JP2019158990A - Colored resin composition, color filter substrate, and reflection type liquid crystal display - Google Patents

Abstract

To provide a colored resin composition with which a red pixel or a green pixel having higher luminance and higher color purity can be formed with the use of external light or light from a light source, such as a backlight.SOLUTION: A colored resin composition contains a pyrromethene derivative, a yellow colorant, and a binder resin.EFFECT: When a light source having a wide wavelength range, such as white light is used, the pyrromethene derivative emits red and green light, and the yellow colorant absorbs light in a blue region, and thereby a pixel having extremely high luminance and excellent color purity can be obtained.SELECTED DRAWING: None

Description

  The present invention relates to a colored resin composition, a color filter substrate using the same, and a reflective liquid crystal display device.

  Liquid crystal display devices equipped with color filters are used in various applications such as portable information terminals, televisions, notebook computers, etc., taking advantage of characteristics such as light weight, thinness, and low power consumption. A color filter generally has pixels of each color formed using a colored resin composition.

  In recent years, there has been an increasing demand for higher color purity for displaying a wide color gamut by expanding the color reproduction range of a display device and higher luminance for displaying an image brighter. In response to these demands, various studies on the colored resin composition constituting the pixel of the color filter have been advanced, and in particular, the enhancement of high color purity and high brightness of the red pixel and the green pixel has been studied.

  Examples of the red resin composition include an alkali-soluble resin, a colorant, and a solvent. As the colorant, a diketopyrrolopyrrole pigment having a bromine group, C.I. I. There has been proposed a resin composition containing Pigment Red 177 and a yellow colorant, wherein the ratio of the yellow colorant in the total colorant is 5 to 50% by mass (for example, see Patent Document 1).

  Examples of the green resin composition include a colorant, a resin, a polymerizable compound, and a polymerization initiator, and the colorant (A) includes C.I. I. Pigment blue 16 and C.I. I. A green colored resin composition containing Pigment Green 59 has been proposed (see, for example, Patent Document 2).

  On the other hand, a pyromethene derivative has been proposed as a light emitting material, and a color conversion film including a layer made of a cured product of a color conversion composition that includes a pyromethene derivative and a binder resin and converts incident light into light having a longer wavelength than the incident light. Has been proposed (see, for example, Patent Document 3).

Japanese Patent Laid-Open No. 2006-176058 JP 2017-120407 A International Publication No. 2016/190283

  The techniques of Patent Documents 1 and 2 do not satisfy the recent demand for higher brightness. Patent Document 3 discloses nothing about the yellow colorant and the color filter substrate, and has not studied the improvement of color purity and luminance, which are problems of conventional displays.

  An object of the present invention is to provide a colored resin composition capable of forming a red pixel or a green pixel with higher brightness and higher color purity by using light from a light source such as external light or a backlight. To do.

  The present invention is a colored resin composition containing a pyromethene derivative, a yellow colorant and a binder resin.

  According to the colored resin composition of the present invention, when a light source having a wide wavelength region such as white light is used, the pyromethene derivative emits red or green light, and the yellow colorant absorbs light in the blue region. Is very high, and a pixel excellent in color purity can be obtained.

  The colored resin composition of the present invention contains a pyromethene derivative, a yellow colorant and a binder resin. The binder resin has an action of holding each component of the colored resin composition. Since the pyromethene derivative absorbs a part of light in the visible light region and has an action as an organic light-emitting material that emits light by being converted into light of a specific wavelength, the luminance can be greatly improved. In the present invention, by containing a yellow colorant together with the pyromethene derivative, the yellow colorant absorbs light other than light having a wavelength absorbed by the pyromethene derivative, so that the color purity can be improved.

  The colored resin composition of the present invention contains a pyromethene derivative. The pyromethene derivative has a color conversion function and is excellent in fluorescence quantum yield and durability. Since the pyromethene derivative exhibits light emission characteristics with high fluorescence quantum yield, it can emit light with high efficiency.

  As the pyromethene derivative, a compound represented by the following general formula (1) is preferable.

X is C—R ⁷ or N. R ^{1 to} R ⁹ may be the same as or different from each other, and are hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl Ether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, sulfo group It is selected from a condensed ring and an aliphatic ring formed between a group, a phosphine oxide group, and an adjacent substituent.

  In all of the above groups, hydrogen may be deuterium. The same applies to the compound described below or a partial structure thereof. In the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms includes 6 to 40 carbon atoms including the carbon number contained in the substituent substituted on the aryl group. An aryl group. The same applies to other substituents that define the number of carbon atoms.

  Moreover, in all the above groups, the substituents in the case of substitution include alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, thiol groups, alkoxy groups, alkylthio groups. , Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group , A sulfo group and a phosphine oxide group are preferable, and specific substituents which are preferable in the description of each substituent are preferable. Moreover, these substituents may be further substituted with the above-mentioned substituents.

  “Unsubstituted” in the case of “substituted or unsubstituted” means that a hydrogen atom or a deuterium atom is substituted. In the compound described below or a partial structure thereof, the case of “substituted or unsubstituted” is the same as described above.

  Among all the above groups, the alkyl group is, for example, a saturated aliphatic hydrocarbon such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, etc. Represents a group, which may or may not have a substituent. There are no particular limitations on the additional substituent when it is substituted, and examples thereof include an alkyl group, a halogen, an aryl group, a heteroaryl group, and the like, and this point is common to the following description. Further, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably in the range of 1 to 20 and more preferably 1 to 8 from the viewpoint of availability and cost.

  The cycloalkyl group represents, for example, a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, etc., which may or may not have a substituent. . Although carbon number of an alkyl group part is not specifically limited, Preferably it is the range of 3-20.

  The heterocyclic group refers to, for example, an aliphatic ring having atoms other than carbon such as a pyran ring, piperidine ring, and cyclic amide in the ring, which may or may not have a substituent. Good. Although carbon number of a heterocyclic group is not specifically limited, Preferably it is the range of 2-20.

  An alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group or a butadienyl group, which may or may not have a substituent. . Although carbon number of an alkenyl group is not specifically limited, Preferably it is the range of 2-20.

  The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, and the like. It may not have.

  An alkynyl group refers to, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent. Although carbon number of an alkynyl group is not specifically limited, Preferably it is the range of 2-20.

  The alkoxy group refers to, for example, a functional group having an aliphatic hydrocarbon group bonded through an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group has a substituent. May not be included. Although carbon number of an alkoxy group is not specifically limited, Preferably it is the range of 1-20.

  The alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Preferably it is the range of 1-20.

  An aryl ether group refers to a functional group to which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Also good. Although carbon number of an aryl ether group is not specifically limited, Preferably, it is the range of 6-40.

  An aryl thioether group is one in which the oxygen atom of the ether bond of the aryl ether group is substituted with a sulfur atom. The aromatic hydrocarbon group in the aryl thioether group may or may not have a substituent. The number of carbon atoms of the arylthioether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

  The aryl group is, for example, phenyl group, biphenyl group, terphenyl group, naphthyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, phenanthryl group, anthracenyl group, benzophenanthryl group, benzoanthracene group. An aromatic hydrocarbon group such as a nyl group, a chrycenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a benzofluoranthenyl group, a dibenzoanthracenyl group, a perylenyl group, or a helicenyl group. Among these, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, a fluoranthenyl group, and a triphenylenyl group are preferable. The aryl group may or may not have a substituent. Although carbon number of an aryl group is not specifically limited, Preferably it is 6-40, More preferably, it is the range of 6-30.

When R ^{1 to} R ⁹ are substituted or unsubstituted aryl groups, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, or an anthracenyl group, and a phenyl group, biphenyl Group, terphenyl group, and naphthyl group are more preferable. More preferred are a phenyl group, a biphenyl group, and a terphenyl group, and a phenyl group is particularly preferred.

  When each substituent is further substituted with an aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, or an anthracenyl group. A phenyl group and a naphthyl group are more preferable. Particularly preferred is a phenyl group.

  Heteroaryl group is, for example, pyridyl group, furanyl group, thienyl group, quinolinyl group, isoquinolinyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, triazinyl group, naphthyridinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, Benzofuranyl group, benzothienyl group, indolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzocarbazolyl group, carbolinyl group, indolocarbazolyl group, benzofurocarbazolyl group, benzothienocarbazolyl Group, dihydroindenocarbazolyl group, benzoquinolinyl group, acridinyl group, dibenzoacridinyl group, benzimidazolyl group, imidazopyridyl group, benzoxazolyl group, benzothiazolyl group, phenanthrolinyl group, etc. Atoms other than hydrogen shows a cyclic aromatic group having a single or a plurality of rings. However, the naphthyridinyl group is any of 1,5-naphthyridinyl group, 1,6-naphthyridinyl group, 1,7-naphthyridinyl group, 1,8-naphthyridinyl group, 2,6-naphthyridinyl group, and 2,7-naphthyridinyl group. Indicate. The heteroaryl group may or may not have a substituent. Although carbon number of a heteroaryl group is not specifically limited, Preferably it is 2-40, More preferably, it is the range of 2-30.

When R ^{1 to} R ⁹ are a substituted or unsubstituted heteroaryl group, examples of the heteroaryl group include pyridyl group, furanyl group, thienyl group, quinolinyl group, pyrimidyl group, triazinyl group, benzofuranyl group, benzothienyl group, indolyl group. Group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzimidazolyl group, imidazopyridyl group, benzoxazolyl group, benzothiazolyl group and phenanthrolinyl group are preferable, and pyridyl group, furanyl group, thienyl group and quinolinyl group are preferable. More preferred. Particularly preferred is a pyridyl group.

  When each substituent is further substituted with a heteroaryl group, the heteroaryl group includes pyridyl, furanyl, thienyl, quinolinyl, pyrimidyl, triazinyl, benzofuranyl, benzothienyl, indolyl, dibenzo A furanyl group, a dibenzothienyl group, a carbazolyl group, a benzimidazolyl group, an imidazopyridyl group, a benzoxazolyl group, a benzothiazolyl group, and a phenanthrolinyl group are preferable, and a pyridyl group, a furanyl group, a thienyl group, and a quinolinyl group are more preferable. Particularly preferred is a pyridyl group.

