JP7209471B2 - PHOTOSENSITIVE COLOR RESIN COMPOSITION, CURED PRODUCT, COLOR FILTER AND DISPLAY DEVICE - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive colored resin composition, a cured product, a color filter, and a display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. Recently, an organic light-emitting display device such as an organic EL display, which has high visibility due to self-luminescence, is also attracting attention as a next-generation image display device. As for the performance of these image display devices, there is a strong demand for higher image quality such as higher color rendering, higher contrast, and higher definition, and lower power consumption.

Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and the light passes through a color filter to express colors. In the organic light-emitting display device, color adjustment of pixels may be performed using a color filter, or a color image may be formed by using a color filter for a white light-emitting organic light-emitting element in the same manner as a liquid crystal display device.

As a recent trend, there is a demand for power saving in image display devices, and there is a particular demand for high brightness color filters in order to improve the utilization efficiency of the backlight. This is especially a big issue for mobile displays. Although battery capacity has increased due to technological evolution, the amount of electricity stored in mobile phones is still finite, and on the other hand, power consumption tends to increase as screen sizes increase. Image display devices including color filters influence the design and performance of mobile terminals because they are directly linked to the usable time and charging frequency of mobile terminals.

Here, the color filter is generally composed of a transparent substrate, a colored layer formed on the transparent substrate and composed of colored patterns of the three primary colors of red, green, and blue, and a colored layer formed on the transparent substrate so as to partition each colored pattern. and a formed light blocking portion.
As one method for forming such a colored layer, a photosensitive colored resin composition containing a coloring material, an alkali-soluble resin, and a photopolymerizable compound is applied onto a substrate, and then passed through a predetermined mask pattern. A method of forming a patterned colored layer by exposing and then developing is known (for example, Patent Document 1).

On the other hand, in Patent Document 2, when a colored layer for a color filter is patterned by etching using a resist as a mask, when removing the resist on the colored layer after etching, it is difficult to remove it together with the resist. A coloring composition containing a resin component containing a siloxane resin and an organic coloring material for the purpose of forming a colored layer, wherein the content of the organic coloring material in the total solid content of the coloring composition is 20 to 90 mass. %, the content of the resin component in the total solid content of the coloring composition is 10 to 80% by mass, and the content of the siloxane resin with respect to the total mass of the resin component is 80 to 100% by mass, the coloring composition is disclosed.

Further, Patent Document 3 discloses that a cured film or pattern excellent in transparency, chemical resistance, and environmental resistance can be used as a transparent flattening film to be coated on a thin film transistor element in a liquid crystal display at a low temperature. For the purpose of being able to form with, polysiloxane, a (meth) acrylic polymer, a compound containing two or more (meth) acryloyl groups, a polymerization initiator, and a solvent, characterized by comprising a negative photosensitive However, Patent Document 3 does not disclose any photosensitive colored resin composition containing a coloring material.

JP 2010-44195 A International Publication No. 2015/174189 JP 2015-18226 A

An object of the present invention is to provide a photosensitive colored resin composition capable of forming a colored layer with high brightness while having good developability. In addition, the present invention provides a cured product of the photosensitive colored resin composition, a color filter having a high-brightness colored layer using the photosensitive colored resin composition, and a high-brightness color filter using the color filter. An object of the present invention is to provide a display device.

The photosensitive colored resin composition according to the present invention comprises a silicon-containing compound (A) containing at least one compound represented by the following general formula (A1) and a compound represented by the following general formula (A2): , a photopolymerizable compound (B), a photoinitiator (C), and a coloring material (D),
The total content of the compound represented by the general formula (A1) and the compound represented by the general formula (A2) exceeds 10.0 parts by mass with respect to 100 parts by mass of the photopolymerizable compound (B). is .

（一般式（Ａ１）において、Ｒは、水素原子、エーテル結合（－Ｏ－）を含んでいてもよい炭素数１以上１０以下の炭化水素基、又は反応性基を有する基であり、当該反応性基を有する基が、チオエーテル結合（－Ｓ－）、エーテル結合（－Ｏ－）及びカルボニル結合（－ＣＯ－）から選択される少なくとも１種の２価の連結基を含んでいてもよい、直鎖又は分岐のアルキル基において、少なくとも１つのメチル基を、チオール基、（メタ）アクリロイル基、ビニル基及びエポキシ基からなる群から選ばれる少なくとも１種の反応性基に置き換えた一価の基であり、複数あるＲはそれぞれ同一でも異なっていてもよく、全てのＲのうち少なくとも一部が前記反応性基を有する基である。Ｌは直接結合又は－Ｏ－結合であり、ｎは２以上３０以下の整数を表す。
一般式（Ａ２）において、Ｒ’は、水素原子、エーテル結合（－Ｏ－）を含んでいてもよい炭素数１以上１０以下の炭化水素基、又は式：－（ＣＨ_２）_ａ－ＳｉＡ_２Ｈで表される基（ａは１以上３以下の整数であり、Ａは、（メタ）アクリロイルオキシアルコキシ基、メルカプトアルコキシ基又はグリシジルオキシ基を表す。）であり、複数あるＲ’はそれぞれ同一でも異なっていてもよく、全てのＲ’のうち少なくとも一部が前記式：－（ＣＨ_２）_ａ－ＳｉＡ_２Ｈで表される基である。Ｒ”は、炭素数１以上３以下のアルキレン基であり、複数あるＲ”は同一でも異なっていてもよく、Ｌ’は直接結合又は炭素数１以上３以下のアルキレン基であり、ｎ’は２以上３０以下の整数を表す。）

