JP2023101372A - Optical film, colored layer formation composition, dipyrromethene cobalt complex, and display device - Google Patents

Abstract

To provide an optical film which can selectively and effectively absorb light with wavelengths of about 500nm and is highly resistant to light.SOLUTION: The optical film includes a transparent base material and a colored layer, the colored layer containing a pigment (A), the pigment (A) containing a color material of which absorption maximum wavelength is in the range of 470-530 nm, and the color material being a dipyrromethene cobalt complex with the structure expressed by the following formula (I), in which R1 to R7 being applied to a predetermined reaction formula and the R1 to R7 being combined so that the free energy change before and after a reaction will be at least -1.0 kcal/mol.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an optical film, a composition for forming a colored layer, a dipyrromethene cobalt complex, and a display device.

2. Description of the Related Art A display device is often used in an environment where external light is incident regardless of whether it is indoors or outdoors. External light incident on the display device is reflected on the surface of the display device, causing deterioration in display quality such as deterioration in visibility. Among them, in a self-luminous display device such as an organic light-emitting display device, electrodes and many other metal wirings strongly reflect external light, and display quality is likely to deteriorate.
A circularly polarizing plate is sometimes arranged on the display surface side of the display device in order to reduce the reflectance of the display device and suppress the reflection of external light.

On the other hand, display devices are generally required to have high color purity. Color purity indicates the range of colors that can be displayed by a display device, and is also called color reproduction range. Therefore, high color purity means a wide color reproduction range and good color reproducibility. As means for improving color reproducibility, for example, a method of separating colors using a color filter for a white light source of a display device, and a method of correcting a monochromatic light source with a color filter to narrow the half value width are known.

For example, the following color filters have been proposed.
- A color correction filter containing a first colorant having a specific structure and a second colorant having an absorption maximum in the wavelength range of 420 to 480 nm (Patent Document 1).
- A display filter having a resin layer containing a dipyrromethene dye, the resin being a polyester resin having a specific glass transition temperature (Patent Document 2).
In Patent Document 1, the color purity of the white light source is improved by combining specific color materials. In Patent Document 2, the maximum absorption wavelength of the dye is set to an appropriate value according to the type of light source, and by selectively absorbing sub-emission from the light source, color purity is improved.

Japanese Patent No. 6142398 JP 2006-251076 A

However, when a circularly polarizing plate is used, the light emitted from the display device is also absorbed by the circularly polarizing plate, resulting in a large decrease in luminance. If the emission intensity is increased to compensate for the decrease in luminance, the life of the light emitting element is shortened. Furthermore, there is also the problem that it is difficult to reduce the thickness of the display device due to the thickness of the circularly polarizing plate itself.
In order to improve the color reproducibility of a display device using a conventional color filter, it is necessary to increase the thickness of the color filter and increase the density of the colorant, which can lead to poor display quality such as deterioration of pixel shape and viewing angle characteristics. I have a problem to lower it.

As a result of extensive studies, the present inventors have found that a dipyrromethene complex (dipyrromethene cobalt complex) whose central element is cobalt selectively and efficiently emits light with a wavelength of around 500 nm (external light or secondary light emission from the light source of the display device). It is effective for lower reflectance, higher brightness, thinner film, and improved color reproducibility of display devices. I have found that there are cases where it is not.

Therefore, the present invention provides an optical film that can selectively and efficiently absorb light with a wavelength of about 500 nm and has excellent light resistance, and an optical film that can selectively and efficiently absorb light with a wavelength of about 500 nm. A composition for forming a colored layer capable of forming a colored layer having excellent properties, a dipyrromethene cobalt complex capable of selectively and efficiently absorbing light in the vicinity of a wavelength of 500 nm and having excellent light resistance, and an optical film using the above-mentioned optical film The purpose is to provide a display device.

ここで、Ｒ^１～Ｒ^７は各々独立に、水素原子、ハロゲン原子、脂肪族炭化水素基、アルコキシ基、アルキルチオ基、芳香族炭化水素基、複素環基、水酸基、メルカプト基、ニトロ基、置換アミノ基、非置換アミノ基、シアノ基、スルホ基、エステル基、及びアシル基からなる群から選ばれた一価基を示す。

［２］前記ジピロメテンコバルト錯体は、Ｒ^５が水素原子である［１］の光学フィルム。
［３］前記ジピロメテンコバルト錯体は、Ｒ^１～Ｒ^４がアルキル基であり、Ｒ^１とＲ^２の炭素数の和が３以上かつＲ^３とＲ^４の炭素数の和が３以上である［１］又は［２］の光学フィルム。
［４］前記ジピロメテンコバルト錯体は、Ｒ^１～Ｒ^４のうち少なくとも１つが水素原子又はハロゲン原子である［１］又は［２］の光学フィルム。
［５］前記ジピロメテンコバルト錯体は、Ｒ^１及びＲ^３が各々独立に水素原子又はハロゲン原子であり、Ｒ^２及びＲ^４が各々独立に炭素数１～４のアルキル基であるか、又は、Ｒ^１及びＲ^３が各々独立に炭素数１～４のアルキル基であり、Ｒ^２及びＲ^４が各々独立にハロゲン原子である［４］の光学フィルム。
［６］前記ジピロメテンコバルト錯体は、下記式（Ｉ－１）で表される構造を有し、かつアセトン溶液のモル吸光係数が１９００００Ｌ／（ｍｏｌ・ｃｍ）以上である［１］～［５］のいずれかに記載の光学フィルム。

ここで、Ｒ^１～Ｒ^５は前記の通りであり、Ｒ^８及びＲ^９は各々独立に炭素数１～６のアルキル基を示す。
［７］前記ジピロメテンコバルト錯体は、Ｒ^８及びＲ^９が各々独立にメチル基又はエチル基である［６］の光学フィルム。
［８］色素（Ａ）と、光重合性化合物（Ｂ）と、光重合開始剤（Ｃ）とを含有し、
前記色素（Ａ）は、吸収極大波長が４７０～５３０ｎｍの範囲内にある色材を含有し、
前記色材は、下記式（Ｉ）で表される構造を有するジピロメテンコバルト錯体であって、前記式（Ｉ）中のＲ^１～Ｒ^７を下記反応式（ＩＩ）に当てはめ、量子化学計算プログラムＧａｕｓｓｉａｎ１６を用い、計算手法Ｂ３ＬＹＰ、基底関数６－３１Ｇ（ｄ，ｐ）（ただし、周期表においてＫｒより原子番号が大きな元素には基底関数ＬａｎＬ２ＤＺを割り当てる）にて計算した反応前後の自由エネルギー変化が－１．０ｋｃａｌ／ｍｏｌ以上となるようにＲ^１～Ｒ^７が組み合わされたジピロメテンコバルト錯体を含有する、着色層形成用組成物。

ここで、Ｒ^１～Ｒ^７は各々独立に、水素原子、ハロゲン原子、脂肪族炭化水素基、アルコキシ基、アルキルチオ基、芳香族炭化水素基、複素環基、水酸基、メルカプト基、ニトロ基、置換アミノ基、非置換アミノ基、シアノ基、スルホ基、エステル基、及びアシル基からなる群から選ばれた一価基を示す。

［９］前記ジピロメテンコバルト錯体は、Ｒ^５が水素原子である［８］の着色層形成用組成物。
［１０］前記ジピロメテンコバルト錯体は、Ｒ^１～Ｒ^４がアルキル基であり、Ｒ^１とＲ^２の炭素数の和が３以上かつＲ^３とＲ^４の炭素数の和が３以上である［８］又は［９］の着色層形成用組成物。
［１１］前記ジピロメテンコバルト錯体は、Ｒ^１～Ｒ^４のうち少なくとも１つが水素原子又はハロゲン原子である［８］又は［９］の着色層形成用組成物。
［１２］前記ジピロメテンコバルト錯体は、Ｒ^１及びＲ^３が各々独立に水素原子又はハロゲン原子であり、Ｒ^２及びＲ^４が各々独立に炭素数１～４のアルキル基であるか、又は、Ｒ^１及びＲ^３が各々独立に炭素数１～４のアルキル基であり、Ｒ^２及びＲ^４が各々独立にハロゲン原子である［１１］の着色層形成用組成物。
［１３］前記ジピロメテンコバルト錯体は、下記式（Ｉ－１）で表される構造を有し、かつアセトン溶液のモル吸光係数が１９００００Ｌ／（ｍｏｌ・ｃｍ）以上である［８］～［１２］のいずれかに記載の着色層形成用組成物。

ここで、Ｒ^１～Ｒ^５は前記の通りであり、Ｒ^８及びＲ^９は各々独立に炭素数１～６のアルキル基を示す。
［１４］前記ジピロメテンコバルト錯体は、Ｒ^８及びＲ^９が各々独立にメチル基又はエチル基である［１３］の着色層形成用組成物。
［１５］非重合性添加剤（Ｄ）をさらに含有する［８］～［１４］のいずれかの着色層形成用組成物。
［１６］透明基材と、前記透明基材の少なくとも一方面側に積層された着色層とを備え、
前記着色層は、［８］～［１５］のいずれかの着色層形成用組成物の硬化物である、光学フィルム。
［１７］下記式（Ｉ－１）で表される構造を有し、かつアセトン溶液のモル吸光係数が１９００００Ｌ／（ｍｏｌ・ｃｍ）以上である、ジピロメテンコバルト錯体。

ここで、Ｒ^１～Ｒ^５は各々独立に、水素原子、ハロゲン原子、脂肪族炭化水素基、アルコキシ基、アルキルチオ基、芳香族炭化水素基、複素環基、水酸基、メルカプト基、ニトロ基、置換アミノ基、非置換アミノ基、シアノ基、スルホ基、エステル基、及びアシル基からなる群から選ばれた一価基を示し、Ｒ^８及びＲ^９は各々独立に炭素数１～６のアルキル基を示す。
［１８］Ｒ^８及びＲ^９が各々独立にメチル基又はエチル基である［１７］のジピロメテンコバルト錯体。
［１９］Ｒ^５が水素原子である［１７］又は［１８］のジピロメテンコバルト錯体。
［２０］Ｒ^１～Ｒ^４がアルキル基であり、Ｒ^１とＲ^２の炭素数の和が３以上かつＲ^３とＲ^４の炭素数の和が３以上である［１７］～［１９］のいずれかのジピロメテンコバルト錯体。
［２１］Ｒ^１～Ｒ^４のうち少なくとも１つが水素原子又はハロゲン原子である［１７］～［１９］のいずれかのジピロメテンコバルト錯体。
［２２］Ｒ^１及びＲ^３が各々独立に水素原子又はハロゲン原子であり、Ｒ^２及びＲ^４が各々独立に炭素数１～４のアルキル基であるか、又は、Ｒ^１及びＲ^３が各々独立に炭素数１～４のアルキル基であり、Ｒ^２及びＲ^４が各々独立にハロゲン原子である［２１］のジピロメテンコバルト錯体。
［２３］アセトン溶液の吸収極大波長が４７０～５３０ｎｍである［１７］～［２２］のいずれかのジピロメテンコバルト錯体。
［２４］［１］～［７］のいずれかの光学フィルムを備える、表示装置。
［２５］［１６］の光学フィルムを備える、表示装置。 The present invention has the following aspects.
[1] A transparent substrate and a colored layer laminated on at least one side of the transparent substrate,
The colored layer contains a dye (A),
The dye (A) contains a coloring material having a maximum absorption wavelength within the range of 470 to 530 nm,
The coloring material is a dipyrromethene cobalt complex having a structure represented by the following formula (I), wherein R ¹ to R ⁷ in the formula (I) are applied to the following reaction formula (II), and quantum chemical Free energies before and after the reaction calculated using the calculation program Gaussian16, using the calculation method B3LYP and basis functions 6-31G(d, p) (however, elements with atomic numbers greater than Kr in the periodic table are assigned basis functions LanL2DZ). An optical film containing a dipyrromethene cobalt complex in which R ¹ to R ⁷ are combined such that the change is −1.0 kcal/mol or more.