  Halogen represents an atom selected from fluorine, chlorine, bromine and iodine. The carbonyl group, carboxyl group, ester group, and carbamoyl group may or may not have a substituent. Here, examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, and these substituents may be further substituted.

  An amino group is a substituted or unsubstituted amino group. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, and a branched alkyl group. As the aryl group and heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group, and a quinolinyl group are preferable. These substituents may be further substituted. Although carbon number is not specifically limited, Preferably it is 2-50, More preferably, it is 6-40, Most preferably, it is the range of 6-30.

  Examples of silyl groups include trimethylsilyl groups, triethylsilyl groups, tert-butyldimethylsilyl groups, propyldimethylsilyl groups, vinyldimethylsilyl groups, and other alkylsilyl groups, phenyldimethylsilyl groups, tert-butyldiphenylsilyl groups, An arylsilyl group such as a phenylsilyl group or a trinaphthylsilyl group is shown. Substituents on silicon may be further substituted. Although carbon number of a silyl group is not specifically limited, Preferably it is the range of 1-30.

A siloxanyl group refers to a silicon compound group via an ether bond such as a trimethylsiloxanyl group. Substituents on silicon may be further substituted. The boryl group is a substituted or unsubstituted boryl group. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, an aryl ether group, an alkoxy group, and a hydroxyl group. Of these, an aryl group and an aryl ether group are preferable. The sulfo group is a substituted or unsubstituted sulfo group. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, an aryl ether group, and an alkoxy group. Of these, a linear alkyl group and an aryl group are preferable. The phosphine oxide group is a group represented by -P (= O) R ¹⁰ R ¹¹ . R ¹⁰ and R ¹¹ are selected from the same group as R ^{1 to} R ⁹ .

A condensed ring and an aliphatic ring formed between adjacent substituents are any two adjacent substituents (for example, R ¹ and R ^{2 in} the general formula (1)) bonded to each other to be conjugated or non-conjugated. Forming a cyclic skeleton. As a constituent element of such a condensed ring and an aliphatic ring, in addition to carbon, an element selected from nitrogen, oxygen, sulfur, phosphorus and silicon may be included. Moreover, these condensed rings and aliphatic rings may be condensed with another ring.

Since the compound represented by the general formula (1) exhibits a high emission quantum yield and has a small half-value width of the emission spectrum, it is possible to achieve both efficient color conversion and high color purity. Furthermore, the compound represented by the general formula (1) has various properties such as luminous efficiency, color purity, thermal stability, light stability and dispersibility by introducing an appropriate substituent at an appropriate position. And physical properties can be adjusted. For example, as compared to the case where R ¹ , R ³ , R ⁴ and R ⁶ are all hydrogen, at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted group. In the case of an aryl group, a substituted or unsubstituted heteroaryl group, better thermal stability and light stability are exhibited.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted alkyl group, the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, C1-C6 alkyl groups, such as a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group, are preferable. Furthermore, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group from the viewpoint of excellent thermal stability. Also, from the viewpoint of preventing concentration quenching and improving the emission quantum yield, this alkyl group is more preferably a sterically bulky tert-butyl group. Further, from the viewpoint of ease of synthesis and availability of raw materials, a methyl group is also preferably used as this alkyl group.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group or a naphthyl group, more preferably A phenyl group and a biphenyl group. Particularly preferred is a phenyl group.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted heteroaryl group, the heteroaryl group is preferably a pyridyl group, a quinolinyl group or a thienyl group, more preferably a pyridyl group , A quinolinyl group. Particularly preferred is a pyridyl group.

R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different, and a substituted or unsubstituted alkyl group is preferable because of good solubility in a binder resin and a solvent. In this case, the alkyl group is preferably a methyl group from the viewpoints of ease of synthesis and availability of raw materials.

R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different and when they are substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups, better thermal stability and This is preferable because it shows light stability. In this case, R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different, and are more preferably substituted or unsubstituted aryl groups.

  Some substituents improve multiple properties, but all have limited substituents that exhibit sufficient performance. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, by introducing a plurality of types of substituents into the compound represented by the general formula (1), it is possible to obtain a compound that is balanced in light emission characteristics, color purity, and the like.

In particular, R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different, and in the case of a substituted or unsubstituted aryl group, for example, R ¹ ≠ R ⁴ , R ³ ≠ R ⁶ , R It is preferable to introduce a plurality of types of substituents such as ¹ ≠ R ³ or R ⁴ ≠ R ⁶ . Here, “≠” indicates a group having a different structure. For example, R ¹ ≠ R ⁴ indicates that R ¹ and R ⁴ are groups having different structures. By introducing a plurality of types of substituents as described above, an aryl group that affects the color purity and an aryl group that affects the light emission efficiency can be introduced at the same time, so fine adjustment is possible.

Among these, R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ is preferable from the viewpoint of improving the light emission efficiency and the color purity in a balanced manner. In this case, for the compound represented by the general formula (1), one or more aryl groups that affect the color purity are introduced into the pyrrole rings on both sides, and the aryl that affects the luminous efficiency at other positions. Since groups can be introduced, both of these properties can be maximized. When R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ , it is more preferable that R ¹ = R ⁴ and R ³ = R ⁶ from the viewpoint of improving both heat resistance and color purity.

  As the aryl group mainly affecting the color purity, an aryl group substituted with an electron donating group is preferable. The electron donating group is an atomic group that donates electrons to a substituted atomic group by an induced effect or a resonance effect in organic electronic theory. Examples of the electron donating group include those having a negative value as the Hammett's rule substituent constant (σp (para)). The Hammett's rule substituent constant (σp (para)) can be cited from the Chemical Handbook, Basic Revised 5th edition (II-380).

Specific examples of the electron donating group include, for example, an alkyl group (σp of methyl group: −0.17), an alkoxy group (σp of methoxy group: −0.27), an amino group (σp of —NH ₂ : − 0.66). In particular, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, a tert-butyl group, and a methoxy group are more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable. When these are used as the above-described electron donating group, quenching due to aggregation of molecules is prevented in the compound represented by the general formula (1). be able to. Although the substitution position of the substituent is not particularly limited, it is necessary to suppress the twisting of the bond in order to increase the light stability of the compound represented by the general formula (1). It is preferable to bond to the position or para position. On the other hand, as the aryl group mainly affecting the luminous efficiency, an aryl group having a bulky substituent such as a tert-butyl group, an adamantyl group, or a methoxy group is preferable.

R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, and when they are substituted or unsubstituted aryl groups, R ¹ , R ³ , R ⁴ and R ⁶ are the same or different. It may be a substituted or unsubstituted phenyl group. At this time, R ¹ , R ³ , R ⁴ and R ⁶ are more preferably selected from the following Ar-1 to Ar- ⁶ , respectively. In this case, preferred combinations of R ¹ , R ³ , R ⁴ and R ⁶ include combinations shown in Table 1-1 to Table 1-11, but are not limited thereto.

R ² and R ⁵ are preferably any one of hydrogen, an alkyl group, a carbonyl group, an ester group, and an aryl group. Among these, hydrogen or an alkyl group is preferable from the viewpoint of thermal stability, and hydrogen is more preferable from the viewpoint of easily obtaining a narrow half-value width in the emission spectrum.

R ⁸ and R ⁹ are preferably an alkyl group, aryl group, heteroaryl group, fluorine, fluorine-containing alkyl group, fluorine-containing heteroaryl group or fluorine-containing aryl group. In particular, R ⁸ and R ⁹ are more preferably fluorine or a fluorine-containing aryl group because a higher fluorescence quantum yield is obtained with respect to excitation light. Further, R ⁸ and R ⁹ are more preferably fluorine for ease of synthesis.

  Here, the fluorine-containing aryl group is an aryl group containing fluorine, and examples thereof include a fluorophenyl group, a trifluoromethylphenyl group, and a pentafluorophenyl group. The fluorine-containing heteroaryl group is a heteroaryl group containing fluorine, and examples thereof include a fluoropyridyl group, a trifluoromethylpyridyl group, and a trifluoropyridyl group. The fluorine-containing alkyl group is an alkyl group containing fluorine, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group.

In the general formula (1), X is preferably C—R ⁷ from the viewpoint of light stability. When X is C—R ⁷ , the durability of the compound represented by the general formula (1) tends to be easily influenced by the substituent R ⁷ . Specifically, when R ⁷ is hydrogen, the reactivity of this site is high, and this site tends to react with moisture and oxygen in the air. In addition, when R ⁷ is a substituent having a high degree of freedom of movement of a molecular chain such as an alkyl group, the compounds tend to aggregate with time in the colored resin composition. Therefore, R ⁷ is preferably a group that is rigid and has a low degree of freedom of movement and does not easily cause aggregation. Specifically, R ⁷ is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Either is preferable.

X is C—R ⁷ and R ⁷ is preferably a substituted or unsubstituted aryl group from the viewpoint of giving a higher fluorescence quantum yield, being harder to thermally decompose, and from the viewpoint of light stability. As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, and an anthracenyl group are preferable from the viewpoint of not impairing the emission wavelength.

Furthermore, in order to increase the light stability of the compound represented by the general formula (1), it is preferable to moderately suppress the twist of the carbon-carbon bond between R ⁷ and the pyromethene skeleton. From this point of view, R ⁷ is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group. Of these, a phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted terphenyl group are more preferable. Particularly preferred is a substituted or unsubstituted phenyl group.

R ⁷ is preferably a moderately bulky substituent. When R ⁷ has a certain amount of bulkiness, aggregation of molecules can be prevented, and as a result, the luminous efficiency and durability of the compound represented by the general formula (1) are further improved.

A more preferred example of such a bulky substituent includes the structure of R ⁷ represented by the following general formula (2).

  In the general formula (2), r is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether Group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, sulfo group, phosphine oxide group Selected from the group consisting of k is an integer of 1 to 3. When k is 2 or more, r may be the same or different.

