignment film, an electrode layer, a color filter, etc. between two glass substrates.

The protective film, polarizing element, and light-transmitting adhesive layer may be appropriately selected from previously known ones.

As the protective film, suitable examples include triacetyl cellulose film (TAC film), cycloolefin polymer film, etc.

As the light-transmitting adhesive layer, for example, an adhesive sheet such as OCA (Optical Clear Adhesive) is suitable, and a cured product of a liquid curable adhesive layer composition containing a polymerizable compound such as OCR (Optically Clear Resin) can also be used.

The surface functional layer 30 in FIG. 2 is a layer that is located on the surface of the display panel in the display device and is endowed with various functions. It can be one layer or two or more layers. The surface functional layer 30 is a layer having at least one function of a hard coating layer, an anti-reflection layer, an anti-glare layer, an anti-fouling layer, and an anti-static layer. The surface functional layer 30 can be the same as the surface functional layer described in the display surface film of one embodiment of the present invention.

(Backlight device)

The backlight device 20 illuminates the display panel 10 from the back side of the display panel 10. As the backlight device 20, a known backlight device can be used, and the backlight device 20 can be any of an edge-lit type or a direct-lit type backlight device. In addition, as the light source of the backlight, LED, CCFL (Cold Cathode Fluorescent Lamp) and the like can be cited. The backlight using quantum dots as the light source is easy to improve color reproducibility.

The display device of one embodiment of the present invention has an optical film containing the tetrazopyrin compound of the present invention, and is therefore suitable for use in a display device using a white LED as a light source. Among them, if an optical film containing the tetrazopyrin compound of the present invention is used, in order to appropriately remove orange light near 590nm and to correct the chromaticity of white light to a better one, it is better to use a display device with a white LED as a light source, that is, a method of obtaining white light by combining blue light from a blue-emitting LED with a yellow-emitting phosphor, or a method of obtaining white light by combining a blue-emitting LED with green and red-emitting phosphors.

The display device of one embodiment of the present invention is provided with an optical film containing the tetrazopyrin compound of the present invention. The optical film may not be the display surface film of one embodiment of the present invention.

There is no particular limitation on the placement of the optical film, as long as it is placed between the backlight source and the observer of the display device.

Regarding the display device of one embodiment of the present invention, for example, in FIG. 2 , the light-transmitting adhesive layer 16 and the protective film 17 between the display element 15 and the polarizing element 18 may be optical films containing the tetrazopyrin compound of the present invention, and the protective film 11, the protective film 13, or the light-transmitting adhesive layer 14 may also be optical films containing the tetrazopyrin compound of the present invention.

The display device of one embodiment of the present invention is not limited to the above examples, as long as a previously known structure is appropriately selected and adopted.

The display device of one embodiment of the present invention may also be provided with a touch panel, for example, on the side closer to the observer than the display panel 10 in FIG. 2, through, for example, a light-transmitting bonding layer.

Implementation example

The following is a detailed description of the present invention by showing an embodiment. The implementation of the present invention is not limited to the description.

(Synthesis Example 1: Synthesis of Compound 1)

(1) Synthesis of intermediate 1

40g of 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraazaporphyrin copper, 49.8g of N-bromosuccinimide (NBS), and 400g of dimethylformamide (DMF) were heated in 400ml of toluene at 75-80°C for 4 hours. The obtained reaction solution was concentrated, and 300ml of methanol was added to the concentrated reaction solution to precipitate the precipitate. The precipitate was filtered and dried to obtain 57g of the following intermediate 1 as a blue powder.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 915 (M+)

‧Element analysis values: CHN measured values (42.01%, 3.80%, 12.00%); theoretical values (41.97%, 3.96%, 12.24%)