Here, each of R ¹ to R ⁷ independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a nitro group, a substituted It represents a monovalent group selected from the group consisting of amino groups, unsubstituted amino groups, cyano groups, sulfo groups, ester groups and acyl groups.

[2] The optical film of [1], wherein in the dipyrromethene-cobalt complex, ^R5 is a hydrogen atom.
[3] In the dipyrromethene-cobalt complex, R ¹ to R ⁴ are alkyl groups, the sum of the carbon numbers of R ¹ and R ² is 3 or more, and the sum of the carbon numbers of R ³ and R ⁴ is 3 or more. The optical film of [1] or [2].
[4] The optical film of [1] or [2], wherein at least one of R ¹ to R ⁴ in the dipyrromethene-cobalt complex is a hydrogen atom or a halogen atom.
[5] In the dipyrromethene cobalt complex, R ¹ and R ³ are each independently a hydrogen atom or a halogen atom, and R ² and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, or , R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, and R ² and R ⁴ are each independently a halogen atom.
[6] The dipyrromethene cobalt complex has a structure represented by the following formula (I-1) and has a molar absorption coefficient of 190000 L/(mol cm) or more in acetone solution [1] to [ 5], the optical film according to any one of the above.

Here, R ¹ to R ⁵ are as defined above, and R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 6 carbon atoms.
[7] The optical film of [6], wherein in the dipyrromethene cobalt complex, ^R8 and ^R9 are each independently a methyl group or an ethyl group.
[8] Containing a dye (A), a photopolymerizable compound (B), and a photopolymerization initiator (C),
The dye (A) contains a coloring material having a maximum absorption wavelength within the range of 470 to 530 nm,
The coloring material is a dipyrromethene cobalt complex having a structure represented by the following formula (I), wherein R ¹ to R ⁷ in the formula (I) are applied to the following reaction formula (II), and quantum chemical Free energies before and after the reaction calculated using the calculation program Gaussian16, using the calculation method B3LYP and basis functions 6-31G(d, p) (however, elements with atomic numbers greater than Kr in the periodic table are assigned basis functions LanL2DZ). A colored layer-forming composition containing a dipyrromethene-cobalt complex in which R ¹ to R ⁷ are combined so that the change is −1.0 kcal/mol or more.

Here, each of R ¹ to R ⁷ independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a nitro group, a substituted It represents a monovalent group selected from the group consisting of amino groups, unsubstituted amino groups, cyano groups, sulfo groups, ester groups and acyl groups.

[9] The composition for forming a colored layer according to [8], wherein ^R5 is a hydrogen atom in the dipyrromethene-cobalt complex.
[10] In the dipyrromethene-cobalt complex, R ¹ to R ⁴ are alkyl groups, the sum of the carbon numbers of R ¹ and R ² is 3 or more, and the sum of the carbon numbers of R ³ and R ⁴ is 3 or more. A composition for forming a colored layer according to [8] or [9].
[11] The composition for forming a colored layer according to [8] or [9], wherein at least one of R ¹ to R ⁴ in the dipyrromethene-cobalt complex is a hydrogen atom or a halogen atom.
[12] In the dipyrromethene cobalt complex, R ¹ and R ³ are each independently a hydrogen atom or a halogen atom, and R ² and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, or , R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, and R ² and R ⁴ are each independently a halogen atom.
[13] The dipyrromethene-cobalt complex has a structure represented by the following formula (I-1) and has a molar extinction coefficient of 190000 L/(mol cm) or more in acetone solution [8]-[ 12], the composition for forming a colored layer according to any one of above.

Here, R ¹ to R ⁵ are as defined above, and R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 6 carbon atoms.
[14] The composition for forming a colored layer according to [13], wherein in the dipyrromethene cobalt complex, R ⁸ and R ⁹ are each independently a methyl group or an ethyl group.
[15] The composition for forming a colored layer according to any one of [8] to [14], further containing a non-polymerizable additive (D).
[16] A transparent substrate and a colored layer laminated on at least one side of the transparent substrate,
The optical film, wherein the colored layer is a cured product of the composition for forming a colored layer according to any one of [8] to [15].
[17] A dipyrromethene cobalt complex having a structure represented by the following formula (I-1) and having a molar extinction coefficient in acetone solution of 190000 L/(mol·cm) or more.

Here, R ¹ to R ⁵ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a nitro group, a substituted a monovalent group selected from the group consisting of an amino group, an unsubstituted amino group, a cyano group, a sulfo group, an ester group and an acyl group, wherein each of R ⁸ and R ⁹ is independently an alkyl group having 1 to 6 carbon atoms; indicates
[18] The dipyrromethene cobalt complex of [17], wherein ^R8 and ^R9 are each independently a methyl group or an ethyl group.
[19] The dipyrromethene cobalt complex of [17] or [18], wherein ^R5 is a hydrogen atom.
[20] R ¹ to R ⁴ are alkyl groups, the total number of carbon atoms of R ¹ and R ² is 3 or more, and the total number of carbon atoms of R ³ and R ⁴ is 3 or more [17] to [19] The dipyrromethene cobalt complex of any one of
[21] The dipyrromethene cobalt complex of any one of [17] to [19], wherein at least one of R ¹ to R ⁴ is a hydrogen atom or a halogen atom.
[22] R ¹ and R ³ are each independently a hydrogen atom or a halogen atom, R ² and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ³ are each independently The dipyrromethene cobalt complex of [21], wherein each of R ² and R ⁴ is independently an alkyl group having 1 to 4 carbon atoms and each is independently a halogen atom.
[23] The dipyrromethene cobalt complex of any one of [17] to [22], which has an acetone solution absorption maximum wavelength of 470 to 530 nm.
[24] A display device comprising the optical film of any one of [1] to [7].
[25] A display device comprising the optical film of [16].

According to the present invention, an optical film that can selectively and efficiently absorb light with a wavelength of about 500 nm and has excellent light resistance, can selectively and efficiently absorb light with a wavelength of about 500 nm, and has a light resistance A composition for forming a colored layer capable of forming a colored layer having excellent properties, a dipyrromethene cobalt complex capable of selectively and efficiently absorbing light in the vicinity of a wavelength of 500 nm and having excellent light resistance, and an optical film using the above-mentioned optical film A display device can be provided.

1 is a cross-sectional view of an optical film according to one embodiment of the present invention; FIG. FIG. 4 is a cross-sectional view of an optical film according to another embodiment of the invention; FIG. 4 is a cross-sectional view of an optical film according to another embodiment of the invention; FIG. 4 is a cross-sectional view of an optical film according to another embodiment of the invention; FIG. 4 is a cross-sectional view of an optical film according to another embodiment of the invention; FIG. 4 is a cross-sectional view of an optical film according to another embodiment of the invention; FIG. 4 is a cross-sectional view of an optical film according to another embodiment of the invention; FIG. 4 is a cross-sectional view of an optical film according to another embodiment of the invention;

[Optical film]
An optical film according to one embodiment of the present invention will be described in detail below with reference to FIG.

As shown in FIG. 1, the optical film 1 has a colored layer 10, a transparent substrate 20, and a functional layer 30. As shown in FIG. The functional layer 30 has a low refractive index layer 31 and a hard coat layer 32 . That is, the optical film 1 has a transparent substrate 20 located on one side of the colored layer 10, and the colored layer 10, the transparent substrate 20, the hard coat layer 32, and the low refractive index layer 31 are laminated in this order. It is a laminated body.

The thickness of the optical film 1 is, for example, preferably 10 to 140 μm, more preferably 15 to 120 μm, even more preferably 20 to 100 μm. The intensity|strength of the optical film 1 can be improved more as the thickness of the optical film 1 is more than the said lower limit. When the thickness of the optical film 1 is equal to or less than the above upper limit, the optical film 1 can be made lighter, which is advantageous for thinning the display device.
Each layer constituting the optical film 1 will be described below.

≪Colored layer≫
The colored layer 10 contains a dye (A).
In a preferred embodiment, the colored layer 10 is a cured product of the colored layer-forming composition of the present invention. The colored layer-forming composition of the present invention contains a dye (A), a photopolymerizable compound (B), and a photopolymerization initiator (C). When the colored layer 10 is a cured product of the composition for forming a colored layer of the present invention, the colored layer 10 contains a dye (A) and a polymer of a photopolymerizable compound (B).
The colored layer 10 and the colored layer-forming composition of the present invention may further contain a non-polymerizable additive (D). The colored layer-forming composition of the present invention may further contain a solvent (E).

The thickness of the colored layer 10 is preferably 0.5 to 10 μm, for example. Color purity can be improved as the thickness of the colored layer 10 is more than the said lower limit, and both color purity and luminance efficiency can be compatible. When the thickness of the colored layer 10 is equal to or less than the above upper limit, it is advantageous for thinning the display device.
The thickness of the colored layer 10 is obtained by observing a cross section of the optical film 1 in the thickness direction with a microscope or the like.

<Dye (A)>
The dye (A) contains a coloring material having a maximum absorption wavelength within the range of 470 to 530 nm (hereinafter also referred to as "first coloring material").
When the maximum absorption wavelength of the first colorant is equal to or greater than the above lower limit, it is difficult to reduce the luminance of blue light emission. When the maximum absorption wavelength of the first coloring material is equal to or less than the above upper limit, it is difficult to reduce the luminance of green light emission. Therefore, it is easy to achieve both color purity and luminance efficiency by controlling the absorption wavelength and absorption intensity.

The half width of the absorption spectrum of the first coloring material is preferably 15 to 30 nm, more preferably 15 to 25 nm. When the half width of the absorption spectrum of the first coloring material is within the above numerical range, it is easy to achieve both color purity and luminance efficiency.