  From the viewpoint that a higher emission quantum yield can be provided, r is preferably a substituted or unsubstituted aryl group. Among these aryl groups, a phenyl group and a naphthyl group are particularly preferable examples. When r is an aryl group, k in the general formula (2) is preferably 1 or 2, and more preferably 2 from the viewpoint of further preventing aggregation of molecules. Furthermore, when k is 2 or more, it is preferable that at least one of r is substituted with an alkyl group. As an alkyl group in this case, a methyl group, an ethyl group, and a tert-butyl group are particularly preferable examples from the viewpoint of thermal stability.

  Further, from the viewpoint of controlling the fluorescence wavelength and absorption wavelength, and increasing the compatibility with the solvent, r is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen. , A methyl group, an ethyl group, a tert-butyl group, and a methoxy group are more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable. When r is a tert-butyl group or a methoxy group, it is more effective for preventing quenching due to aggregation between molecules.

Further, as another embodiment of the compounds represented by the general formula (1), it is preferred that at least one of R ¹ to R ⁷ is an electron withdrawing group. In particular, (1) at least one of R ^{1 to} R ⁶ is an electron withdrawing group, (2) R ⁷ is an electron withdrawing group, or (3) at least one of R ^{1 to} R ^6. It is preferred that one is an electron withdrawing group and R ⁷ is an electron withdrawing group. Thus, by introducing an electron withdrawing group into the pyromethene skeleton of the above compound, the electron density of the pyromethene skeleton can be greatly reduced. Thereby, stability with respect to the oxygen of the said compound improves more, As a result, durability of the said compound can be improved more.

  The electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from a substituted atomic group by an induced effect or a resonance effect in organic electron theory. Examples of the electron withdrawing group include those having a positive value as the Hammett's rule substituent constant (σp (para)). The Hammett's rule substituent constant (σp (para)) can be cited from the Chemical Handbook, Basic Revised 5th edition (II-380). In addition, although a phenyl group also has the example which takes the above positive values, in this invention, a phenyl group is not contained in an electron withdrawing group.

Examples of electron withdrawing groups include, for example, -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -I (σp: +0.18), -CO ₂ R ¹² (σp: when R ¹² is an ethyl group +0.45), -CONH ₂ (σp: +0.38), -COR ¹² (when σp: R ¹² is a methyl group +0.49),- _{CF 3 (σp: +0.50),} - SO 2 R 12 (σp: when ^{R 12} is a methyl group _{+0.69), - NO 2 (σp} : +0.81) , and the like. R ¹² each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, substituted or unsubstituted A substituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms are represented. Specific examples of these groups include the same examples as described above.

  Preferred electron withdrawing groups include fluorine, fluorine-containing aryl groups, fluorine-containing heteroaryl groups, fluorine-containing alkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups, substituted or unsubstituted amide groups, Examples thereof include a substituted or unsubstituted sulfonyl group or a cyano group. This is because they are difficult to decompose chemically.

  More preferable examples of the electron withdrawing group include a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, or a cyano group. This is because these lead to effects of preventing concentration quenching and improving the emission quantum yield. Particularly preferred electron withdrawing groups are substituted or unsubstituted ester groups.

Among them, at least one of R ² and R ⁵ may be the same or different from each other, and being a substituted or unsubstituted ester group can improve durability without deteriorating color purity. preferable. In particular, both R ² and R ⁵ may be the same or different, and a substituted or unsubstituted ester group is particularly preferable from the viewpoint of improving durability.

As one of preferable examples of the compound represented by the general formula (1), R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different and each is a substituted or unsubstituted alkyl group. In addition, there is a case where X is C—R ⁷ and R ⁷ is a group represented by the general formula (2). In this case, R ⁷ is particularly preferably a group represented by the general formula (2) in which r is included as a substituted or unsubstituted phenyl group.

Further, as another preferred example of the compound represented by the general formula (1), R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different, and the above Ar-1 To Ar-6, and X is C—R ⁷ and R ⁷ is a group represented by the general formula (2). In this case, R ⁷ is more preferably a group represented by the general formula (2) in which r is included as a tert-butyl group or a methoxy group, and is represented by the general formula (2) in which r is included as a methoxy group. It is particularly preferred that

Further, as another preferred example of the compound represented by the general formula (1), R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different, and may be substituted or unsubstituted. An alkyl group, and R ² and R ⁵ may be the same or different from each other, are substituted or unsubstituted ester groups, X is C—R ⁷ , and R ⁷ has the general formula The case where it is group represented by (2) is mentioned. In this case, R ⁷ is particularly preferably a group represented by the general formula (2) in which r is included as a substituted or unsubstituted phenyl group.

Further, as another preferred example of the compound represented by the general formula (1), R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different, and the above Ar-1 To Ar-6, and R ² and R ⁵ may be the same or different, each is a substituted or unsubstituted ester group, X is C—R ⁷ , and R ⁷ is The case where it is group represented by General formula (2) is mentioned. In this case, R ⁷ is more preferably a group represented by the general formula (2) in which r is included as a tert-butyl group or a methoxy group, and is represented by the general formula (2) in which r is included as a methoxy group. It is particularly preferred that

  As a compound represented by General formula (1), the compound which has a structure shown below is mentioned, for example.

  The compound represented by the general formula (1) can be synthesized, for example, by the methods described in JP-T-8-509471 and JP-A-2000-208262. That is, the target pyromethene metal complex is obtained by reacting a pyromethene compound and a metal salt in the presence of a base.

For the synthesis of a pyromethene-boron fluoride complex, see J.A. Org. Chem. , Vol. 64, no. 21, pp. 7813-7819 (1999), Angew. Chem. , Int. Ed. Engl. , Vol. 36, pp. With reference to the method described in 1333-1335 (1997) etc., the compound represented by General formula (1) is compoundable. For example, after heating the compound represented by the following general formula (7) and the compound represented by the general formula (8) in 1,2-dichloroethane in the presence of phosphorus oxychloride, the following general formula (9) A method of reacting the represented compound in 1,2-dichloroethane in the presence of triethylamine, thereby obtaining a compound represented by the general formula (1) can be mentioned. However, the present invention is not limited to this. Here, R ^{1 to} R ⁹ are the same as described above. J represents a halogen.

  Furthermore, when introducing an aryl group or a heteroaryl group, a method of generating a carbon-carbon bond using a coupling reaction between a halogenated derivative and a boronic acid or a boronic acid esterified derivative can be mentioned. However, the present invention is not limited to this. Similarly, when introducing an amino group or a carbazolyl group, for example, there is a method of generating a carbon-nitrogen bond by using a coupling reaction between a halogenated derivative and an amine or a carbazole derivative under a metal catalyst such as palladium. However, the present invention is not limited to this.

  When the pyromethene derivative is used in a red resin composition, it preferably absorbs light other than red light and emits red light. In addition, the red light emission as used in the field of this invention refers to the light emission observed in the area | region with a wavelength of 580 to 780 nm. In the present invention, it is preferable that a peak wavelength of light emission is observed in a red region having a wavelength of 580 nm or more and 780 nm or less in spectroscopic analysis of a region having a wavelength of 400 nm or more and 780 nm or less. Here, the peak wavelength of light emission can be measured using, for example, an F-2500 type spectrofluorometer (manufactured by Hitachi, Ltd.).

  The wavelength of light absorbed by the pyromethene derivative is preferably shorter than the light emitted, and preferably includes light in the wavelength range of 400 to 579 nm. In general, the higher the energy of the excitation light, the easier the material is decomposed. However, the excitation light in the wavelength range of 400 to 579 nm is of relatively low excitation energy. For this reason, decomposition | disassembly of the pyromethene derivative in a colored resin composition can be suppressed. It is more preferable to absorb light (green) in the wavelength range of 500 to 579 nm. By absorbing light in the green region, the wavelength selectivity in the red region is further improved, so that the color purity of the red resin composition can be further improved.

  On the other hand, when the pyromethene derivative is used in a green resin composition, it preferably absorbs light other than green and emits green light. Note that the green light emission referred to in the present invention refers to light emission observed in a wavelength region of 500 nm or more and 579 nm or less. In the present invention, it is preferable that the peak wavelength of light emission is observed in the green region having a wavelength of 500 nm or more and 579 nm or less in the spectroscopic analysis of the region having a wavelength of 400 nm or more and 780 nm or less.

  The wavelength of light absorbed by the pyromethene derivative is preferably shorter than the light emitted, and preferably includes light (blue) in the wavelength range of 400 to 499 nm. By absorbing light in the blue region, the wavelength selectivity in the green region is further improved, so that the color purity of the green resin composition can be further improved.

  From the viewpoint of further improving the luminance, the content of the pyromethene derivative in the colored resin composition of the present invention is preferably 1 part by weight or more, preferably 5 parts by weight or more with respect to 100 parts by weight of the yellow colorant described later. More preferred. On the other hand, the content of the pyromethene derivative is preferably 100 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the yellow colorant, from the viewpoint of further improving luminance by suppressing concentration quenching. .

  The colored resin composition of the present invention may contain a light emitting material other than the pyromethene derivative. Here, the light emitting material in the present invention refers to a material that emits light having a wavelength different from that of light when irradiated with some light. Examples of the luminescent material include inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots. Among these, organic light emitting materials are preferable from the viewpoints of dispersibility, reduction of usage, and reduction of environmental load. Here, the organic light emitting material refers to an organic light emitting material.

  Examples of organic light-emitting materials other than pyromethene derivatives include compounds having derivatives aryl rings such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, indene and derivatives thereof; furan, pyrrole, Heteroaryl such as thiophene, silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine Compounds having a ring and derivatives thereof; borane derivatives, etc .; 1,4-distyrylbenzene, 4,4′-bis (2- (4-diphenylaminophenyl) ethenyl) biphe , Stilbene derivatives such as 4,4′-bis (N- (stilben-4-yl) -N-phenylamino) stilbene; aromatic acetylene derivatives; tetraphenylbutadiene derivatives; aldazine derivatives; diketopyrrolo [3,4-c Pyrrole derivatives; coumarin derivatives such as coumarin 6, coumarin 7, coumarin 153; azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole and metal complexes thereof; cyanine compounds such as indocyanine green; Xanthene compounds such as fluorescein, eosin and rhodamine; thioxanthene compounds; polyphenylene compounds; naphthalimide derivatives; phthalocyanine derivatives and metal complexes thereof; porphyrin derivatives and metal complexes thereof; Oxazine compounds such as Nile Blue; helicene compounds; aromatics such as N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine Examples of amine derivatives include organometallic complex compounds such as iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re).