(In the general formula (A1), R is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond (-O-), or a group having a reactive group, and the reaction group having a sexual group, thioether bond (-S-), ether bond (-O-) and carbonyl bond (-CO-) may contain at least one divalent linking group selected from A monovalent group in which at least one methyl group in a linear or branched alkyl group is replaced with at least one reactive group selected from the group consisting of a thiol group, a (meth)acryloyl group, a vinyl group and an epoxy group and a plurality of R may be the same or different, and at least a portion of all R is a group having the reactive group L is a direct bond or -O- bond, n is 2 represents an integer greater than or equal to 30 or less.
In general formula (A2), R′ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond (—O—), or the formula: —(CH ₂ ) _a —SiA ₂ A group represented by H (a is an integer of 1 or more and 3 or less, and A represents a (meth)acryloyloxyalkoxy group, a mercaptoalkoxy group, or a glycidyloxy group), and a plurality of R' are each the same However, they may be different, and at least part of all R's are groups represented by the above formula: --(CH ₂ ) _a --SiA ₂ H. R ″ is an alkylene group having 1 to 3 carbon atoms, a plurality of R ″ may be the same or different, L′ is a direct bond or an alkylene group having 1 to 3 carbon atoms, and n′ is represents an integer of 2 or more and 30 or less. )

The present invention provides a cured product of the photosensitive colored resin composition according to the present invention.

A color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the cured product according to the present invention. and

The present invention provides a display device having the color filter according to the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive colored resin composition which can form a high-intensity colored layer can be provided, having favorable developability. Further, according to the present invention, a cured product of the photosensitive colored resin composition, a color filter having a high-brightness colored layer using the photosensitive colored resin composition, and a high A bright display device can be provided.

FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. FIG. 2 is a schematic diagram showing an example of the display device of the present invention. FIG. 3 is a schematic diagram showing another example of the display device of the present invention.

Hereinafter, the photosensitive colored resin composition, cured product, color filter, and display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, as well as radiation. Electromagnetic waves with wavelengths in the invisible region include ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. Radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less and electron beams.
In the present specification, (meth)acryl represents acrylic and methacrylic, (meth)acrylate represents acrylate and methacrylate, and (meth)acryloyl represents acryloyl and methacryloyl.
Also, in the present specification, C.I. I. Pigment Red as "PR", C.I. I. pigment green as "PG", C.I. I. Pigment yellow is abbreviated as "PY" as appropriate.

[Photosensitive colored resin composition]
The photosensitive colored resin composition according to the present invention includes a silicon-containing compound (A) containing at least one compound represented by the following general formula (A1) and a compound represented by the following general formula (A2): , a photopolymerizable compound (B), a photoinitiator (C), and a coloring material (D),
The total content of the compound represented by the general formula (A1) and the compound represented by the general formula (A2) exceeds 10.0 parts by mass with respect to 100 parts by mass of the photopolymerizable compound (B) and
The reactive group possessed by the compound represented by the general formula (A1) and the compound represented by the general formula (A2) is characterized by being a group capable of forming a crosslinked structure by light irradiation or heating.

（一般式（Ａ１）において、Ｒは、水素原子、酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基、又は反応性基を有する基であり、複数あるＲはそれぞれ同一でも異なっていてもよく、全てのＲのうち少なくとも一部が反応性基を有する基である。Ｌは直接結合又は－Ｏ－結合であり、ｎは２以上３０以下の整数を表す。
一般式（Ａ２）において、Ｒ’は、水素原子、酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基、又は反応性基を有する基であり、複数あるＲ’はそれぞれ同一でも異なっていてもよく、全てのＲ’のうち少なくとも一部が反応性基を有する基である。Ｒ”は、炭素数１以上３以下のアルキレン基であり、複数あるＲ”は同一でも異なっていてもよく、Ｌ’は直接結合又は炭素数１以上３以下のアルキレン基であり、ｎ’は２以上３０以下の整数を表す。）