(2) Synthesis of intermediate 2

Disperse 7.25g of the intermediate 1 obtained above, 4.93g of 2-methoxyphenylboronic acid, 3.44g of sodium carbonate, and 0.92g of tetrakis(triphenylphosphine)palladium in a mixed solvent of 70ml of toluene, 40ml of water, and 20ml of ethanol, and react at 80-85°C for 30 hours. After the reaction, cool the reaction solution to room temperature, add 200ml of toluene and 200ml of water, and extract the reaction product in toluene. The toluene solution is concentrated under reduced pressure to obtain a residue. The residue is dispersed with methanol, filtered and dried to obtain 7.3g of the following intermediate 2 as a blue powder.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 1024 (M+H), ‧Elemental analysis value: CHN measured value (70.10%, 6.33%, 11.00%); theoretical value (70.32%, 6.30%, 10.93%)

(3) Synthesis of compound 1

Disperse 6.5 g of the intermediate 2 obtained above in 65 ml of dichloromethane, add 41.1 g of a dichloromethane solution of boron tribromide (1 mol/L) dropwise at 5°C, stir for 1 hour at 5°C, and then stir for 3 hours at room temperature (25°C). Filter the precipitate, wash with 20 ml of dichloromethane and 200 ml of water, and dry to obtain 4.9 g of the following compound 1 as a blue powder.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 968 (M+)

‧Element analysis values: CHN measured values (69.30%, 5.75%, 11.50%); theoretical values (69.44%, 5.83%, 11.57%)

[Chemistry 10] Compound 1

(Synthesis Example 2: Synthesis of Compound 2)

(1) Synthesis of intermediate 3

In the synthesis of intermediate 2 in Synthesis Example 1, 4.93 g of 3-methoxyphenylboronic acid was used instead of 4.93 g of 2-methoxyphenylboronic acid. In the same manner as the synthesis of intermediate 2 in Synthesis Example 1, 8.0 g of the following intermediate 3 was obtained as a blue powder.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 1024 (M+H)

‧Element analysis values: CHN measured values (70.30%, 6.20%, 10.70%); theoretical values (70.32%, 6.30%, 10.93%)

(2) Synthesis of compound 2

In the above-mentioned Synthesis Example 1, except that 6.5 g of Intermediate 3 was used instead of 6.5 g of Intermediate 2, 5.5 g of the following Compound 2 was obtained as a blue powder in the same manner as the above-mentioned Synthesis Example 1.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 968 (M+), ‧Elemental analysis value: CHN measured value (69.48%, 5.80%, 11.61%); theoretical value (69.44%, 5.83%, 11.57%)

(Synthesis Example 3: Synthesis of Compound 3)

(1) Synthesis of intermediate 4

In the synthesis of intermediate 2 in Synthesis Example 1, 4.93 g of 4-methoxyphenylboronic acid was used instead of 4.93 g of 2-methoxyphenylboronic acid. In the same manner as the synthesis of intermediate 2 in Synthesis Example 1, 7.1 g of the following intermediate 4 was obtained as a blue powder.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 1024 (M+H), ‧Elemental analysis value: CHN measured value (70.29%, 6.35%, 10.80%); theoretical value (70.32%, 6.30%, 10.93%)

[Chemistry 13] Intermediate 4

(2) Synthesis of compound 3

In the above-mentioned Synthesis Example 1, except that 6.5 g of Intermediate 4 was used instead of 6.5 g of Intermediate 2, 5.0 g of the following Compound 3 was obtained as a blue powder in the same manner as the above-mentioned Synthesis Example 1.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 968 (M+), ‧Elemental analysis value: CHN measured value (69.38%, 5.86%, 11.62%); theoretical value (69.44%, 5.83%, 11.57%)

(Comparative Synthesis Example 1: Comparative Synthesis of Compound 1)