  When the colored resin composition is a red resin composition, it preferably contains an organic light-emitting material that absorbs light other than green and emits green light together with a pyromethene derivative that emits red light. The wavelength of the light to be absorbed is preferably shorter than that of the emitted light, and preferably includes blue light. By combining a pyromethene derivative that emits red light and an organic light-emitting material that emits green light, the light emission of the organic light-emitting material that emits green light is absorbed by the pyromethene derivative that emits red light, so that the luminance can be further improved. . The organic light emitting material that emits green light may be a pyromethene derivative or an organic light emitting material other than the pyromethene derivative.

  When combining a pyromethene derivative that emits red light and an organic light emitting material that emits green light, the content of the organic light emitting material that emits green light is 100 parts by weight of the pyromethene derivative that emits red light from the viewpoint of further improving luminance. Is preferably 0.1 parts by weight or more, and more preferably 10 parts by weight or more. On the other hand, the content of the organic light-emitting material that emits green light is 500 weights or less with respect to 100 parts by weight of the pyromethene derivative that emits red light from the viewpoint of improving compatibility with the binder resin and the reactive monomer. Preferably, 150 weight or less is more preferable.

  The colored resin composition of the present invention contains a yellow colorant. Examples of the colorant include organic pigments, inorganic pigments, dyes, and the like. Two or more of these may be contained. Among these, organic pigments and dyes are preferable from the viewpoint of transparency of the colored resin composition. The organic pigment may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment and the like, if necessary.

  Examples of the yellow colorant include CI pigment yellow (hereinafter, “PY”) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, and 137. 138, 139, 147, 148, 150, 153, 154, 166, 168, 185, 231 and the like. From the viewpoint of coloring power and absorption band, PY129, 138, 139, 150, and 185 are preferable, and PY139, 150, and 185 are more preferable.

  The colored resin composition of the present invention may contain a colorant other than the yellow colorant.

  Examples of the red colorant include C.I. I. Pigment Red (hereinafter “PR”) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217, 220, 223, 224, 226 227, 228, 240, 242, 254, 264, 269, 291 and the like. From the viewpoint of further improving the luminance, PR242, 254, and 291 are preferable, and 242 and 291 are more preferable.

  Examples of the orange colorant include C.I. I. Pigment orange (hereinafter “PO”) 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 72, 73, 74, 77, 84, and the like. . From the viewpoint of further improving luminance, PO71 is preferable, and from the viewpoint of further improving color purity, PO73 is preferable.

  Examples of the green colorant include C.I. I. Pigment green (hereinafter “PG”) 7, 10, 36, 58, 59, and the like.

  Examples of the blue colorant include C.I. I. Pigment blue (hereinafter “PB”) 15: 3, 15: 4, 15: 6, 16, 21, 22, 60, 64, triarylmethane dyes, and the like.

  Examples of purple colorants include C.I. I. Pigment violet (hereinafter “PV”) 19, 23, 29, 30, 37, 40, 50, xanthene dyes, and the like (all numbers are color index No.).

  When the colored resin composition of the present invention is a red resin composition, it preferably contains a red colorant and / or an orange colorant, and the color purity of the red resin composition can be further improved. Furthermore, the red colorant can be colored deeper red. In addition, the orange colorant can further improve the luminance because it efficiently transmits the light necessary for the organic light emitting material to emit red light.

  When the colored resin composition of the present invention is a red resin composition, the content of the yellow colorant in the red resin composition is based on 100 parts by weight of the total content of the colorant from the viewpoint of further improving the luminance. 50 parts by weight or more is preferable, and 55 parts by weight or more is more preferable. On the other hand, the content of the yellow colorant is preferably 99 parts by weight or less and more preferably 80 parts by weight or less with respect to 100 parts by weight of the total content of the colorants, from the viewpoint of further improving the color purity.

  When the colored resin composition of the present invention contains a red colorant, the content of the red colorant is 100 parts by weight of the total content of the colorant from the viewpoint of improving the color purity and coloring deep red. The amount is preferably 5 parts by weight or more, more preferably 15 parts by weight or more. On the other hand, the content of the red colorant is preferably 60 parts by weight or less and more preferably 45 parts by weight or less with respect to 100 parts by weight of the total content of the colorants from the viewpoint of further improving the luminance.

  When the colored resin composition of the present invention contains an orange colorant, the content of the orange colorant is 5 parts by weight or more with respect to 100 parts by weight of the total content of the colorant from the viewpoint of further improving the luminance. Preferably, 15 parts by weight or more is more preferable. On the other hand, the content of the orange colorant is preferably 70 parts by weight or less and more preferably 50 parts by weight or less with respect to 100 parts by weight of the total content of the colorant from the viewpoint of further improving the luminance.

  When the colored resin composition of this invention is a green resin composition, it is preferable to contain a blue colorant, and the color purity of a green resin composition can be improved more.

  When the colored resin composition of the present invention is a green resin composition, the content of the yellow colorant in the green resin composition is based on 100 parts by weight of the total content of the colorant from the viewpoint of further improving the luminance. 50 parts by weight or more is preferable, and 55 parts by weight or more is more preferable. On the other hand, the content of the yellow colorant is preferably 99 parts by weight or less and more preferably 95 parts by weight or less with respect to 100 parts by weight of the total content of the colorant from the viewpoint of further improving the color purity.

  When the colored resin composition of the present invention contains a blue colorant, the content of the blue colorant is 100 parts by weight of the total content of the colorant from the viewpoint of further improving the color purity and coloring deep green. Is preferably 0.1 parts by weight or more, and more preferably 1 part by weight or more. On the other hand, the content of the blue colorant is preferably 50 parts by weight or less and more preferably 20 parts by weight or less with respect to 100 parts by weight of the total content of the colorants from the viewpoint of further improving the luminance.

  The colored resin composition of the present invention contains a binder resin. Examples of the binder resin include acrylic resin, epoxy resin, polyimide resin, urethane resin, urea resin, polyvinyl alcohol resin, melamine resin, polyamide resin, polyamideimide resin, polyester resin, polyolefin resin, and polymer dispersant. It is done. Two or more of these may be contained. Among these, an acrylic resin is preferable from the viewpoint of stability.

  Examples of the acrylic resin include a polymer of an unsaturated carboxylic acid and a copolymer of an unsaturated carboxylic acid and another ethylenically unsaturated compound. Among these, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferable.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and vinyl acetic acid. Two or more of these may be used.

  Examples of the ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, isopropyl methacrylate, n-propyl methacrylate, and n-acrylate. Butyl, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, Unsaturated carboxylic acid alkyl esters such as n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate; styrene, p-methylstyrene, o-methyl Aromatic vinyl compounds such as styrene, m-methylstyrene and α-methylstyrene; Unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Vinyl acetate and propionic acid Carboxylic acid vinyl esters such as vinyl; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile; aliphatic conjugated dienes such as 1,3-butadiene and isoprene; polystyrene having an acryloyl group or a methacryloyl group at the terminal; Examples thereof include macromonomers such as polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone.

  The acrylic resin preferably has an ethylenically unsaturated group in the side chain, and can improve the sensitivity when the colored resin composition has photosensitivity. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group. As a method for introducing an ethylenically unsaturated group into the side chain of an acrylic resin, when the acrylic resin has a carboxyl group or a hydroxyl group, an ethylenically unsaturated compound having an epoxy group, acrylic chloride, methacrylic acid, etc. Examples of the method include addition reaction of chloride and the like, and addition of a compound having an ethylenically unsaturated group using isocyanate.

  As an acrylic resin having an ethylenically unsaturated group in the side chain, for example, “Cyclomer” (registered trademark) P (ACA) Z250 (a 45% by weight solution of dipropylene glycol monomethyl ether, acid, manufactured by Daicel Ornex Co., Ltd.) 110 mg KOH / g, weight average molecular weight 20,000) and the like.

  The colored resin composition of the present invention preferably contains a reactive monomer and a photopolymerization initiator. By containing these, radicals are generated by ultraviolet irradiation, the colored resin composition is cured, and pattern processability can be imparted.

  Examples of reactive monomers include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylate, anhydrous Phthalic acid propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin-modified epoxy di (meth) acrylate, oligomer such as alkyd-modified (meth) acrylate, tripropylene glycol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetra Limethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, bisphenoxyethanol full Examples thereof include orange acrylate, dicyclopentanedienyl diacrylate, alkyl-modified products thereof, alkyl ether-modified products, and alkyl ester-modified products. Two or more of these may be contained.

  The photopolymerization initiator refers to a compound that decomposes and / or reacts with light (including ultraviolet rays or electron beams) to generate radicals. Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, anthraquinone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, oxime ester compounds, triazine compounds, phosphorus compounds, and titanates. Examples thereof include inorganic photopolymerization initiators. Two or more of these may be contained. In order to easily adjust the content of the photopolymerization initiator to a preferable range described later, a nitrocarbazole-based oxime ester compound that is sensitive to h-line is preferable.