The first colorant contains a specific dipyrromethene cobalt complex (hereinafter also referred to as "complex (I)").
Complex (I) has a structure represented by the following formula (I), and the change in free energy before and after the reaction calculated by applying R ¹ to R ⁷ in formula (I) to the following reaction formula (II). (hereinafter also referred to as "ΔG") is -1.0 kcal/mol or more, and R ¹ to R ⁷ are combined. Even if it has a structure represented by formula (I), a compound having a ΔG of less than −1.0 kcal/mol does not correspond to complex (I).

Here, each of R ¹ to R ⁷ independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a nitro group, a substituted It represents a monovalent group selected from the group consisting of amino groups, unsubstituted amino groups, cyano groups, sulfo groups, ester groups and acyl groups.
When a monovalent group has carbon atoms (aliphatic hydrocarbon groups, alkoxy groups, alkylthio groups, aromatic hydrocarbon groups, heterocyclic groups, substituted amino groups, ester groups, acyl groups, etc.), the monovalent group is substituted. You may have a group.

Reaction formula (II) is a reaction formula between boron dipyrromethene represented by the following formula (III) and singlet oxygen. ΔG before and after the reaction between boron dipyrromethene and singlet oxygen correlates with ΔG before and after the reaction between complex (I) and singlet oxygen. By calculating ΔG using boron dipyrromethene having the same substituents as R ¹ to R ⁷ in complex (I) as an alternative structure, the structure itself of the dipyrromethene cobalt complex, which has a large number of electrons and requires a large calculation load, can be obtained. It is possible to calculate ΔG in a shorter time than calculation using the structure.

ΔG is calculated using the quantum chemical calculation program Gaussian16, the calculation method B3LYP, and the basis functions 6-31G (d, p) (however, elements with atomic numbers larger than Kr in the periodic table are assigned basis functions LanL2DZ). value. More specifically, using the quantum chemistry calculation program Gaussian16, calculation method B3LYP, basis functions 6-31G (d, p) (however, elements with atomic numbers greater than Kr in the periodic table are assigned basis functions LanL2DZ) , the value of the free energy obtained as a result of structural optimization calculation and vibrational calculation of boron dipyrromethene represented by the following formula (III), and the free energy obtained as a result of structural optimization calculation and vibrational calculation of singlet oxygen is subtracted from the value of free energy obtained as a result of structural optimization calculation and vibration calculation on the right side of reaction formula (II).

ΔG varies depending on the groups or atoms represented by R ¹ to R ⁷ in formula (II). Therefore, R ¹ to R ⁷ in formula (II) are selected so that ΔG is −1.0 kcal/mol or more.
If ΔG is −1.0 kcal/mol or more, the dipyrromethene cobalt complex has excellent light resistance, and the colored layers and optical films containing it also have excellent light resistance.
ΔG is preferably 0.0 kcal/mol or more, more preferably 0.3 kcal/mol or more. A larger ΔG is more preferable, and the upper limit is not particularly limited.

In formula (I), the halogen atoms for R ¹ to R ⁷ include fluorine, chlorine, bromine and iodine atoms.
Aliphatic hydrocarbon groups for R ¹ to R ⁷ include alkyl groups and alkenyl groups.

Alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group and iso-pentyl group. , 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3- methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1, 2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1 -ethyl-2-methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group , n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-octyl 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group , 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1-cyclo-hexyl-2,2-dimethylpropyl group, and the like.
One or more hydrogen atoms of these alkyl groups may be substituted with a substituent such as a halogen atom or an alkoxy group.
Alkyl groups may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is, for example, 1-20.

Examples of alkenyl groups include vinyl, propenyl, 1-butenyl, iso-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2 -methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxyvinyl group, 2-cyano-2-methylsulfonevinyl group and the like.
An alkenyl group may be linear or branched. The number of carbon atoms in the alkenyl group is, for example, 2-20.

Alkoxy groups for R ¹ to R ⁷ include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, t-butoxy, and n-pentoxy. group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group and the like.
Alkoxy groups may be linear or branched. The number of carbon atoms in the alkoxy group is, for example, 1-20.

Alkylthio groups for R ¹ to R ⁷ include methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, iso-butylthio, sec-butylthio, t-butylthio and n-pentylthio. group, iso-pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, 1,1-dimethylpropylthio group and the like.
Alkylthio groups may be linear or branched. The number of carbon atoms in the alkylthio group is, for example, 1-20.

Examples of aromatic hydrocarbon groups for R ¹ to R ⁷ include aralkyl groups and aryl groups. at least one hydrogen atom of the aromatic hydrocarbon group is a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group, It may be substituted with a substituent such as an unsubstituted amino group, cyano group, sulfo group, ester group or acyl group.
Aralkyl groups include benzyl, nitrobenzyl, cyanobenzyl, hydroxybenzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, dichlorobenzyl, methoxybenzyl, ethoxybenzyl, trifluoromethylbenzyl, Naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethylnaphthylmethyl group and the like.
The aralkyl group has, for example, 7 to 20 carbon atoms.
Aryl groups include phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl, dimethylphenyl, trimethylphenyl, dichlorophenyl, methoxyphenyl, ethoxyphenyl, trifluoromethylphenyl, N , N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group and the like.
The number of carbon atoms in the aryl group is, for example, 6-20.

The heterocyclic group for R ¹ to R ⁷ includes a heteroaryl group and the like.
Heteroaryl groups include pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazoyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, benzofuranyl, and indoyl groups. be done.
The carbon number of the heteroaryl group is, for example, 4-20.

Examples of substituted amino groups for R ¹ to R ⁷ include alkylcarbonylamino groups and arylcarbonylamino groups.
An acetylamino group, an ethylcarbonylamino group, a butylcarbonylamino group etc. are mentioned as an alkylcarbonylamino group.
The number of carbon atoms in the alkylcarbonylamino group is, for example, 2-20.
The arylcarbonylamino group includes a phenylaminocarbonyl group, a 4-methylphenylaminocarbonyl group, a 2-methoxyphenylaminocarbonyl group, a 4-n-propylphenylaminocarbonyl group and the like.
The carbon number of the arylcarbonylamino group is, for example, 7-20.

Ester groups for R ¹ to R ⁷ include alkoxycarbonyl groups, alkenyloxycarbonyl groups, aralkyloxycarbonyl groups and the like.
Alkoxycarbonyl groups include, for example, methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, n-butoxycarbonyl, t-butoxycarbonyl, 2,2-dimethylpropyloxycarbonyl and 2,4-dimethylbutyloxy. A carbonyl group is mentioned.
The number of carbon atoms in the alkoxycarbonyl group is, for example, 2-20.
The alkenyloxycarbonyl group includes an allyloxycarbonyl group, a 2-butenoxycarbonyl group and the like.
The number of carbon atoms in the alkenyloxycarbonyl group is, for example, 3-20.
The aralkyloxycarbonyl group includes a benzyloxycarbonyl group, a phenethyloxycarbonyl group and the like.
The aralkyloxycarbonyl group has, for example, 8 to 20 carbon atoms.

Acyl groups for R ¹ to R ⁷ include formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group and sec-butylcarbonyl group. , t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group, nitrobenzylcarbonyl group and the like.
The carbon number of the acyl group is, for example, 1-20.

When the monovalent group in R ¹ to R ⁷ has carbon atoms, the number of carbon atoms in the monovalent group is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. When the number of carbon atoms is equal to or less than the above upper limit, the molecular weight of the complex (I) is relatively low, and light with a wavelength of around 500 nm can be sufficiently absorbed at a low coloring material concentration.
When the monovalent group has carbon atoms, the lower limit of the carbon number is the same as the lower limit of the carbon number range shown in the explanation of each monovalent group.

In formula (I), R ¹ to R ⁴ are alkyl groups, and it is preferable that the sum of the carbon numbers of R ¹ and R ² is 3 or more and the sum of the carbon numbers of R ³ and R ⁴ is 3 or more. . In this case, ΔG tends to be large and the light resistance tends to be improved. A possible reason for this is that the steric hindrance by R ¹ or R ² and the steric hindrance by R ³ or R ⁴ suppress the attack of singlet oxygen on the meso position of the dipyrromethene structure. Furthermore, the compatibility with the resin constituting the coating film is improved, it becomes possible to exist stably in the coating film, and the light resistance is improved. More preferably, each of the sum of the carbon numbers of R ¹ and R ² and the sum of the carbon numbers of R ³ and R ⁴ is 4 or more. The upper limit of each of the sum of the carbon numbers of R ¹ and R ² and the sum of the carbon numbers of R ³ and R ⁴ is 12, preferably 8, for example.

In formula (I), it is also preferred that at least one of R ¹ to R ⁴ is a hydrogen atom or a halogen atom. In this case, ΔG tends to increase and the light resistance tends to improve. In this case, R ¹ and R ³ are each independently a hydrogen atom or a halogen atom, R ² and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ³ are each More preferably, they are independently alkyl groups having 1 to 4 carbon atoms, and each of R ² and R ⁴ is independently a halogen atom.

In formula (I), it is preferred that ^R5 is a hydrogen atom. In this case, ΔG tends to increase and the light resistance tends to improve.

In formula (I), it is preferred that R ⁶ and R ⁷ are each independently an ester group. In this case, ΔG tends to increase and the light resistance tends to improve. A possible reason for this is that the bulky structures of R ⁶ and R ⁷ suppress attacks on the meso position of the dipyrromethene structure by singlet oxygen.
Among ester groups, an alkoxycarbonyl group having 2 to 7 carbon atoms is preferable, and an alkoxycarbonyl group having 2 to 3 carbon atoms is more preferable. In this case, the molecular weight of the complex (I) becomes relatively low, and the coloring material concentration can be lowered.

A preferable example of the complex (I) has a structure represented by the following formula (I-1), and an acetone solution (a solution obtained by dissolving the dipyrromethene cobalt complex in acetone) having a molar extinction coefficient of 190000 L/ (mol·cm) or more dipyrromethene cobalt complexes. Such a dipyrromethene cobalt complex is excellent in light resistance. In addition, the molecular weight is relatively low, and the coloring material concentration can be lowered.

Here, R ¹ to R ⁵ are as defined above, and R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 6 carbon atoms. Preferably, R ⁸ and R ⁹ are each independently a methyl group or an ethyl group.

If the molar extinction coefficient is 190000 L/(mol·cm) or more, the light resistance tends to be more excellent.
The molar extinction coefficient is preferably 200000 L/(mol·cm) or more, more preferably 210000 L/(mol·cm) or more. Although the upper limit of the molar extinction coefficient is not particularly limited, it is, for example, 300000 L/(mol·cm).
The molar extinction coefficient is measured by the method described in Examples below.
The above molar extinction coefficient varies depending on the groups or atoms represented by R ¹ to R ⁵ , R ⁸ and R ⁹ in formula (I-1). Therefore, R ¹ to R ⁵ , R ⁸ and R ⁹ in formula (I-1) are selected so that the molar extinction coefficient is 190000 L/(mol·cm) or more.