In a nitrogen atmosphere, add 1.34 g of 2-tert-butyl-2-cis-butenedinitrile and 0.33 g of cuprous chloride to 30 ml of n-pentanol, heat to 90°C, and then drop 1.52 g of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) into the mixture over 30 minutes. After the dropwise addition, stir the mixture at 125°C for 8 hours. After cooling the reaction mixture to room temperature, add 100 ml of methanol, and then drop 50 ml of water. Separate the precipitated solid by filtration. After dissolving the solid in toluene, it was purified by silica gel column chromatography [developing liquid: toluene/n-hexane (volume ratio: 2/1)] to obtain 0.82 g of the following comparative compound 1 as a blue solid.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 599 (M+), ‧Elemental analysis value: CHN measured value (64.06%, 6.71%, 18.67%); theoretical value (64.03%, 6.72%, 18.69%)

(Comparative Synthesis Example 2: Comparative Synthesis of Compound 2)

1.57 g of vanadium trichloride was added to 50 g of 1-pentanol, and 1.02 g of ammonia gas was introduced into the reaction solution at 20°C for 1 hour. After stirring at 20-30°C for 1 hour, 5.38 g of 2-tert-butyl-2-butene dinitrile was added, and stirring was continued at 125°C for 6 hours. Then, about 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water (the weight ratio of methanol to water was 1:1) was added and stirred. The precipitate was filtered, washed with methanol and dried to obtain 5.46 g of the following comparative compound 2 as a blue solid.

Based on the following analysis results, the obtained compound was confirmed to be the target compound.

‧MS (ESI) (m/z): 603 (M+), ‧Elemental analysis value: CHN measured value (63.70%, 6.71%, 18.55%) ; Theoretical value (63.67%, 6.60%, 18.56%)

(Implementation Example 1)

(1) Preparation of ink composition

With respect to 1 mass part of compound 1 of Synthesis Example 1, 79 mass parts of pentaerythritol triacrylate (trade name M305, manufactured by Toagosei Co., Ltd.), 3 mass parts of 1-hydroxycyclohexyl phenyl ketone (trade name Irgacure 184, manufactured by BASF), and 296 mass parts of methyl ethyl ketone as a solvent were mixed, and pressure filtration was performed to obtain ink composition 1 of Example 1.

(2) Film production

The ink composition obtained in (1) was applied to a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., "OA-10G") having a thickness of 0.7 mm using a rotary coater. The coating was then dried on a heating plate at 80°C for 3 minutes to obtain a coating. The coating was irradiated with ultraviolet light at 254 nm, which was equivalent to 500 mJ/ ^cm2 , using an ultra-high pressure mercury lamp to obtain a cured film, thereby producing the film 1 of Example 1.

Furthermore, the thickness of the cured film is adjusted in such a way that the transmittance of the minimum transmission wavelength in the wavelength range of 380nm~750nm in the transmission spectrum of the following cured film becomes 40%.

(Example 2~3)

(1) Preparation of ink composition

In Example 1 (1), compound 1 is changed to compound 2~3. In addition, the ink compositions 2~3 of Examples 2~3 are obtained in the same manner as in Example 1 (1).

(2) Film production

In Example 1 (2), ink composition 1 is changed to ink composition 2~3 respectively. Otherwise, films 2~3 of Examples 2~3 are obtained in the same manner as in Example 1 (2).

(Comparison example 1~2)

(1) Comparative preparation of ink compositions

In Example 1 (1), Compound 1 was changed to Comparative Compounds 1-2. In addition, the comparative ink compositions 1-2 of Comparative Examples 1-2 were obtained in the same manner as in Example 1 (1).

(2) Film production

In Example 1 (2), ink composition 1 is changed to comparative ink compositions 1-2 respectively. In addition, comparative films 1-2 of comparative examples 1-2 are obtained in the same manner as in Example 1 (2).

[evaluate]

<Measurement of transmission spectrum of cured film>

The transmission spectra of the films obtained in the examples and comparative examples were measured using the "microspectroscopy device OSP-SP200" manufactured by Olympus.