  More specifically, examples of the benzophenone compound include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, and 4-methoxy-4′-dimethylaminobenzophenone. Examples of acetophenone compounds include 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propane, “Irgacure” (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone), 379 (2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) and the like. As an anthraquinone compound, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthra Examples include quinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, and 2-phenylanthraquinone. Examples of the imidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer. An example of the benzothiazole compound is 2-mercaptobenzothiazole. Examples of the benzoxazole-based compound include 2-mercaptobenzoxazole. Examples of the triazine compound include 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine. Examples of the oxime ester compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (“IRGACURE” (registered trademark) OXE01, manufactured by BASF Corporation), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) ("IRGACURE" OXE03), "IRGACURE" OXE04, "Adeka Arcles “(Registered trademark) NCI-930,“ ADEKA ARKLES ”NCI-831,“ ADEKA ARKLES ”N-1919, PBG-345 manufactured by Changzhou Power Electronics New Materials Co., Ltd., and the like. Among these, an oxime ester compound is preferable from the viewpoint of high sensitivity, and a nitrocarbazole-based oxime ester compound is more preferable from the viewpoint of suppressing a decrease in luminance when oxygen is blocked. As the nitrocarbazole-based oxime ester compound, NCI-831, PBG-345 and the like are preferable.

  In the colored resin composition of the present invention, the content of the photopolymerization initiator is 0.1 parts by weight or more with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer from the viewpoint of further promoting photocuring. Preferably, 0.5 weight part or more is more preferable. On the other hand, the content of the photopolymerization initiator is 45 with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer from the viewpoint of improving the solvent resistance by suppressing the elution of the remaining photopolymerization initiator. Part by weight or less is preferable and 35 parts by weight or less is more preferable.

  The colored resin composition of the present invention may contain an organic solvent. Examples of the organic solvent include diethylene glycol monobutyl ether acetate, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, ethylene glycol monobutyl ether acetate, diethyl oxalate, ethyl acetoacetate, Cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentylpropionate, propylene glycol monomethyl ether propionate, pentyl acetate, propylene glycol monomethyl ether Acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene Glycol monoethyl ether, diethylene glycol monomethyl ether, monoethyl ether, methyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate , Isopentylbutanol acetate, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexanone, xylene, ethylbenzene, solvent naphtha, compounds represented by the following general formula (6), and the like. It is done. Two or more of these may be contained. Among these, a compound represented by the following general formula (6) is preferable from the viewpoint of solubility of the pyromethene derivative.

In the general formula ^{(6), R} 18 ~R ²⁰ each independently represents an alkyl group having 1 to 10 carbon atoms.

  A compound represented by the following structural formula (10) and a compound represented by the following structural formula (11) are more preferable.

  Examples of the compound represented by the general formula (6) include “Examide” (registered trademark) B-100, M-100 (all of which are manufactured by Idemitsu Kosan Co., Ltd.).

  The content of the compound represented by the general formula (6) in the colored resin composition of the present invention is the total of the organic solvents from the viewpoint of further improving the luminance by dissolving the pyromethene derivative more uniformly in the colored resin composition. The content is preferably 0.1 parts by weight or more and more preferably 10 parts by weight or more with respect to 100 parts by weight. On the other hand, the content of the compound represented by the general formula (6) is preferably 80 parts by weight or less with respect to 100 parts by weight of the total solvent content from the viewpoint of compatibility with the binder resin and the reactive monomer. 60 parts by weight or less is more preferable, and 40 parts by weight or less is more preferable.

  The colored resin composition of the present invention preferably contains a compound represented by the following general formula (3) and a compound represented by the following general formula (4).

In the general formula (3), Y represents a hydroxyl group or —R ¹⁰ —OH, and Z represents a hydroxyl group or R ¹¹ —OH. However, R < ¹⁰ > -R < ¹¹ > represents a C1-C5 alkylene group each independently. R ^{12 to} R ¹³ each independently represent hydrogen or an alkyl group having 1 to 15 carbon atoms. In the general formula (4), R ^{14 to} R ¹⁵ each independently represent hydrogen or an alkyl group having 1 to 15 carbon atoms.

  By containing the compound represented by the general formula (4), the oxidative decomposition of the organic light emitting material can be suppressed, and the luminance can be further improved. From the viewpoint of improving the compatibility of the compound represented by the general formula (4) in the colored resin composition and more effectively suppressing the photodecomposition of the organic light emitting material, it is represented by the general formula (3). It is preferable to combine with a compound.

From the viewpoint of further improving the compatibility of the compound represented by the general formula (4) in the colored resin composition, Y and Z in the general formula (3) are hydroxyl groups, or R ^{10 to} R ¹¹ are carbon numbers. It is preferable that it is 1-3 alkylene groups. R ^{12 to} R ¹³ are preferably hydrogen or an alkyl group having 1 to 5 carbon atoms.

  Examples of the compound represented by the general formula (3) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9- Bis [4- (2-hydroxyethoxy) phenyl] fluorene and the like can be mentioned.

  In the colored resin composition of the present invention, the content of the compound represented by the general formula (3) is from the viewpoint of further improving the compatibility of the compound represented by the general formula (4) in the colored resin composition. , 0.1 part by weight or more is preferable with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer, and more preferably 1 part by weight or more. On the other hand, the content of the compound represented by the general formula (3) is based on 100 parts by weight of the total content of the binder resin and the reactive monomer from the viewpoint of further improving the pattern processability of the colored resin composition. 30 parts by weight or less is preferable, 20 parts by weight or less is more preferable, and 10 parts by weight or less is more preferable.

From the viewpoint of further suppressing the photodecomposition of the organic light emitting material in the general formula (3), R ^{14 to} R ¹⁵ in the general formula (4) are preferably an alkyl group having 10 to ¹⁵ carbon atoms. As the compound represented by the general formula (4), a compound represented by the following structural formula (12) is more preferable.

  In the colored resin composition of the present invention, the content of the compound represented by the general formula (4) is the general formula (3) from the viewpoint of further improving luminance by suppressing photolysis of the organic light emitting material. 0.1 weight part or more is preferable with respect to 100 weight part of content of the represented compound, and 1 weight part or more is more preferable. On the other hand, the content of the compound represented by the general formula (4) is 100 parts by weight of the compound represented by the general formula (3) from the viewpoint of further improving the pattern processability of the colored resin composition. The amount is preferably 30 parts by weight or less, and more preferably 20 parts by weight or less.

  The colored resin composition of the present invention preferably contains a compound represented by the following general formula (5) from the viewpoint of suppressing the oxidative decomposition of the organic light emitting material and further improving the luminance.

In said general formula (5), R < ¹⁶ > -R < ¹⁷ > represents a C1-C10 alkyl group each independently. From the viewpoint of compatibility in the colored resin composition, R ¹⁶ and R ¹⁷ are preferably an alkyl group having 5 to 10 carbon atoms.

  Examples of the compound represented by the general formula (5) include dimethyl 3,3′-dithiopropionate, dioctyl 3,3′-dithiodipropionate, and the like. Dioctyl 3,3'-dithiodipropionate is more preferred.

  In the colored resin composition of the present invention, the content of the compound represented by the general formula (5) is selected from the viewpoint of further suppressing the oxidative decomposition of the organic light emitting material when performing the heat treatment. 0.01 parts by weight or more is preferable and 0.1 parts by weight or more is more preferable with respect to 100 parts by weight of the total content. On the other hand, the content of the compound represented by the general formula (5) is based on 100 parts by weight of the total content of the binder resin and the reactive monomer from the viewpoint of further improving the pattern processability of the colored resin composition. 10 parts by weight or less is preferable, 3 parts by weight or less is more preferable, and 1 part by weight or less is more preferable.

  The colored resin composition of the present invention may contain additives such as an adhesion improver, a surfactant, a polymerization inhibitor, an antioxidant, an ultraviolet curing aid, and a sensitization aid.

  By containing the adhesion improving agent, the development adhesion between the colored resin composition and the substrate can be improved. Examples of the adhesion improving agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples include silane coupling agents such as trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Two or more of these may be contained.

  The content of the adhesion improver is 0.1 with respect to 100 parts by weight of the total content of the binder resin and the monomer having an ethylenically unsaturated group from the viewpoint of improving the development adhesion between the colored resin composition and the substrate. Part by weight or more is preferable, and 1 part by weight or more is more preferable. On the other hand, from the viewpoint of suppressing aggregation of the resin, 30 parts by weight or less is preferable and 15 parts by weight or less is more preferable with respect to 100 parts by weight of the total content of the binder resin and the monomer having an ethylenically unsaturated group.

  By containing the surfactant, the coating property and the uniformity of the coating film surface can be improved. Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; lauryldimethylamine oxide and lauryl. Amphoteric surfactants such as carboxymethylhydroxyethyl imidazolium betaine; Nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate; Fluorosurfactant; Silicone surfactant Is mentioned. Two or more of these may be contained.

  The content of the surfactant is preferably 0.01 parts by weight or more with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer, from the viewpoint of improving the coatability of the colored resin composition. More preferred are parts by weight. On the other hand, the content of the surfactant is preferably 10 parts by weight or less and more preferably 5 parts by weight or less with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer from the viewpoint of improving the surface uniformity. .

  By containing a polymerization inhibitor, stability can be improved. Polymerization inhibitors generally inhibit or stop polymerization due to radicals generated by heat, light, radical initiators, etc., and are used to prevent gelation of thermosetting resins or to stop polymerization during polymer production. Is done. Examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2,5-bis (1,1-dimethylbutyl) hydroquinone, Catechol, tert-butylcatechol and the like can be mentioned. Two or more of these may be contained.

  From the viewpoint of improving the temporal stability of the colored resin composition, the content of the polymerization inhibitor is preferably 0.001 part by weight or more with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer. More preferred is 01 parts by weight or more. On the other hand, the content of the polymerization inhibitor is 10 parts by weight or less with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer, from the viewpoint of further improving the pattern processability and temporal stability of the colored resin composition. Is preferably 1 part by weight or less.