The method for producing complex (I) is not particularly limited, and for example, it can be produced according to the method described in JP-A-2002-212456.
By appropriately selecting R ¹ to R ⁷ in formula (I), the maximum absorption wavelength of complex (I) can be controlled.

The dye (A) may further contain a second colorant having a maximum absorption wavelength within the range of 560-620 nm. Color purity can be further improved by containing the second coloring material.
The half width of the absorption spectrum of the second coloring material is preferably 15 to 55 nm.

The dye (A) may further contain a coloring material other than the first coloring material and the second coloring material.
Other coloring materials include a third coloring material having the lowest transmittance wavelength in the range of 650 to 780 nm in the wavelength range of 380 to 780 nm. By further containing the third colorant, the decrease in luminance efficiency can be minimized and the color purity can be further improved.

The dye (A) is a porphyrin structure, a merocyanine structure, a phthalocyanine structure, an azo structure, a cyanine structure, a squarylium structure, a coumarin structure, a polyene structure, a quinone structure, a tetradiporphyrin structure, a pyrromethene structure, or an indigo structure. Alternatively, it preferably contains a metal complex thereof. When the dye (A) contains these compounds or metal complexes thereof, both color purity and luminance efficiency can be achieved, and display quality can be further improved.
The dye (A) may contain one of these compounds or metal complexes thereof, or may contain two or more thereof. These compounds or metal complexes thereof may be contained in the first colorant, may be contained in the second colorant, or may be contained in the third colorant. It may be contained in two or more kinds of coloring materials.

The content of the dye (A) is preferably 0.01 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, based on the solid content of the composition for forming a colored layer. When the content of the dye (A) is not less than the above lower limit value, and when the content of the dye (A) is not more than the above upper limit value, external light and secondary emission from the light source of the display device can be effectively absorbed. can be done. When the content of the dye (A) is equal to or less than the above upper limit, aggregation and association of the dye can be suppressed.
The solid content of the composition for forming a colored layer is the total of all components other than the solvent (E). The content of the dye (A) with respect to the solid content of the colored layer-forming composition can be regarded as the content of the dye (A) with respect to the total mass of the colored layer.

<Photopolymerizable compound (B)>
The photopolymerizable compound (B) is a compound that polymerizes and cures when irradiated with active energy rays such as ultraviolet rays.
Examples of the photopolymerizable compound (B) include monofunctional (meth)acrylates, bifunctional (meth)acrylates, and trifunctional or higher (meth)acrylates. The photopolymerizable compound (B) preferably contains a bifunctional or higher (meth)acrylate.
In this specification, "(meth)acrylate" is a generic term for both acrylate and methacrylate, and "(meth)acryloyl" is a generic term for both acryloyl and methacryloyl.

Monofunctional (meth)acrylates are compounds having one (meth)acryloyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2 - ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, 2 - ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phosphoric acid (meth)acrylate, ethylene oxide-modified phosphoric acid (meth)acrylate, phenoxy (meth)acrylate, ethylene oxide Modified phenoxy (meth)acrylate, propylene oxide-modified phenoxy (meth)acrylate, nonylphenol (meth)acrylate, ethylene oxide-modified nonylphenol (meth)acrylate, propylene oxide-modified nonylphenol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (Meth) acrylate, methoxypropylene glycol (meth) acrylate, 2-(meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-(meth) acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrogen phthalate, 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl ( Adamantyl acrylate with monovalent mono(meth)acrylate derived from meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, 2-adamantane, adamantanediol adamantane derivative mono(meth)acrylates such as

A bifunctional (meth)acrylate is a compound having two (meth)acryloyl groups, and includes, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di( meth)acrylate, nonanediol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tri Di(meth)acrylates such as propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentylglycol di(meth)acrylate, and neopentylglycol hydroxypivalate di(meth)acrylate. (Meth)acrylates are mentioned.

Tri- or higher functional (meth)acrylates are compounds having three or more (meth)acryloyl groups, for example, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tris-2-hydroxyethyl isocyanurate tri(meth)acrylate, tri(meth)acrylate such as glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, Trifunctional (meth)acrylate compounds such as ditrimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta Tri- or higher polyfunctional (meth)acrylate compounds such as (meth)acrylate, ditrimethylolpropane penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, and these (meth) Polyfunctional (meth)acrylate compounds in which a part of acrylate is substituted with an alkyl group or ε-caprolactone are mentioned.

Urethane (meth)acrylate may be used as the photopolymerizable compound (B). Examples of urethane (meth)acrylates include those obtained by reacting a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer with a (meth)acrylate monomer having a hydroxyl group.
Examples of urethane (meth)acrylates include pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate toluene diisocyanate. Examples include urethane prepolymers, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymers, and dipentaerythritol pentaacrylate isophorone diisocyanate urethane prepolymers.

The (meth)acrylates described above may be used alone or in combination of two or more. Moreover, the (meth)acrylate described above may be a monomer in the colored layer-forming composition, or may be a partially polymerized oligomer.

The content of the photopolymerizable compound (B) is preferably 50 to 99% by mass, more preferably 70 to 99% by mass, based on the solid content of the composition for forming a colored layer. When the content of the photopolymerizable compound (B) is at least the above lower limit, the effect of suppressing fading can be further enhanced. When the content of the photopolymerizable compound (B) is equal to or less than the above upper limit, the handleability of the composition for forming a colored layer can be further enhanced.

<Photoinitiator (C)>
Examples of the photopolymerization initiator (C) include those that generate radicals when irradiated with active energy rays such as ultraviolet rays.
Examples of the photopolymerization initiator (C) include benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin alkyl ethers such as benzoin isopropyl ether), phenylketones [e.g., acetophenones (e.g., acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.), 2- Alkylphenyl ketones such as hydroxy-2-methylpropiophenone; cycloalkylphenyl ketones such as 1-hydroxycyclohexylphenyl ketone, etc.], aminoacetophenones {2-methyl-1-[4-(methylthio)phenyl]- 2-morpholinoaminopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 etc.}, anthraquinones (anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2- t-butyl anthraquinone, 1-chloroanthraquinone, etc.), thioxanthones (2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenones (benzophenone, etc.), xanthones, phosphine oxides (eg, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.). One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.

The content of the photopolymerization initiator (C) is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the composition for forming a colored layer. When the content of the photopolymerization initiator (C) is at least the above lower limit, the composition for forming a colored layer can be sufficiently cured. When the content of the photopolymerization initiator (C) is equal to or less than the above upper limit, it is difficult for unreacted photopolymerization initiator (D) to remain, and deterioration of reliability can be suppressed.

<Nonpolymerizable additive (D)>
By including the non-polymerizable additive (D) in the colored layer-forming composition, various functions can be imparted to the colored layer 10 .
Non-polymerizable additives (D) include, for example, radical scavengers, peroxide decomposers, singlet oxygen quenchers, leveling agents, antifoaming agents, antioxidants, photosensitizers, antifouling agents, An electrically conductive material is mentioned. The non-polymerizable additive (D) may be used singly or in combination of two or more.
The non-polymerizable additive (D) is selected from radical scavengers, peroxide decomposers and singlet oxygen quenchers because it has a function of preventing deterioration of the dye (A) due to light, heat, etc. 1 or more are preferable.

The radical scavenger has a function of scavenging radicals when the dye (A) is oxidatively deteriorated, and has a function of suppressing autoxidation, thereby suppressing dye deterioration (fading). Examples of radical scavengers include hindered amine light stabilizers, aromatic amine antioxidants, phenol antioxidants, etc. Hindered amine light stabilizers having a molecular weight of 2000 or more are particularly preferred. When the hindered amine light stabilizer has a molecular weight of 2000 or more, a high effect of suppressing fading can be obtained. It is believed that this is because the hindered amine light stabilizer is difficult to volatilize and many molecules remain in the colored layer 10, resulting in a sufficient anti-fading effect.
Examples of hindered amine light stabilizers having a molecular weight of 2000 or more include Chimassorb 2020FDL, Chimassorb 944FDL and Tinuvin 622 manufactured by BASF, Adekastab LA-63P manufactured by ADEKA Corporation, and the like.

The peroxide decomposer ionically decomposes a hydroperoxide (ROOH, R is an alkyl group, O is an oxygen atom, and H is a hydrogen atom) into an inactive compound and suppresses the generation of radicals. It is a kind of antioxidant with function. By including the peroxide decomposer in the non-polymerizable additive (D), the oxidative deterioration of the dye (A) can be suppressed, and the life of the light-emitting element having the colored layer 10 can be extended. When the peroxide decomposing agent corresponds to a singlet oxygen quencher described later, the singlet oxygen quencher is excluded from the peroxide decomposing agent in this specification.
Examples of peroxide decomposers include sulfur-based antioxidants and phosphorus-based antioxidants. Examples of sulfur-based antioxidants include didodecyl 3,3′-thiodipropionate and 2-mercaptobenzimidazole. Phosphorus antioxidants include, for example, trihexyl phosphite, trioleyl phosphite, trioctyl phosphite, tris(2-ethylhexyl) phosphite, tris(2,4-di-tert-butyl phenyl), tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, triphenyl phosphite, tris(2-methylphenyl) phosphite, tris( 4-methylphenyl), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane and the like.

A singlet oxygen quencher is a compound that suppresses oxidative deterioration of the dye (A) due to singlet oxygen. By containing a singlet oxygen quencher in the non-polymerizable additive (D), it is possible to suppress oxidative deterioration of the dye (A) and to extend the life of the light-emitting element having the colored layer 10 .
Singlet oxygen quenchers include transition metal complexes, dyes (excluding dye (A)), amines, phenols, sulfides and the like. Materials that are particularly preferably used as the singlet oxygen quencher include transition metal complexes of dialkyl phosphates, dialkyldithiocarbamates, benzenedithiols, and similar dithiols. Nickel, copper, or cobalt is preferably used as the central metal. be done. Examples of singlet oxygen quenchers include NKX1199 (bis[2′-chloro-3-methoxy-4-(2-methoxyethoxy)dithiobenzyl]nickel) and NKX113 (bis(dithiobenzyl) manufactured by Hayashibara Co., Ltd. nickel), NKX114 (bis[4-(dimethylamino)dithiobenzyl]nickel), Tokyo Chemical Industry Co., Ltd. D1781 (dibutyldithiocarbamate nickel (II)), B1350 (bis(dithiobenzyl)nickel (II)) , B4360 (bis[4,4′-dimethoxy(dithiobenzyl)]nickel(II)), T3204 (tetrabutylammonium bis(3,6-dichloro-1,2-benzenedithiolato)nickelate) and the like.