In the above transmission spectrum measured, the transmittance difference between the transmittance of the minimum transmission wavelength (the wavelength at which the transmittance takes the minimum value) in the wavelength range of 380nm~750nm and the transmittance of the baseline is calculated: △T(%), and the transmittance T _1/2 (%) when the △T(%) becomes 1/2 is calculated. In the valley of the minimum transmission wavelength of the given transmission spectrum, the half-value width is calculated based on the difference between the maximum wavelength from the baseline to the minimum wavelength that meets T _1/2 (%) (the width of the valley). Furthermore, the minimum transmission wavelength in the transmission spectrum is equivalent to the maximum absorption wavelength in the absorption spectrum.

[Table 2]

(Results summary)

It is clear that the films containing the tetraazaporphyrin compound of the present invention in Examples 1 to 3 have higher transmittance of the side absorption (550nm) and suppressed side absorption compared with the films containing the tetraazaporphyrin compound of Comparative Examples 1 and 2. It is believed that the reason is that in the films containing the tetraazaporphyrin compound of the present invention in Examples 1 to 3, the self-coordination of the tetraazaporphyrin compound of the present invention is suppressed and the side absorption is reduced. It is believed that the reason is that the tetraazaporphyrin compound of the present invention is not easy to self-coordinate due to having a specific substituent, and the compatibility with the light-curing adhesive component is improved, and the pigment molecules can be dispersed more evenly.

In addition, in Examples 1 to 3, the transmittance of the membrane containing the tetraazaporphyrin compound having a hydroxyl group at the adjacent position of the benzene ring in Example 1 is also higher at 550nm, and the side absorption is reduced. The reason is speculated that the hydroxyl group at the adjacent position of the benzene ring bonded to the tetraazaporphyrin skeleton interacts with the central metal, thereby suppressing the vertical amplitude movement of the tetraazaporphyrin skeleton. The vertical amplitude movement of the tetraazaporphyrin skeleton is a factor in the formation of the vibration energy level that causes the side absorption.

That is, it is believed that by substituting a hydroxyl group at the adjacent position of the benzene ring, the configuration of the benzene ring is fixed in a form orthogonal to the plane of the tetraazaporphyrin skeleton, so that the hydroxyl group is located on the plane of the tetraazaporphyrin skeleton, thereby interacting with the central metal (Figure 3).

1: Support body

2: Adhesive layer or bonding layer

30: Surface functional layer

40: Display surface film

Claims (10)

A tetrazoporphyrin compound represented by the following general formula (1): [In the general formula (1), any one of the two substituents of ^R1 and ^R2 , ^R3 and ^R4 , ^R5 and ^R6 , and ^R7 and ^R8 is independently a group selected from the following Group A, and the other substituent is independently a group selected from the following Group B, M is a divalent metal atom or a metal oxide, Group A: a hydrogen atom and an aliphatic hydrocarbon group having 1 to 12 carbon atoms; Group B: a monovalent group represented by the following general formula (2): [Chemical 2] (In the general formula (2), Ar represents an aromatic hydrocarbon group with a valence of (n+1), Q represents -OH, -SH, or -NH ₂ , n is an integer of 1 to 7, and * represents the bonding position with the tetrazoporphyrin skeleton)]. The tetraazaporphyrin compound of claim 1, wherein in the aromatic hydrocarbon group of the general formula (2), Q is bonded to at least one carbon atom adjacent to the carbon atom bonded to the tetraazaporphyrin skeleton. An ink composition comprising the tetrazoporphyrin compound of claim 1 or 2 and a binder component. A film comprising at least one of the ink composition of claim 3 and a cured product thereof. An optical material comprising the tetrazoporphyrin compound of claim 1 or 2. An optical film comprising the tetrazoporphyrin compound of claim 1 or 2. A display device comprising the optical film of claim 6. An ink composition for display surface film, comprising the tetrazoporphyrin compound of claim 1 or 2, and a binder component. A display surface film, comprising the tetrazoporphyrin compound of claim 1 or 2. A display device having a display surface film as claimed in claim 9.