  By containing the antioxidant, it is possible to suppress oxidative decomposition of the organic light-emitting material when performing the heat treatment. Examples of the antioxidant include phenolic compounds, phosphorus compounds, sulfur compounds, disulfide compounds and the like. Two or more of these may be contained. Examples of phenolic compounds include 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- {3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane. Examples of the phosphorus-based antioxidant include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine. Pin-6-yl] oxy] ethyl] amine, tetraphenyl (tetratridecyl) pentaerythritol tetraphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene-di-phosphonite, tetrakis (2,4-di-tert-butylphenyl) 4,3′-biphenylene-di-phosphonite, tetrakis (2,4-di-tert-butylphenyl) 3,3′-biphenylene-di-phosphonite, and the like. . These compounds include, for example, “Adeka Stub” (registered trademark) 1500 (manufactured by ADEKA), “Hostanox” (registered trademark) P-EPQ (manufactured by Clariant Japan), JPP-613M (Johoku Chemical Industry). Etc.) and so on. Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3 ′. -Thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5.5] An undecane etc. are mentioned. As other antioxidants, “ADEKA ARKLES” (registered trademark) GPA-5001 (manufactured by ADEKA Corporation) and the like are sold.

  The content of the antioxidant is 0.01 parts by weight or more with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer, from the viewpoint of further suppressing the oxidative decomposition of the organic light emitting material when performing the heat treatment. Is preferable, and 0.1 part by weight or more is more preferable. On the other hand, the content of the antioxidant is preferably 10 parts by weight or less with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer, from the viewpoint of further improving the pattern processability of the colored resin composition. More preferred are parts by weight or less.

  Examples of the ultraviolet curing aid include polyfunctional thiol compounds. Examples of the polyfunctional thiol compound include trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis. And polyfunctional thiol compounds such as (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). Two or more of these may be contained.

  From the viewpoint of improving the development adhesion between the colored resin composition and the substrate, the content of the ultraviolet curing aid is 0.01 parts by weight or more with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer. Preferably, 0.1 weight part or more is more preferable. On the other hand, from the viewpoint of suppressing aggregation of the binder resin, 10 parts by weight or less is preferable and 5 parts by weight or less is more preferable with respect to 100 parts by weight of the total content of the binder resin and the reactive monomer.

  Examples of the sensitization aid include aromatic or aliphatic tertiary amines and thioxanthone compounds.

  The colored resin composition of the present invention is prepared by, for example, preparing a colorant dispersion by dispersing a colorant containing a yellow colorant, a binder resin, and, if necessary, a solvent and other components with a disperser. If necessary, it can be obtained by blending other organic light-emitting materials, reactive monomers, photopolymerization initiators, organic solvents and other components. Examples of the disperser include a sand mill, a ball mill, a bead mill, a three roll mill, and an attritor. Among these, a bead mill excellent in dispersion efficiency is preferable. Examples of the dispersed beads include zirconia beads, alumina beads, and glass beads. Among these, zirconia beads are preferable. When a pigment is contained as a colorant, it is preferable to add a solvent or the like to the pigment powder in advance and make secondary particles (particle diameter of about 1 to 50 μm) finer by a disperser.

  The color filter substrate of the present invention has pixels comprising the colored resin composition of the present invention and / or a cured product thereof on the substrate. The color filter substrate of the present invention may further have a black matrix, a flattened film, a photospacer, a transparent electrode, an alignment film, and the like as necessary.

  Examples of pixel pattern shapes include rectangles, stripes, squares, polygons, undulations, and uneven shapes. The width of the pixel is preferably 0.5 μm or more, and preferably 1 μm or more, from the viewpoint of increasing the opening area and improving the transmittance. On the other hand, from the viewpoint of displaying a denser image, it is preferably 400 μm or less, more preferably 100 μm or less, and even more preferably 50 m or less.

  The film thickness of the pixel is preferably 1.0 m or more and more preferably 1.5 μm or more from the viewpoint of displaying a high color gamut. On the other hand, the film thickness of the pixel is preferably 10 μm or less and more preferably 5 μm or less from the viewpoint of improving the transmittance.

  Examples of the substrate include quartz glass, aluminoborosilicate glass, aluminosilicate glass, alkali aluminosilicate glass, soda lime glass coated with silica on the surface, organic plastic film, and sheet. It is done. Note that when the display device including the color filter substrate of the present invention is a reflective display device, the substrate may be opaque.

  A black matrix (hereinafter, “BM”) is formed between a pixel and a pixel adjacent to the pixel to increase the contrast of the display image. The BM may be formed by overlapping a part of pixels adjacent to each other (color overlap BM). However, the display image is improved by suppressing the step of the pixel, and high light shielding properties are obtained. Therefore, it is preferable to separately form a resin BM containing a resin and a light shielding material.

  Examples of the resin forming the resin BM include an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, and a siloxane resin. Among these, a polyimide resin having high heat resistance and high organic solvent resistance is preferable.

  Examples of the light shielding material forming the resin BM include black organic pigments, mixed color organic pigments, and inorganic pigments. Examples of the black organic pigment include carbon black, resin-coated carbon black, perylene black, and aniline black. Examples of the mixed-color organic pigment include those obtained by mixing pigments such as red, blue, green, purple, yellow, magenta, and cyan, and making them pseudo black. Examples of inorganic pigments include graphite, titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other fine metal particles, metal oxides, composite oxides, metal sulfides, metal nitrides, metals Carbide etc. are mentioned. Among these, titanium black, titanium nitride, titanium carbide, and carbon black are preferable, and titanium black is more preferable.

  The resin BM may further contain an adhesion improver, a polymer dispersant, a polymerization initiator, an acid generator, a base generator, a surfactant, and the like.

  The thickness of the BM is preferably 0.5 μm or more and more preferably 1.0 μm or more from the viewpoint of improving the light shielding property and the resistance value. On the other hand, from the viewpoint of improving flatness, the film thickness is preferably 10 μm or less, and more preferably 5 μm or less.

  The planarizing film is formed in order to planarize a step generated when a pixel or a BM is formed. The planarization film may be formed on the entire surface of the pixel or BM, or a pattern may be formed to selectively planarize a portion to be planarized. When the planarizing film is formed on the entire surface of the pixel or BM, it is preferable to use a thermosetting resin composition, and when forming a pattern, it is preferable to use a photosensitive resin composition.

  Examples of the resin for forming the planarizing film include those exemplified as the resin for forming the resin BM.

  The planarization film may further contain an adhesion improver, a polymerization initiator, an acid generator, a base generator, a surfactant, and the like.

  The thickness of the planarization film is preferably 0.5 μm or more, and more preferably 1.0 μm or more, from the viewpoint of flatness and suppressing elution of impurities from the pixel. On the other hand, from the viewpoint of improving transparency, the film thickness is preferably 5 μm or less, and more preferably 3 μm or less.

  The photo spacer is formed in order to adjust a gap between the color filter substrate and the thin film transistor (TFT) substrate.

  Examples of the resin that forms the photospacer include those exemplified as the resin that forms the resin BM. Acrylic resins, urethane resins, and siloxane resins that have good mechanical properties, transparency, and pattern processability are preferred.

  The photospacer may contain inorganic oxide fine particles, metal fine particles, resin fine particles and the like as fillers, and can improve the mechanical properties. Examples of the inorganic oxide fine particles include fine particles of silica, alumina, titania, barium sulfate, and the like. Examples of the metal fine particles include fine particles such as gold, silver, and copper. Examples of the resin fine particles include fine particles such as acrylic, styrene, silicone, and fluorine-containing polymer.

  The transparent electrode is formed as a counter electrode of the pixel electrode of the TFT substrate. In the liquid crystal display, in the case of the vertical alignment (VA) method, it is necessary to form a transparent electrode on the CF, but in the case of the in-plane switching (IPS) method or the fringe field switching (FFS) method, the transparent electrode is formed on the CF. The transparent electrode need not be formed.

  The transparent electrode is preferably formed of, for example, Indium-Tin-Oxide (ITO), Indium-Zinc-Oxide (InZnO), or the like.

  The alignment film is formed to align liquid crystal molecules in the liquid crystal cell. The alignment film is preferably a light distribution film formed by a photo-alignment method because uniform liquid crystallinity can be realized without generation of static electricity or dust. Examples of the resin for forming the alignment film include polyamic acid resins, polyimide resins, polyamic acid ester resins, polyester resins, polyamide resins, siloxane resins, cellulose resins, polyacetal resins, polystyrene resins, An acrylic resin, an epoxy resin, etc. are mentioned. In addition, these resins may contain, for example, an azobenzene structure or a stilbene structure as a structural site where photoisomerization occurs upon light irradiation.

  The alignment film may further contain an adhesion improver, a polymerization initiator, a surfactant, and the like.

  The thickness of the alignment film is preferably 0.001 μm or more, more preferably 0.005 μm or more, from the viewpoint of improving liquid crystal alignment. On the other hand, from the viewpoint of improving transparency, the film thickness is preferably 0.5 μm or less, and more preferably 0.05 μm or less.

  The alignment film is preferably subjected to a photo-alignment process or a rubbing process. Since the light distribution treatment can suppress display unevenness due to foreign matter or static electricity compared to the rubbing treatment, an alignment film subjected to the photo-alignment treatment is preferable from the viewpoint of yield.

  The color filter substrate of the present invention is preferably obtained, for example, by applying the above-described colored resin composition on a substrate, forming a pattern by photolithography, etc., and then curing by heat treatment to form pixels. In the case where the color filter substrate has the resin BM, it is preferable to form a pattern by applying a composition for forming the resin BM on the substrate before pixel formation. In the case where the color filter substrate has a planarization film, it is preferable to apply a material for forming the planarization film after pixel formation and perform pattern processing as necessary.

  Examples of the coating method and pattern forming method of the composition for forming the resin BM include a coloring resin composition coating method and a pattern forming method described later. In addition, when using a non-photosensitive composition as a composition which forms resin BM, it is preferable to perform the patterning using a photoresist. The obtained resin BM may be heat-treated.

  Examples of the method for applying the colored resin composition for forming the pixel include a dipping method, a roll coater method, a spinner method, a die coating method, and a wire bar coating method. The obtained coating film may be dried under reduced pressure. In the case of drying under reduced pressure, it is preferable to heat the inside of the vacuum chamber at 100 ° C. or lower in order to prevent the dry solvent from recondensing on the inner wall of the vacuum chamber. The vacuum drying pressure is preferably equal to or lower than the vapor pressure of the solvent to be used, and is preferably 1 to 1000 Pa. The drying time under reduced pressure is preferably 10 to 600 seconds. Further, heat drying using an oven or a hot plate, that is, semi-cure may be performed. The semi-cure conditions can be appropriately selected depending on the components of the photosensitive resin composition, and the heating temperature is generally 60 to 200 ° C. and the heating time is generally 1 to 60 minutes.