The content of the non-polymerizable additive (D) is preferably 0.1 to 50% by mass, more preferably 5 to 30% by mass, based on the solid content of the composition for forming a colored layer. When the content of the non-polymerizable additive (D) is at least the above lower limit, various functions can be imparted to the colored layer 10 . When the content of the non-polymerizable additive (D) is equal to or less than the above upper limit, it is easy to maintain curability.

<Solvent (E)>
Examples of the solvent (E) include ethers, ketones, esters, cellosolves and the like. Examples of ethers include dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole and phenetole. mentioned. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone and ethylcyclohexanone. Examples of esters include ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate and γ-butyrolactone. Examples of cellosolves include methyl cellosolve, cellosolve (ethyl cellosolve), butyl cellosolve and cellosolve acetate. The solvent (E) may be used alone or in combination of two or more.

The content of the solvent (E) is preferably 40 to 70% by mass, more preferably 40 to 60% by mass, based on the total mass of the composition for forming a colored layer. When the content of the solvent (E) is within the above range, the solubility of the dye (A) and the non-polymerizable additive (D) is improved, and the stability of the coating liquid (liquid stability) is maintained. good coatability can be obtained.

≪Transparent substrate≫
The transparent substrate 20 is a sheet-like member positioned on one side of the colored layer 10 and forming the optical film 1 .
As a material for forming the transparent substrate 20, a translucent resin film can be used. For example, transparent resins such as polyolefins, polyesters, polyacrylates, polyamides, polyimides, polyarylates, polycarbonates, triacetyl cellulose, polyvinyl alcohol, polyvinyl chloride, cycloolefin copolymers, norbornene-containing resins, polyethersulfones, polysulfones, and inorganic glasses available. Examples of polyolefin include polyethylene and polypropylene. Examples of polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and the like. Examples of polyacrylates include polymethyl methacrylate and the like. Polyamides include, for example, nylon 6, nylon 66, and the like. Among these, a film made of polyethylene terephthalate (PET), a film made of triacetyl cellulose (TAC), a film made of polymethyl methacrylate (PMMA), and a film made of polyester other than PET can be preferably used.
The transmittance of the transparent substrate 20 is preferably 90% or more, for example. The transmittance of the transparent substrate 20 can be measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.).

The transparent base material 20 may be provided with an ultraviolet absorbing ability. By adding an ultraviolet absorber to the resin that is the raw material of the transparent base material 20, the transparent base material 20 can be provided with an ultraviolet absorbing ability.

Examples of the ultraviolet absorber include salicylate-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.
These ultraviolet absorbers may be used alone or in combination of two or more.

When the transparent substrate 20 is to be provided with an ultraviolet absorbing ability, the ultraviolet shielding rate is preferably 85% or more. Here, the ultraviolet shielding rate is a value measured according to JIS L1925, and calculated by the following formula (I).
UV shielding rate (%) = 100 - (average UV transmittance (%) with a wavelength of 290 to 400 nm) (I)
If the UV shielding rate is less than 85%, the effect of suppressing fading in the light resistance of the dye (A) is reduced.

The thickness of the transparent substrate 20 is preferably 10 to 100 μm, for example. The intensity|strength of the optical film 1 can be improved more as the thickness of the transparent base material 20 is more than the said lower limit. When the thickness of the transparent substrate 20 is equal to or less than the above upper limit, the optical film 1 can be made thinner.
The thickness of the transparent base material 20 is obtained by measuring using a digital caliper or the like.

≪Function layer≫
The functional layer 30 is located on one side or the other side of the colored layer 10 . By having the functional layer 30, the optical film 1 can exhibit various functions.
Functions of the functional layer 30 include an antireflection function, an antiglare function, an oxygen barrier function, an antistatic function, an antifouling function, a strengthening function, an ultraviolet absorbing function (ultraviolet absorbing power), and the like.
The functional layer 30 may be a single layer or multiple layers. The functional layer 30 may have one type of function, or may have two or more types of functions.

When the optical film 1 has an antireflection function, the functional layer 30 functions as an antireflection layer. Examples of the antireflection layer include a hard coat layer 32, an antiglare layer 34, and a low refractive index layer 31 having a lower refractive index than the transparent substrate 20, which will be described later. The low refractive index layer 31 can be formed by using a material having a lower refractive index than the materials of the hard coat layer 32, the antiglare layer 34, and the transparent base material 20 for the functional layer.
For adjusting the refractive index of the low refractive index layer 31, lithium fluoride (LiF), magnesium fluoride ( _MgF2 ), _sodium hexafluoroaluminum (cryolite, cryolite, _3NaF.AlF3 , _Na3AlF6 ), Fine particles such as aluminum fluoride (AlF ₃ ) or silica fine particles may be blended. As the silica fine particles, it is effective to lower the refractive index of the low refractive index layer 31 by using porous silica fine particles, hollow silica fine particles, or the like having voids inside the particles. In addition, the composition for forming the low refractive index layer 31 (the composition for forming the low refractive index layer) contains the photopolymerization initiator (D), the additive (B), and the solvent (E) described in the colored layer 10. It may be blended as appropriate.
The refractive index of the low refractive index layer 31 is preferably 1.20 to 1.55.
Although the thickness of the low refractive index layer 31 is not particularly limited, it is preferably 40 nm to 1 μm, for example.

When the optical film 1 has an antiglare function, the functional layer 30 functions as an antiglare layer 34 . The anti-glare layer 34 is a layer that has minute unevenness on the surface, and that the unevenness scatters external light, suppresses glare, and improves display quality. When combined with the low refractive index layer 31, the low refractive index layer 31 and the antiglare layer 34 constitute an antireflection layer.
The anti-glare layer 34 contains at least one selected from organic fine particles and inorganic fine particles, if necessary.
Organic fine particles are materials that form fine irregularities on the surface and provide the function of scattering external light. Examples of organic fine particles include translucent resin materials such as acrylic resins, polystyrene resins, styrene-(meth)acrylate copolymers, polyethylene resins, epoxy resins, silicone resins, polyvinylidene fluoride, and polyethylene fluoride resins. Resin particles consisting of In order to adjust the refractive index and the dispersibility of the resin particles, two or more kinds of resin particles having different materials (refractive indexes) may be mixed and used.
Inorganic fine particles are materials that adjust sedimentation and aggregation of organic fine particles. Examples of inorganic fine particles that can be used include silica fine particles, metal oxide fine particles, and various mineral fine particles. Examples of silica fine particles that can be used include colloidal silica and silica fine particles surface-modified with reactive functional groups such as (meth)acryloyl groups. Examples of metal oxide fine particles that can be used include alumina (aluminum oxide), zinc oxide, tin oxide, antimony oxide, indium oxide, titania (titanium dioxide), and zirconia (zirconium dioxide). Mineral fine particles include, for example, mica, synthetic mica, vermiculite, montmorillonite, iron montmorillonite, bentonite, beidellite, saponite, hectorite, stevensite, nontronite, magadiite, islarite, kanemite, layered titanate, smectite, synthetic Smectite and the like can be used. Mineral fine particles may be either natural products or synthetic products (including substituted products and derivatives), and a mixture of both may be used. Among the fine mineral particles, layered organoclays are more preferred. A layered organic clay is a swelling clay in which an organic onium ion is introduced between layers. The organic onium ion is not limited as long as it can be organized by utilizing the cation exchange property of the swelling clay. When layered organoclay minerals are used as fine mineral particles, the synthetic smectites described above can be suitably used. Synthetic smectite has the function of increasing the viscosity of the coating liquid for forming the antiglare layer, suppressing the sedimentation of resin particles and inorganic fine particles, and adjusting the irregular shape of the surface of the antiglare layer 34 (functional layer 30). have.

The functional layer 30 functions as an oxygen barrier layer 33 when the optical film 1 has an oxygen barrier function. The oxygen permeability of the oxygen barrier layer 33 is 10 cm ³ /(m ² ·day·atm) or less, preferably 5 cm ³ /(m ² ·day·atm) or less, and 1 cm ³ /(m ² ·day·atm) or less. ) below is more preferred. When the oxygen permeability of the oxygen barrier layer 33 is equal to or lower than the above upper limit value, the functional layer 30 can be provided with a sufficient oxygen barrier function. The lower limit of the oxygen permeability of the oxygen barrier layer 33 is not particularly limited, and may be 0 cm ³ /(m ² ·day·atm).
The oxygen permeability of the oxygen barrier layer 33 is a value measured using an oxygen permeability measuring device under the conditions of 30° C. and 60% relative humidity.

When the optical film 1 has an antistatic function, the functional layer 30 functions as an antistatic layer. The antistatic layer includes, for example, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO) and other metal oxide fine particles, polymeric conductive compositions, and antistatic materials such as quaternary ammonium salts. A layer containing an agent is included.
The antistatic layer may be provided on the outermost surface of the functional layer 30 or may be provided between the functional layer 30 and the transparent substrate 20 . Alternatively, an antistatic layer may be formed by adding an antistatic agent to any of the layers constituting the functional layer 30 described above. When an antistatic layer is provided, the optical film preferably has a surface resistance value of 1.0×10 ⁶ to 1.0×10 ¹² (Ω/cm).

When the optical film 1 has an antifouling function, the functional layer 30 functions as an antifouling layer. The antifouling layer enhances antifouling properties by imparting both or one of water repellency and oil repellency. Examples of the antifouling layer include layers containing antifouling agents such as silicon oxides, fluorine-containing silane compounds, fluoroalkylsilazanes, fluoroalkylsilanes, fluorine-containing silicon compounds, and perfluoropolyether group-containing silane coupling agents. be done.
The antifouling layer may be provided on the outermost surface of the functional layer 30, and the antifouling layer may be formed by adding an antifouling agent to the outermost layer of the functional layer 30 described above. .

When the optical film 1 has a reinforcing function, the functional layer 30 functions as a reinforcing layer. The reinforcing layer is a layer that enhances the strength of the optical film. Examples of the reinforcing layer include the hard coat layer 32 . Examples of the hard coat layer 32 include a layer formed of a hard coat agent containing monofunctional, bifunctional, or trifunctional (meth)acrylate or urethane (meth)acrylate.

When the optical film 1 has ultraviolet absorption ability, the functional layer 30 functions as an ultraviolet absorption layer. Examples of the ultraviolet absorbing layer include triazines such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(2H-benzotriazole-2- yl)-4-methylphenol and other layers containing UV absorbers such as benzotriazoles.
The content of the ultraviolet absorber is preferably 0.1 to 5% by weight with respect to the total weight of the material forming the ultraviolet absorbing layer. When the content of the ultraviolet absorber is at least the above lower limit value, the functional layer 30 can be provided with sufficient ultraviolet absorbability. When the content of the ultraviolet absorber is equal to or less than the above upper limit, it is possible to avoid insufficient hardness due to a decrease in the curing component.

In the optical film 1, the UV shielding rate of one or both of the transparent substrate 20 and the functional layer 30 is preferably 85% or more, preferably 90% or more, more preferably 95% or more, and may be 100%. Light resistance can be improved as an ultraviolet shielding rate is more than the said lower limit.
The ultraviolet shielding rate can be measured according to the method described in JIS L1925.
The UV shielding rate can be adjusted by imparting UV absorbing ability to one or both of the transparent substrate 20 and the functional layer 30 .

The thickness of the functional layer 30 is, for example, preferably 0.04 to 25 μm, more preferably 0.1 to 20 μm, even more preferably 0.2 to 15 μm. When the thickness of the functional layer 30 is at least the above lower limit, it is easy to impart various functions to the optical film 1 . If the thickness of the functional layer 30 is equal to or less than the above upper limit, it is advantageous for thinning the display device.
The thickness of the functional layer 30 is obtained by observing a cross section of the optical film 1 in the thickness direction with a microscope or the like.

[Method for producing optical film]
The optical film 1 of this embodiment can be manufactured by a conventionally known method.
For example, the composition for forming a colored layer is applied to one surface of the transparent substrate 20, dried (removing the solvent (E)) as necessary, and irradiated with an active energy ray to apply the composition for forming a colored layer. The colored layer 10 is obtained by curing.
The light source for curing the colored layer-forming composition by irradiating active energy rays to form the colored layer 10 can be used without limitation as long as it generates active energy rays. As active energy rays, radiation (gamma rays, X-rays, etc.), light energy rays such as ultraviolet rays, visible rays, and electron beams (EB) can be used, and usually ultraviolet rays and electron beams are often used. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge tube, or the like can be used as a lamp that emits ultraviolet rays. As irradiation conditions, the amount of ultraviolet irradiation is usually 100 to 1000 mJ/cm ² .

Next, a hard coat layer 32 is obtained by applying a hard coat agent to the other surface of the transparent substrate 20 and curing the hard coat agent by irradiating active energy rays in the same manner as for the colored layer 10 .
By forming the low refractive index layer 31 on the obtained hard coat layer 32, the optical film 1 in which the functional layer 30 is located on the other surface of the transparent substrate 20 is obtained.
The method for forming the low refractive index layer 31 is not limited, and the hard coat layer 32 is coated with a composition for forming a low refractive index layer and irradiated with an active energy ray to be cured. A coating method, an ion beam method, a plasma vapor deposition method, or the like can be used.

[Other embodiments]
As shown in FIG. 2, the optical film has a transparent substrate 20 located on one side of the colored layer 10, and comprises the colored layer 10, the transparent substrate 20, the oxygen barrier layer 33, the hard coat layer 32, the low refractive index The index layer 31 may be the optical film 2 laminated in this order. In the optical film 2 , the oxygen barrier layer 33 , the hard coat layer 32 and the low refractive index layer 31 constitute the functional layer 30 . As the oxygen barrier layer 33, the same layer as the oxygen barrier layer described above can be used. In this case, it is preferable that the functional layer 30 and the transparent substrate 20 have an ultraviolet shielding property with an ultraviolet shielding rate of 85% or more.
Since the optical film 2 of this embodiment has the oxygen barrier layer 33 , it is superior to the optical film 1 in oxygen barrier properties.

As shown in FIG. 3, the optical film has a transparent substrate 20 located on one side of the colored layer 10, and the colored layer 10, the transparent substrate 20, and the antiglare layer 34 are laminated in this order. It may be the optical film 3 . In the optical film 3 , the antiglare layer 34 constitutes the functional layer 30 . As the antiglare layer 34, the same layer as the antiglare layer described above can be used. In this case, it is preferable that the functional layer 30 and the transparent substrate 20 have an ultraviolet shielding property with an ultraviolet shielding rate of 85% or more.
Since the optical film 3 of the present embodiment has the antiglare layer 34, it is superior in display quality.

As shown in FIG. 4, the optical film has a transparent substrate 20 positioned on one side of the colored layer 10, and the colored layer 10, the transparent substrate 20, the antiglare layer 34, and the low refractive index layer 31 are The optical film 4 may be laminated in this order. In the optical film 4 , the antiglare layer 34 and the low refractive index layer 31 constitute the functional layer 30 . In this case, it is preferable that the functional layer 30 and the transparent substrate 20 have an ultraviolet shielding property with an ultraviolet shielding rate of 85% or more.
Since the optical film 4 of the present embodiment has the low refractive index layer 31 and the antiglare layer 34, it is superior in display quality.

As shown in FIG. 5, the optical film has a transparent substrate 20 located on one side of the colored layer 10 and a functional layer 30 located on the other side of the colored layer 10. The transparent substrate 20, The optical film 5 may be formed by laminating the colored layer 10, the hard coat layer 32, and the low refractive index layer 31 in this order. In the optical film 5 , the hard coat layer 32 and the low refractive index layer 31 constitute the functional layer 30 . In this case, the functional layer 30 preferably has an ultraviolet shielding property with an ultraviolet shielding rate of 85% or more.
Since the optical film 5 of the present embodiment has the colored layer 10 and the functional layer 30 on one surface of the transparent substrate 20, the display quality is superior.

As shown in FIG. 6, the optical film has a transparent substrate 20 located on one side of the colored layer 10 and a functional layer 30 located on the other side of the colored layer 10. The transparent substrate 20, The optical film 6 may be formed by laminating the colored layer 10, the oxygen barrier layer 33, the hard coat layer 32, and the low refractive index layer 31 in this order. In the optical film 6 , the oxygen barrier layer 33 , hard coat layer 32 and low refractive index layer 31 constitute the functional layer 30 . In this case, the functional layer 30 preferably has an ultraviolet shielding property with an ultraviolet shielding rate of 85% or more.
Since the optical film 6 of this embodiment has the oxygen barrier layer 33 , it is superior to the optical film 5 in oxygen barrier properties.

As shown in FIG. 7, the optical film has a transparent substrate 20 located on one side of the colored layer 10 and a functional layer 30 located on the other side of the colored layer 10. The transparent substrate 20, The colored layer 10 and the antiglare layer 34 may be the optical film 7 laminated in this order. In the optical film 7 , the antiglare layer 34 constitutes the functional layer 30 . In this case, the functional layer 30 preferably has an ultraviolet shielding property with an ultraviolet shielding rate of 85% or more.
Since the optical film 7 of the present embodiment has the antiglare layer 34, it is superior in display quality.

As shown in FIG. 8, the optical film has a transparent substrate 20 located on one side of the colored layer 10 and a functional layer 30 located on the other side of the colored layer 10. The transparent substrate 20, The optical film 8 may be formed by laminating the colored layer 10, the antiglare layer 34, and the low refractive index layer 31 in this order. In the optical film 8 , the antiglare layer 34 and the low refractive index layer 31 constitute the functional layer 30 . In this case, the functional layer 30 preferably has an ultraviolet shielding property with an ultraviolet shielding rate of 85% or more.
Since the optical film 8 of the present embodiment has the low refractive index layer 31 and the antiglare layer 34, it is superior in display quality.

As described above, the embodiments of the optical film of the present invention have been described in detail with reference to the drawings, but the specific configuration is not limited to these embodiments. A combination etc. are also included.
For example, although the optical film of the above embodiment has one colored layer 10, the number of colored layers may be two or more.
In the optical film of the above embodiment, the ultraviolet absorbing ability may be imparted to the transparent substrate 20 or to the functional layer 30 such as the hard coat layer 32 .

The optical film of the present invention can selectively and efficiently absorb light with a wavelength of around 500 nm. Therefore, even when the thickness of the optical film is thin or when the concentration of the coloring material is low, light with a wavelength of around 500 nm can be sufficiently absorbed. Therefore, according to the optical film of the present invention, it is possible to reduce the reflectance, increase the brightness, reduce the film thickness, and improve the color reproducibility of the display device. Moreover, the optical film of the present invention is also excellent in light resistance.

[Display device]
A display device of the present invention includes the optical film of the present invention.
Specific examples of the display device include, for example, televisions, monitors, mobile phones, portable game devices, personal digital assistants, personal computers, electronic books, video cameras, digital still cameras, head-mounted displays, navigation systems, sound playback devices ( car audio, digital audio player, etc.), copiers, facsimiles, printers, multifunction printers, vending machines, automated teller machines (ATMs), personal authentication devices, optical communication devices, IC cards, and the like. Among them, metal electrodes and wiring are easily affected by external light reflection, and the usefulness of the present invention is high. is preferred.

EXAMPLES The present invention will be described in more detail below using Examples, but the present invention is not limited to these Examples. "Parts" means "mass parts".

[Materials used]
<Photopolymerizable compound (B)>
UA-306H: Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.).
DPHA: dipentaerythritol hexaacrylate.
PETA: pentaerythritol triacrylate.

<Photoinitiator (C)>
Omnirad TPO: acylphosphine oxide photopolymerization initiator (manufactured by IGM Resins B.V.).

<Nonpolymerizable additive (D)>
Tinuvin249: radical scavenger, hindered amine light stabilizer (HALS) (manufactured by BASF Japan, molecular weight 482).
D1781: Singlet oxygen quencher, bis(dibutyldithiocarbamate)nickel(II), product code D1781 (manufactured by Tokyo Chemical Industry Co., Ltd.).

<Solvent (E)>
MEK: methyl ethyl ketone.
Methyl acetate: Methyl acetate.

[Examples 1 to 18, Comparative Examples 1 to 12]
(Synthesis of dipyrromethene cobalt complex)
The dipyrromethene cobalt complexes (compounds 1 to 18, 1' to 12') shown in Table 1 were synthesized by the following procedure.
In Table 1, Me is a methyl group, Et is an ethyl group, ⁿ Bu is an n-butyl group, ^t Bu is a t-butyl group, and Ph is a phenyl group.

<Synthesis of Compound 1>
[Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
Ethyl 5-formyl-2,4-dimethyl-1H-pyrrole-3-carboxylate (2.5 g) was sealed in a reaction vessel and dissolved in methanol (50 mL), followed by 47% hydrobromic acid (45 g). was added and refluxed for 1 hour. 3,3′,5,5′-Tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide (2.6 g) was obtained by filtering off the precipitated solid. Obtained.

[Synthesis of compound 1]
3,3′,5,5′-Tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide (0.6 g) was sealed in a reaction vessel and methanol (5 mL) was added. , triethylamine (0.17 g) and cobalt acetate tetrahydrate (0.18 g) were added and refluxed for 2 hours. Compound 1 (0.42 g) was obtained by filtering the precipitated solid.

<Synthesis of compound 2>
[Synthesis of 3,3′-dimethyl-5,5′-di-iodo-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 5-formyl-2-iodo-4-methyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 2]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-dimethyl -5,5'-di-iodo-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was used, but synthesized in the same manner.