  When patterning the coating film by photolithography, exposure is preferably performed by a projection exposure method through a photomask. The projection magnification may be either 1: 1 projection exposure or reduced projection exposure. Examples of the projection exposure method include a lens scan exposure method, a mirror projection exposure method, and a stepper exposure method. Among these, a lens scan exposure method that can form dense pixels and can expose a large-area substrate in a short time is preferable. Examples of light used for exposure include g-line (436 nm), h-line (405 nm), i-line (365 nm), broad wavelength including g-line h-line i-line, KrF excimer laser ( 248 nm), ArF excimer laser (193 nm), and the like.

  It is preferable to develop the coating film after exposure with an alkali developer. As the alkali developer, either an organic alkali developer or an inorganic alkali developer can be used. As the inorganic alkaline developer, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is preferably used. As the organic alkali developer, amine-based aqueous solutions such as tetramethylammonium hydroxide aqueous solution and methanolamine are preferably used. In order to improve the uniformity of development, a surfactant is preferably added to the developer. The content of the alkaline substance is preferably 0.02% by weight or more in the alkaline developer from the viewpoint of development solubility in the unexposed area. On the other hand, from the viewpoint of further improving the pattern processability of the exposed portion, it is preferably 2.0% by weight or less in the alkaline developer. Since the developing speed varies depending on the temperature of the developing solution, the developing solution temperature is preferably selected appropriately within a range of 18 to 40 ° C.

  Examples of the developing method include dip development, shower development, and paddle development. It is preferable to appropriately select the temperature, flow rate and shower jet pressure of the developer, the washing temperature after development, the flow rate and the shower jet pressure conditions. In order to remove the residue on the substrate, it is preferable to spray the developer or washing water at a high pressure, and the ejection pressure is preferably 0.01 MPa to 20 MPa.

  The obtained coating film pattern can be cured by heat treatment to obtain pixels. Examples of the heat treatment apparatus include a hot air oven and a hot plate. From the viewpoint of the heat resistance of the pyromethene derivative, the heating temperature is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 180 ° C. or lower. On the other hand, the heating temperature is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher, from the viewpoint of the solvent resistance of the colored resin composition.

  By using the colored resin composition prepared for each color of the pixel, the above process is sequentially performed for the red pixel, the green pixel, and the blue pixel, whereby a color filter substrate can be manufactured. In addition, the patterning order of each color is not particularly limited.

Examples of a method for applying the composition for forming the alignment film include a method for applying a colored resin composition. An alignment film can be obtained by exposing the obtained coating film to linearly polarized ultraviolet light at 0.5 to 10 J / cm ² (in terms of i-line) and subjecting it to a heat treatment. Examples of the heat treatment apparatus include a hot air oven and a hot plate. The heating temperature is preferably 100 to 300 ° C., and the heating time is preferably 5 to 90 minutes.

  The colored resin composition and the color filter substrate of the present invention can be used for, for example, electronic materials, automotive lamps, various illuminations, various display devices, and the like. Since the color filter substrate of the present invention is excellent in luminance and color purity, it can be suitably used for display devices such as liquid crystal display devices, organic EL display devices, electronic paper, and micro LED display devices.

  A liquid crystal display device will be described as an example of a display device using the color filter substrate of the present invention. The liquid crystal display device includes the color filter substrate and the counter substrate of the present invention, and a liquid crystal compound is filled between both the substrates. Furthermore, you may have light sources, such as an external light source, various films, such as a brightness improvement film and a diffuser plate.

  Liquid crystal display devices are classified into transmissive liquid crystal display devices and reflective liquid crystal display devices. In contrast to the transmissive liquid crystal display device that can improve the brightness of the display by increasing the intensity of the backlight light source, in the reflective liquid crystal display device that mainly uses ambient light, the light transmittance of the color filter substrate is low. It becomes one of the factors of display brightness. Since the color filter substrate of the present invention is excellent in luminance, it can be suitably used for a reflective liquid crystal display device called a transflective type or a reflective type.

  The reflective liquid crystal display device has a reflective layer inside. Color purity can be further improved by the light incident from the front surface of the display device being reflected by the reflective layer and transmitted twice through the color filter substrate. The reflection layer only needs to reflect light having a wavelength in the visible light region, and examples thereof include a metal layer such as silver or aluminum, or a multilayer structure made of transparent resins having different refractive indexes. From the viewpoint of reflectance, a metal layer such as silver or aluminum is preferable, and a metal layer formed by sputtering or vapor deposition is more preferable.

  Examples of the reflective liquid crystal display device include devices that display using outdoor light or indoor light, such as wearable terminals, digital signs, digital signage, and electronic shelf labels.

  As an example of a method for manufacturing a display device using the color filter substrate of the present invention, a method for manufacturing a liquid crystal display device will be described below. The color filter substrate and the counter substrate are preferably bonded to each other through a liquid crystal alignment film provided on the substrates and a spacer for maintaining a cell gap. Note that a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured by providing a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, or the like over a counter substrate. Next, it is preferable to seal the injection port after injecting liquid crystal from the injection port provided in the seal portion. Furthermore, a liquid crystal display device can be obtained by mounting an IC driver or the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these examples.

  The structures of the organic light emitting materials R-1 to R3 and G-1 to 2 used in the following examples and comparative examples are shown below.

  Next, an evaluation method in each example and comparative example will be described.

<Measurement of emission peak>
Using a spin coater (1HD2 type; manufactured by Mikasa Co., Ltd.) on a non-alkali glass substrate having a thickness of 0.5 mm, the colored resin composition obtained in each example and comparative example was applied, and an oven at 90 ° C. The coating film was obtained by semi-curing for 10 minutes in (PERFECTOVEN PV-210; manufactured by Davai Espec Co., Ltd.). At this time, the number of rotations was adjusted so that the film thickness of the pixel after the main cure described later becomes 3.0 μm. In addition, the film thickness of the pixel was measured using the Surfcom stylus type film thickness measuring apparatus.

The obtained coating film was exposed to 100 mJ / cm ² using a mask aligner (PEM-6M; manufactured by Union Optics Co., Ltd .; collimation angle θ = 2 °, i-line (365 nm) illuminance = 30 mW / cm ² ). . Next, an aqueous solution at 23 ° C. containing 0.3% by weight of tetramethylammonium hydroxide and 0.3% by weight of “Emulgen” (registered trademark) A-60 (manufactured by Kao Corporation) was used as a developer. Shower development was performed for 1 minute using an automatic developing device (AD-2000; manufactured by Mikasa Co., Ltd.), followed by rinsing with pure water and air drying. Further, the film was cured for 30 minutes in an oven at 150 ° C. to produce pixels, and a color filter substrate was obtained.

  About the obtained pixel, using the F-2500 type spectrofluorometer (made by Hitachi, Ltd.), on the pixel surface, about Examples 23-24 and Comparative Examples 5-6, 8-9, wavelength 460nm For light, Examples 1 to 22 and Comparative Examples 1 to 4 and 7, light having a wavelength of 530 nm was irradiated and the fluorescence spectrum when excited was measured, and the peak wavelength of the fluorescence emission with the maximum intensity was read.

<Measurement of reflectance>
A color filter substrate was obtained in the same manner as described in <Measurement of emission peak>. The obtained color filter substrate was placed on a commercially available white reflecting plate so that the pixels were in contact with the white reflecting plate, and the color filter substrate (CM-2600d, manufactured by Konica Minolta, measurement diameter φ8 mm) The spectrum including reflected light was measured.

Color standard BT. That can reproduce almost natural colors. The color gamut defined by 2020 is defined with the three primary colors red, green, and blue on the spectral locus shown in the chromaticity diagram, and the wavelengths of red, green, and blue correspond to 630 nm, 532 nm, and 467 nm, respectively. From the reflectance at three wavelengths of 470 nm, 530 nm, and 630 nm of the obtained reflection spectrum, the color of the pixel was evaluated according to the following criteria.
Red: 630 nm reflectance (R630) is the largest among the three wavelengths Green: 530 nm reflectance (R530) is the largest among the three wavelengths Blue: 470 nm reflectance (R470 among the three wavelengths) ) Is the largest.

<Evaluation of color purity>
From the reflectance obtained by the method described in <Measurement of reflectance>, the color purity of the red pixel was evaluated according to the following criteria.
A: R630 / (R630 + R530 + R470) ≧ 0.75
A: 0.75> R630 / (R630 + R530 + R470) ≧ 0.55
X: 0.55> R630 / (R630 + R530 + R470).

From the reflectance obtained by the method described in <Measurement of reflectance>, the color purity of the green pixel was evaluated according to the following criteria.
○: R530 / (R630 + R530 + R470) ≧ 0.60
X: 0.60> R530 / (R630 + R530 + R470).

<Evaluation of brightness>
From the reflectance obtained by the method described in <Measurement of reflectance> described above, the luminance of the red pixel was evaluated according to the following criteria.
A: R630 ≧ 98.5
A: 98.5> R630 ≧ 96.5
X: 96.5> R630.

From the reflectance obtained by the method described in <Measurement of reflectance> described above, the luminance of the green pixel was evaluated according to the following criteria.
◯: R530 ≧ 80.0
X: 80.0> R530.

  The raw materials used in Examples and Comparative Examples are shown below.

Synthesis Example 1 Synthesis of pyromethene derivative (R-1)
A mixed solution of 300 mg of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201 mg of 2-methoxybenzoyl chloride and 10 ml of toluene was heated at 120 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, it was evaporated. After washing with 20 ml of ethanol and vacuum drying, 260 mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole was obtained.

  Next, 260 mg of 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole, 4- (4-t-butylphenyl) -2- (4- A mixed solution of 180 mg of methoxyphenyl) pyrrole, 206 mg of methanesulfonic anhydride and 10 ml of degassed toluene was heated at 125 ° C. for 7 hours under a nitrogen stream. After cooling to room temperature, 20 ml of water was poured and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, evaporated, and a pyromethene was obtained as a residue after vacuum drying.