<Synthesis of compound 3>
[Synthesis of 3,3′-dimethyl-5,5′-di-bromo-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesized in the same procedure except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 2-bromo-5-formyl-4-methyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 3]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-dimethyl -5,5'-di-bromo-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was used, but synthesized in the same manner.

<Synthesis of compound 4>
[Synthesis of 3,3′-dimethyl-5,5′-di-chloro-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 2-chloro-5-formyl-4-methyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 4]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-dimethyl -5,5'-di-chloro-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was used, but synthesized in the same procedure.

<Synthesis of compound 5>
[Synthesis of 5,5′-di-methyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 5-formyl-2-methyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 5]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 5,5′-di -Methyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was synthesized in the same procedure.

<Synthesis of Compound 6>
[Synthesis of 3,3′-di-chloro-5,5′-di-methyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 4-chloro-5-formyl-2-methyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 6]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Chloro-5,5'-dimethyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was used, but synthesized in the same manner.

<Synthesis of compound 7>
[Synthesis of 3,3′-di-iodo-5,5′-di-methyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesized in the same procedure except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 5-formyl-4-iodo-2-methyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 7]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Iodo-5,5'-di-methyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was synthesized in the same procedure.

<Synthesis of Compound 8>
[Synthesis of 3,3′-di-bromo-5,5′-di-methyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 4-bromo-5-formyl-2-methyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 8]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Bromo-5,5'-di-methyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was used, but synthesized in the same procedure.

<Synthesis of compound 9>
[Synthesis of 3,3′,5,5′-tetramethyl-4,4′-bis(2,2-dimethylpropoxycarbonyl)-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to 2,2-dimethylpropyl 5-formyl-2,4-dimethyl-1H-pyrrole-3-carboxylate.

[Synthesis of Compound 9]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′,5 ,5'-tetramethyl-4,4'-bis(2,2-dimethylpropoxycarbonyl)-2,2'-dipyrromethene hydrobromide was used, but synthesized in the same manner.

<Synthesis of compound 10>
[Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-methoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to methyl 5-formyl-2,4-dimethyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 10]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′,5 ,5'-tetramethyl-4,4'-di-methoxycarbonyl-2,2'-dipyrromethene hydrobromide was used, but synthesized in the same manner.

<Synthesis of Compound 11>
[Synthesis of 4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 5-formyl-1H-pyrrole-3-carboxylate.

[Synthesis of Compound 11]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 4,4′-di -Ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was synthesized in the same procedure.

<Synthesis of compound 12>
[Synthesis of 5,5′-di-methyl-4,4′-di-methoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to methyl 5-formyl-2-methyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 12]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 5,5′-di -Methyl-4,4'-di-methoxycarbonyl-2,2'-dipyrromethene hydrobromide was synthesized in the same procedure.

<Synthesis of compound 13>
[Synthesis of 3,3′-di-butyl-5,5′-di-ethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 4-butyl-2-ethyl-5-formyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 13]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Butyl-5,5'-di-ethyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide, but synthesized in the same procedure.

<Synthesis of compound 14>
[Synthesis of 3,3′-di-butyl-5,5′-di-ethyl-4,4′-di-methoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to methyl 4-butyl-2-ethyl-5-formyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 14]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Butyl-5,5'-di-ethyl-4,4'-di-methoxycarbonyl-2,2'-dipyrromethene hydrobromide, but synthesized in the same procedure.

<Synthesis of Compound 15>
[Synthesis of 3,3′-di-butyl-5,5′-di-methyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 4-butyl-2-methyl-5-formyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 15]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Butyl-5,5'-di-methyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was used, but synthesized in the same procedure.

<Synthesis of compound 16>
[Synthesis of 3,3′-di-propyl-5,5′-di-methyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 4-propyl-2-methyl-5-formyl-1H-pyrrole-3-carboxylate.

[Synthesis of Compound 16]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Propyl-5,5'-di-methyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was synthesized in the same manner.

<Synthesis of Compound 17>
[Synthesis of 3,3′-di-butyl-5,5′-di-methyl-4,4′-di-methoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to methyl 4-butyl-2-methyl-5-formyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 17]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Butyl-5,5'-di-methyl-4,4'-di-methoxycarbonyl-2,2'-dipyrromethene hydrobromide, but synthesized in the same procedure.

<Synthesis of compound 18>
[Synthesis of 3,3′-di-ethyl-5,5′-di-methyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to ethyl 4-ethyl-2-methyl-5-formyl-1H-pyrrole-3-carboxylate.

[Synthesis of compound 18]
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 3,3′-di -Ethyl-5,5'-di-methyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was synthesized in the same procedure.

<Synthesis of compound 1'>
[Synthesis of 4,4′-di-ethyl-3,3′,5,5′-tetramethyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesis was carried out in the same manner except that ethyl-1H-pyrrole-3-carboxylate was changed to 3-ethyl-5-formyl-2,4-dimethyl-1H-pyrrole.

[Synthesis of compound 1']
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is converted to 4,4′-di -Ethyl-3,3',5,5'-tetramethyl-2,2'-dipyrromethene hydrobromide was synthesized in the same procedure.

<Synthesis of compound 2'>
p-Bromobenzaldehyde (0.27 g), ethyl 2,4-dimethylpyrrole-3-carboxylate (0.50 g), dichloromethane (93 mL), trifluoroacetic acid (0.1 mL) were added to a reaction vessel, Time reflux was performed. 2,3-Dichloro-5,6-dicyano-p-benzoquinone (0.33 g) was added to this solution and stirred at room temperature for 2 hours. After that, triethylamine (3.0 mL) and cobalt (II) acetate tetrahydrate (0.18 g) were added and refluxed for 2 hours. After diluting with dichloromethane, the mixture was washed with pure water, and the remaining organic layer was dried over anhydrous magnesium sulfate. After filtration and concentration, the precipitated powder was collected by suction filtration to obtain compound 2' (0.42 g).

<Synthesis of Compound 3′>
In <Synthesis of Compound 2'> above, synthesis was carried out in the same manner except that p-bromobenzaldehyde was changed to m-cyanobenzaldehyde.

<Synthesis of compound 4'>
In <Synthesis of Compound 2'> above, the procedure was the same except that p-bromobenzaldehyde was changed to p-nitrobenzaldehyde.

<Synthesis of Compound 5′>
In <Synthesis of compound 2′> above, p-bromobenzaldehyde was changed to p-iodobenzaldehyde, and ethyl 2,4-dimethylpyrrole-3-carboxylate was changed to 3-ethyl-2,4-dimethylpyrrole. was synthesized by a similar procedure.

<Synthesis of compound 6'>
In <Synthesis of Compound 2′> above, synthesis was carried out in the same manner except that p-bromobenzaldehyde was changed to p-iodobenzaldehyde.

<Synthesis of Compound 7′>
In <Synthesis of compound 2′>, synthesis was performed in the same manner except that p-bromobenzaldehyde was changed to benzaldehyde.

<Synthesis of compound 8′>
In <Synthesis of Compound 2′> above, synthesis was carried out in the same manner except that p-bromobenzaldehyde was changed to p-cyanobenzaldehyde.

<Synthesis of Compound 9′>
In <Synthesis of Compound 2'> above, synthesis was carried out in the same manner except that p-bromobenzaldehyde was changed to m-iodobenzaldehyde.

<Synthesis of Compound 10′>
In <Synthesis of Compound 2′> above, the same procedure was performed except that p-bromobenzaldehyde was changed to acetaldehyde and ethyl 2,4-dimethylpyrrole-3-carboxylate was changed to 3-ethyl-2,4-dimethylpyrrole. synthesized by the procedure of

<Synthesis of compound 11'>
In <Synthesis of Compound 2′> above, p-bromobenzaldehyde was changed to benzaldehyde, and ethyl 2,4-dimethylpyrrole-3-carboxylate was changed to 2,4-dimethylpyrrole-3-carboxylate-n-butyl. Synthesized by the same procedure except that

<Synthesis of compound 12′>
[Synthesis of 3,3′-dimethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide]
In the above [Synthesis of 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide], 5-formyl-2,4-dimethyl Synthesized in the same procedure except that ethyl-1H-pyrrole-3-carboxylate was changed to 5-formyl-4-methyl-1H-pyrrole.

[Synthesis of compound 12']
In the above [Synthesis of Compound 1], 3,3′,5,5′-tetramethyl-4,4′-di-ethoxycarbonyl-2,2′-dipyrromethene hydrobromide is -Methyl-4,4'-di-ethoxycarbonyl-2,2'-dipyrromethene hydrobromide was synthesized in the same procedure.

(Preparation of coating liquid)
The obtained dipyrromethene cobalt complex was dissolved in a mixed solvent of MEK/methyl acetate=50/50 (mass ratio). The obtained solution, UA-306H, DPHA and PETA (UA-306H/DPHA/PETA=70/20/10 (mass ratio)) as the photopolymerizable compound (B), and Omnirad TPO as the photopolymerization initiator (C). , Tinuvin249 and D1781 (Tinuvin249/D1781 = 70/30 (mass ratio)) as a non-polymerizable additive (D) were mixed to prepare a coating liquid (colored layer forming composition) having the following composition.
Dipyrromethene-cobalt complex: 0.4% by mass relative to the solid content of the coating liquid.
Photopolymerizable compound (B): 94% by mass based on the solid content of the coating liquid.
Photopolymerization initiator (C): 3% by mass relative to the solid content of the coating liquid.
Non-polymerizable additive (D): 2.6% by mass based on the solid content of the coating liquid.
Solvent (E): 70 mass % with respect to the total mass of the coating liquid.

(Formation of coating film)
The above coating solution was spin-coated on a glass substrate and dried in an oven at 80° C. for 60 seconds. After that, the coating film is cured by performing ultraviolet irradiation with an irradiation dose of 150 mJ / cm ² (manufactured by Fusion UV Systems Japan Co., Ltd., light source H bulb) using an ultraviolet irradiation device, and the film thickness after curing is 5.0 μm. A film (cured film) was formed.

(Production of evaluation board)
An 80% polyvinyl alcohol aqueous solution (PVA117, manufactured by Kuraray Co., Ltd.) was applied onto the cured film and dried to form an oxygen barrier layer. Further, a triacetyl cellulose film (TG60UL, manufactured by Fuji Film Co., Ltd., substrate thickness: 60 μm) was adhered to the oxygen barrier layer to prepare an evaluation substrate.

(evaluation)
<Free energy change (ΔG) before and after reaction>
For boron dipyrromethene having the same substituent as the dipyrromethene cobalt complex of each example, using the quantum chemical calculation program Gaussian16, calculation method B3LYP, basis function 6-31G (d, p) (however, from Kr in the periodic table A basis function LanL2DZ is assigned to an element with a large atomic number), ΔG was calculated according to the following procedure. Table 2 shows the results.
(1) Structural optimization calculations and vibrational calculations were performed for boron dipyrromethene having the same substituent as the dipyrromethene cobalt complex of each example, and from the vibrational calculation results, the free energy value G _Co got
(2) Structural optimization calculation and vibrational calculation of singlet oxygen were performed, and the free energy value _GO2 of singlet oxygen was obtained from the result of the vibrational calculation.
(3) Structural optimization and vibrational calculation of the structure in which oxygen is added to the meso position of the boron dipyrromethene structure (the structure on the right side of the reaction formula (II)), and from the results of the vibrational calculation, the boron dipyrromethene obtained the value of the free energy of the oxygen adduct of G _Co+O2 .
(4) ΔG was calculated according to the following formula.
ΔG=G _Co+O2 −(G _Co +G _O2 )

<Molar extinction coefficient (ε) of acetone solution>
Three acetone solutions with different concentrations of the dipyrromethene cobalt complex were prepared, and the absorption spectrum was measured using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), with a wavelength range of 470 to 530 nm. The slope of the approximate straight line when the absorbance at the maximum absorption wavelength was plotted against each concentration was defined as ε. Table 2 shows the results.

<Maximum Absorption Wavelength of Acetone Solution (λ _max )>
An acetone solution of a dipyrromethene cobalt complex is prepared, and the absorption spectrum is measured using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the wavelength at which the absorbance is maximum in the wavelength range of 470 to 530 nm. was taken as λ _max . Table 2 shows the results.

<Maximum absorption wavelength of coating film (λ _max )>
The absorption spectrum of the coating film was measured using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the wavelength at which the absorbance was maximum in the wavelength range of 470 to 530 nm was defined as λ _max . Table 2 shows the results.

<Half width of the coating film>
The absorption spectrum of the coating film was measured using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the half width of the peak with the maximum absorbance in the wavelength range of 470 to 530 nm was calculated. Table 2 shows the results.

<Light resistance>
Using a xenon weather meter tester (manufactured by Suga Test Instruments Co., Ltd., X75), a xenon lamp illuminance of 60 W/cm ² (300 to 400 nm) and a temperature inside the tester are applied to the surface of the evaluation substrate on which the coating film is formed. A light irradiation test was conducted for 120 hours under the conditions of 45° C. and 50% RH. Before and after the test, the transmittance of the evaluation substrate is measured using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and the wavelength showing the minimum transmittance before the test in the wavelength range of 470 to 530 nm. The transmittance difference (ΔT) before and after the test was calculated. Table 2 shows the results.
A: ΔT is less than 10%.
B: ΔT is 10% or more and less than 15%.
C: ΔT is 15% or more.

<Dye density>
In Examples 1, 5, 10, 12 and Comparative Example 11, by changing the content of the dipyrromethene cobalt complex with respect to the solid content in the coating liquid, curing with different concentrations (% by mass) of the dipyrromethene cobalt complex A film was formed, and the transmittance was measured with an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). The concentration (% by mass) of the dipyrromethene metal complex in the cured film when the transmittance was 40% at a film thickness of 5.0 μm was determined and evaluated according to the following criteria. Table 3 shows the results.
A: Concentration less than 0.4%.
B: Concentration of 0.4% or more.

<Compatibility>
The coating films formed in Examples 1, 5, 10, 12 and Comparative Example 11 were visually observed to determine whether or not the dye (dipyrromethene metal complex) was compatible with other components, and evaluated according to the following criteria. . Table 3 shows the results.
A: Compatible.
B: Phase separation and deposition of dye occur and are not compatible.

As shown in the above results, the coating films of Examples 1 to 18 using dipyrromethene-cobalt complexes having a ΔG of −1.0 kcal/mol or more had excellent light resistance. The compatibility between the dipyrromethene cobalt complex and other components was also good. In particular, when the acetone solution of the dipyrromethene-cobalt complex had a molar extinction coefficient of 190000 L/(mol·cm) or more, the absorption efficiency of light near a wavelength of 500 nm was high. Being able to keep the concentration of the dipyrromethene metal complex in the coating film low is also useful in terms of production costs.

1, 2, 3, 4, 5, 6, 7, 8 optical film 10 colored layer 20 transparent substrate 30 functional layer 31 low refractive index layer 32 hard coat layer 33 oxygen barrier layer 34 antiglare layer

EXAMPLES The present invention will be described in more detail below using Examples, but the present invention is not limited to these Examples. "Parts" means "mass parts". Examples 1, 9, and 10, which will be described later, are reference examples.

Claims (25)

A transparent substrate and a colored layer laminated on at least one side of the transparent substrate,
The colored layer contains a dye (A),
The dye (A) contains a coloring material having a maximum absorption wavelength within the range of 470 to 530 nm,
The coloring material is a dipyrromethene cobalt complex having a structure represented by the following formula (I), wherein R ¹ to R ⁷ in the formula (I) are applied to the following reaction formula (II), and quantum chemical Free energies before and after the reaction calculated using the calculation program Gaussian16, using the calculation method B3LYP and basis functions 6-31G(d, p) (however, elements with atomic numbers greater than Kr in the periodic table are assigned basis functions LanL2DZ). An optical film containing a dipyrromethene cobalt complex in which R ¹ to R ⁷ are combined such that the change is −1.0 kcal/mol or more.

Here, each of R ¹ to R ⁷ independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a nitro group, a substituted It represents a monovalent group selected from the group consisting of amino groups, unsubstituted amino groups, cyano groups, sulfo groups, ester groups and acyl groups.

The optical film as claimed in claim 1, wherein in the dipyrromethene cobalt complex, ^R5 is a hydrogen atom. In the dipyrromethene cobalt complex, R ¹ to R ⁴ are alkyl groups, the sum of the carbon numbers of R ¹ and R ² is 3 or more, and the sum of the carbon numbers of R ³ and R ⁴ is 3 or more. 3. The optical film as described in 1 or 2. 3. The optical film according to claim 1, wherein at least one of R ¹ to R ⁴ in the dipyrromethene cobalt complex is a hydrogen atom or a halogen atom. In the dipyrromethene cobalt complex, R ¹ and R ³ are each independently a hydrogen atom or a halogen atom, and R ² and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, and R ² and R ⁴ are each independently a halogen atom. 3. The dipyrromethene-cobalt complex according to claim 1, wherein the complex has a structure represented by the following formula (I-1) and has a molar absorption coefficient of 190000 L/(mol·cm) or more in acetone solution. optical film.

Here, R ¹ to R ⁵ are as defined above, and R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 6 carbon atoms. 7. The optical film as claimed in claim 6, wherein in the dipyrromethene cobalt complex, ^R8 and ^R9 are each independently a methyl group or an ethyl group. Containing a dye (A), a photopolymerizable compound (B), and a photopolymerization initiator (C),
The dye (A) contains a coloring material having a maximum absorption wavelength within the range of 470 to 530 nm,
The coloring material is a dipyrromethene cobalt complex having a structure represented by the following formula (I), wherein R ¹ to R ⁷ in the formula (I) are applied to the following reaction formula (II), and quantum chemical Free energies before and after the reaction calculated using the calculation program Gaussian16, using the calculation method B3LYP and basis functions 6-31G(d, p) (however, elements with atomic numbers greater than Kr in the periodic table are assigned basis functions LanL2DZ). A colored layer-forming composition containing a dipyrromethene-cobalt complex in which R ¹ to R ⁷ are combined so that the change is −1.0 kcal/mol or more.

Here, each of R ¹ to R ⁷ independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a nitro group, a substituted It represents a monovalent group selected from the group consisting of amino groups, unsubstituted amino groups, cyano groups, sulfo groups, ester groups and acyl groups.

9. The composition for forming a colored layer according to claim 8, wherein in the dipyrromethene cobalt complex, ^R5 is a hydrogen atom. In the dipyrromethene cobalt complex, R ¹ to R ⁴ are alkyl groups, the sum of the carbon numbers of R ¹ and R ² is 3 or more, and the sum of the carbon numbers of R ³ and R ⁴ is 3 or more. 9. The composition for forming a colored layer according to 8 or 9. 10. The composition for forming a colored layer according to claim 8, wherein at least one of R ¹ to R ⁴ in the dipyrromethene cobalt complex is a hydrogen atom or a halogen atom. In the dipyrromethene cobalt complex, R ¹ and R ³ are each independently a hydrogen atom or a halogen atom, and R ² and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, and R ² and R ⁴ are each independently a halogen atom. 10. The dipyrromethene cobalt complex according to claim 8 or 9, which has a structure represented by the following formula (I-1) and has a molar absorption coefficient of 190000 L/(mol cm) or more in an acetone solution. A composition for forming a colored layer.

Here, R ¹ to R ⁵ are as defined above, and R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 6 carbon atoms. 14. The composition for forming a colored layer according to claim 13, wherein in the dipyrromethene-cobalt complex, ^R8 and ^R9 are each independently a methyl group or an ethyl group. The composition for forming a colored layer according to claim 8 or 9, further comprising a non-polymerizable additive (D). A transparent substrate and a colored layer laminated on at least one side of the transparent substrate,
The optical film, wherein the colored layer is a cured product of the composition for forming a colored layer according to claim 8 or 9. A dipyrromethene cobalt complex having a structure represented by the following formula (I-1) and having an acetone solution molar absorption coefficient of 190000 L/(mol·cm) or more.

Here, R ¹ to R ⁵ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkylthio group, an aromatic hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a nitro group, a substituted a monovalent group selected from the group consisting of an amino group, an unsubstituted amino group, a cyano group, a sulfo group, an ester group and an acyl group, wherein each of R ⁸ and R ⁹ is independently an alkyl group having 1 to 6 carbon atoms; indicates 18. The dipyrromethene cobalt complex according to claim 17, wherein ^R8 and ^R9 are each independently a methyl group or an ethyl group. 19. The dipyrromethene cobalt complex according to claim 17 or 18, wherein ^R5 is a hydrogen atom. 19. The dipyrro according to claim 17 or 18, wherein R ¹ to R ⁴ are alkyl groups, the total number of carbon atoms of R ¹ and R ² is 3 or more, and the total number of carbon atoms of R ³ and R ⁴ is 3 or more. Methene cobalt complex. 19. The dipyrromethene cobalt complex according to claim 17 or 18, wherein at least one of R ¹ to R ⁴ is a hydrogen atom or a halogen atom. R ¹ and R ³ are each independently a hydrogen atom or a halogen atom, R ² and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ³ are each independently carbon 22. The dipyrromethene cobalt complex according to claim 21, which is an alkyl group of numbers 1 to 4, wherein R ² and R ⁴ are each independently a halogen atom. 19. The dipyrromethene cobalt complex according to claim 17 or 18, which has an absorption maximum wavelength of 470 to 530 nm in an acetone solution. A display device comprising the optical film according to claim 1 . A display device comprising the optical film according to claim 16 .

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