Next, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to a mixed solution of the obtained pyromethene and 10 ml of toluene under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate and evaporated. After purification by silica gel column chromatography and vacuum drying, 0.27 g of reddish purple powder was obtained (yield 70%). The obtained red-violet powder was subjected to ¹ H-NMR analysis with a deuterated chloroform solution using a superconducting FT-NMR apparatus EX-270 (manufactured by JEOL Ltd.). It was confirmed that the reddish purple powder obtained in (1) was [R-1] represented by the structural formula.
¹ H-NMR (CDCl 3 (d = ppm)): 1.19 (s, 18 H), 3.42 (s, 3 H), 3.85 (s, 6 H), 5.72 (d, 1 H), 6 .20 (t, 1H), 6.42-6.97 (m, 16H), 7.89 (d, 4H).

Synthesis Example 2 Synthesis of pyromethene derivative (G-1)
3,5-dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0.4 g), potassium carbonate (2.0 g). Placed in flask and purged with nitrogen. Degassed toluene (30 mL) and degassed water (10 mL) were added thereto, and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 3,5-bis (4-t-butylphenyl) benzaldehyde (3.5 g) as a white solid.

3,5-Bis (4-t-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were added to the reaction solution, dehydrated dichloromethane (200 mL) and trifluoroacetic acid (1 drop). And stirred for 4 hours under a nitrogen atmosphere. A dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, then water (100 mL) was further added and stirred, and the organic layer was separated. did. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. The resulting reaction product was purified by silica gel column chromatography to obtain 0.4 g of compound G-1 (yield 18%). Using a superconducting FT-NMR apparatus EX-270 (manufactured by JEOL Ltd.), the results of ¹ H-NMR analysis using a deuterated chloroform solution are as follows, and the compound obtained above is It was confirmed to be [G-1] represented by the structural formula.

^{1 H-NMR (CDCl3, ppm} ): 7.95 (s, 1H), 7.63-7.48 (m, 10H), 6.00 (s, 2H), 2.58 (s, 6H), 1.50 (s, 6H), 1.37 (s, 18H).

Example 1
5.95 parts by weight of PY139 as a colorant, 3.97 parts by weight of PO71 as a colorant, 8.27 parts by weight of Disper “BYK” (registered trademark) 6919 as a binder resin (polymer dispersant; solid content concentration: 60% by weight) % Propylene glycol monomethyl ether acetate (hereinafter “PGMEA”) solution; manufactured by Big Chemie Japan Co., Ltd., 87.87 parts by weight of “Cyclomer” (registered trademark) P (ACA) Z250 (acrylic resin; solid content) A 45% by weight concentration of dipropylene glycol monomethyl ether (hereinafter “MFDG”) solution; manufactured by Daicel Ornex Co., Ltd., 93.94 parts by weight of PGMEA was dispersed using a mill-type disperser to disperse the pigment. A liquid (r-1) was obtained.

  200 parts by weight of the pigment dispersion (r-1), 0.50 parts by weight of R-1 as a pyromethene derivative, 0.50 parts by weight of G-1, and 35.59 parts by weight of pentaerythritol as a reactive monomer Mixture of triacrylate and pentaerythritol tetraacrylate in a weight ratio of 55/45 ("NK ester" (registered trademark) A-TMM-3L; manufactured by Shin-Nakamura Chemical Co., Ltd.), 3.95 parts by weight of the above general formula ( 3) 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd.), 0.50 parts by weight of the general formula (4) Compound (“ADEKA STAB” (registered trademark) LA-81; manufactured by ADEKA CORPORATION), 0.27 weight of diocti 3,3′-dithiodipropionate which is a compound represented by the above general formula (5) (Manufactured by Sakai Chemical Co., Ltd.), 0.79 parts by weight of “Irgacure” (registered trademark) OXE04 (manufactured by BASF Japan), 3.00 parts by weight of vinyltrimethoxysilane (KBM1003) as an adhesion improver; Manufactured by Shin-Etsu Chemical Co., Ltd.), 0.40 part by weight of “BYK” (registered trademark) -333 (manufactured by Big Chemie Japan), which is a surfactant, and 0.09 part by weight of 2 which is a polymerization inhibitor. , 5-bis (1,1,3,3-tetramethylbutyl) hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.), 180 parts by weight of the solvent “Examide” represented by the structural formula (11) (registered trademark) ) B-100 (manufactured by Idemitsu Kosan Co., Ltd.) 574.42 weight of PGMEA was mixed to prepare a colored resin composition-1.

(Examples 2 to 24, Comparative Examples 1 to 9)
Colored resin compositions -2 to 33 were prepared in the same manner as in Example 1 except that the types and amounts of the respective components were changed as shown in Tables 2 to 8.

The compositions and evaluation results of the examples and comparative examples are shown in Tables 2-8. In Tables 2 to 8, each component is as follows.
A-1: Mixture of 55/45 mass ratio of pentaerythritol triacrylate and pentaerythritol tetraacrylate (“NK ester” (registered trademark) A-TMM-3L; manufactured by Shin-Nakamura Chemical Co., Ltd.)
B-1: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)
C-1: “ADEKA STAB” (registered trademark) LA-81; manufactured by ADEKA Corporation D-1: dioctyl 3,3′-dithiodipropionate (manufactured by Sakai Chemical Co., Ltd.)
E-1: “Irgacure” (registered trademark) OXE04 (manufactured by BASF Japan Ltd.)
F-1: “Cyclomer” (registered trademark) P (ACA) Z250 (manufactured by Daicel Ornex Co., Ltd.)
H-1: Disper “BYK” (registered trademark) 6919 (manufactured by Big Chemie Japan Co., Ltd.)
I-1: Vinyltrimethoxysilane (KBM1003; manufactured by Shin-Etsu Chemical Co., Ltd.)
K-1: “BYK” (registered trademark) -333 (manufactured by Big Chemie Japan Co., Ltd.)
M-1: 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.)
L-1: “Examide” (trademark registration) B-100 (manufactured by Idemitsu Kosan Co., Ltd.)
L-2: PGMEA
L-3: MFDG.

  The colored resin composition of the present invention can be suitably used for a color filter substrate and a reflective liquid crystal display device having the color filter substrate.

Claims (17)

A colored resin composition comprising a pyromethene derivative, a yellow colorant and a binder resin. The colored resin composition according to claim 1, wherein the pyromethene derivative is a compound represented by the following general formula (1).

(X is C—R ⁷ or N. R ^{1 to} R ⁹ may be the same as or different from each other, hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, Hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro Selected from among a condensed ring and an aliphatic ring formed between a group, a silyl group, a siloxanyl group, a boryl group, a sulfo group, a phosphine oxide group, and an adjacent substituent. The colored resin composition according to claim 2, wherein, in the general formula (1), X is C—R ⁷ and R ⁷ is a group represented by the following general formula (2).

(R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero Selected from the group consisting of aryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, sulfo group, phosphine oxide group K is an integer of 1 to 3. When k is 2 or more, r may be the same or different. The colored resin according to claim 2 or 3, wherein in the general formula (1), R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different and each is a substituted or unsubstituted phenyl group. Composition. As the yellow colorant, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and / or C.I. I. The colored resin composition according to any one of claims 1 to 4, comprising Pigment Yellow 185. Furthermore, the coloring resin composition as described in any one of Claims 1-5 containing a red coloring agent and / or an orange coloring agent. Examples of the red and / or orange colorant include C.I. I. Pigment red 242, C.I. I. Pigment red 291, C.I. I. Pigment orange 71 and / or C.I. I. The colored resin composition according to claim 6, comprising Pigment Orange 73. The colored resin composition according to any one of Claims 1 to 7, which contains 50 to 99 parts by weight of the yellow colorant with respect to 100 parts by weight of the total content of the colorant. The colored resin composition according to any one of claims 1 to 8, wherein the pyromethene derivative absorbs green light and exhibits light emission observed in a red region having a peak wavelength of 580 to 780 nm. Other than the pyromethene derivative that absorbs green light and emits light that is observed in the red region having a peak wavelength of 580 to 780 nm, it absorbs blue light and is observed in the green region that has a peak wavelength of 500 to 579 nm. The colored resin composition according to claim 9, further comprising an organic light emitting material exhibiting light emission. The colored resin composition according to any one of claims 1 to 10, comprising 1 to 100 parts by weight of the pyromethene derivative with respect to 100 parts by weight of the yellow colorant. Furthermore, the colored resin composition as described in any one of Claims 1-11 containing a reactive monomer and a photoinitiator. Furthermore, the colored resin composition as described in any one of Claims 1-12 containing the compound represented by the compound represented by the following general formula (3), and the following general formula (4).

(In General Formula (3), Y represents a hydroxyl group or —R ¹⁰ —OH, and Z represents a hydroxyl group or R ¹¹ —OH. However, R ^{10 to} R ¹¹ are each independently an alkylene having 1 to 5 carbon atoms. R ^{12 to} R ¹³ each independently represents hydrogen or an alkyl group having 1 to 15 carbon atoms, and in formula (4), R ^{14 to} R ¹⁵ each independently represent hydrogen or 1 to carbon atoms. Represents 15 alkyl groups.) Furthermore, the coloring resin composition as described in any one of Claims 1-13 containing the compound represented by following General formula (5).

(R ^{16 to} R ¹⁷ each independently represents an alkyl group having 1 to 10 carbon atoms.) Furthermore, the colored resin composition as described in any one of Claims 1-14 containing the compound represented by following General formula (6).

(R ^{18 to} R ²⁰ each independently represents an alkyl group having 1 to 10 carbon atoms.) The color filter board | substrate which has a pixel which consists of the colored resin composition as described in any one of Claims 1-15, and / or its hardened | cured material on a board | substrate. 17. A reflective liquid crystal display device comprising the color filter substrate according to claim 16, a counter substrate, and a liquid crystal compound filled between both substrates.