(In the general formula (A1), R is a hydrocarbon group which may have a hydrogen atom or an oxygen atom and has 1 to 10 carbon atoms and does not have a reactive group, or a group having a reactive group. , a plurality of R may be the same or different, at least a portion of all R is a group having a reactive group.L is a direct bond or -O- bond, n is 2 or more and 30 or less represents an integer of
In general formula (A2), R' is a hydrocarbon group which may have a hydrogen atom or an oxygen atom and has 1 to 10 carbon atoms and does not have a reactive group, or a group having a reactive group. , a plurality of R' may be the same or different, and at least a portion of all R' is a group having a reactive group. R ″ is an alkylene group having 1 to 3 carbon atoms, a plurality of R ″ may be the same or different, L′ is a direct bond or an alkylene group having 1 to 3 carbon atoms, and n′ is represents an integer of 2 or more and 30 or less. )

In addition, the first embodiment of the photosensitive colored resin composition according to the present invention includes a silicon-containing compound (A) containing a compound represented by the general formula (A1), a photopolymerizable compound (B), and light containing an initiator (C) and a coloring material (D),
The content of the compound represented by the general formula (A1) is more than 10.0 parts by mass with respect to 100 parts by mass of the photopolymerizable compound (B),
The reactive group possessed by the compound represented by the general formula (A1) is characterized by being a group capable of forming a crosslinked structure by light irradiation or heating.
In addition, the second embodiment of the photosensitive colored resin composition according to the present invention includes a silicon-containing compound (A) containing a compound represented by the general formula (A2), a photopolymerizable compound (B), and light containing an initiator (C) and a coloring material (D),
The content of the compound represented by the general formula (A2) is more than 10.0 parts by mass with respect to 100 parts by mass of the photopolymerizable compound (B),
The reactive group possessed by the compound represented by the general formula (A2) is characterized by being a group capable of forming a crosslinked structure by light irradiation or heating.
Further, the third embodiment of the photosensitive colored resin composition according to the present invention is a silicon-containing compound (A) containing a compound represented by the general formula (A1) and a compound represented by the general formula (A2) and a photopolymerizable compound (B), a photoinitiator (C), and a coloring material (D),
The total content of the compound represented by the general formula (A1) and the compound represented by the general formula (A2) exceeds 10.0 parts by mass with respect to 100 parts by mass of the photopolymerizable compound (B). and
The reactive group possessed by the compound represented by the general formula (A1) and the compound represented by the general formula (A2) is characterized by being a group capable of forming a crosslinked structure by light irradiation or heating.

In a conventional colored resin composition using an alkali-soluble resin as a binder component, as described in Patent Document 1, the binder component is oxidized by heating during post-baking when forming a colored layer of a color filter. However, there is a problem that the colored layer is colored and the brightness of the colored layer is lowered. On the other hand, in order to make color filter pixels with higher color rendering and lower film thickness, there is a demand for increasing the density of the coloring material contained in the pixels. However, when the concentration of the colorant contained in the colored resin composition is increased, there is a problem that the developability during pattern formation is lowered due to the decrease in the alkali-soluble component. Straight or curved lines become non-uniform, and the problem of deterioration in dimensional accuracy, that is, so-called rippling, is likely to occur.
In addition, the colored layer formed using the coloring composition containing the siloxane resin described in Patent Document 2 may change the color or decrease the brightness due to heating during post-baking. brightness is difficult to achieve.
On the other hand, the photosensitive colored resin composition according to the present invention contains at least one compound selected from compounds represented by the general formula (A1) and compounds represented by the general formula (A2) as a binder component. By containing the silicon-containing compound in excess of 10.0 parts by mass with respect to 100 parts by mass of the photopolymerizable compound, it is possible to form a highly bright colored layer while having good developability.
The photosensitive colored resin composition of the present invention, as a binder component, is at least one selected from the compound represented by the general formula (A1) and the compound represented by the general formula (A2), a reactive group Since the specific silicon-containing compound has excellent heat resistance, decomposition or oxidation of the binder component due to heating during post-baking is suppressed, and coloring of the binder component is suppressed. Furthermore, since the reactive groups of the specific silicon-containing compound form a crosslinked structure, the coating film is less likely to be colored due to heating during post-baking, and a colored layer with high brightness can be formed. it is conceivable that. The specific silicon-containing compound thus suppresses the decrease in brightness due to heating during post-baking, and has even better developability. Therefore, the photosensitive colored resin composition of the present invention has a good It is possible to form a colored layer with high brightness while having developability.
The compound represented by the general formula (A1) and the compound represented by the general formula (A2) have excellent heat resistance because the main chain contains a silicon atom and the bond containing the silicon atom is resistant to oxidation reaction. It is considered that this is because it is stable, oxidizes with difficulty even when heated in an air atmosphere, and has a stable structure. Furthermore, the compound represented by the general formula (A1) and the compound represented by the general formula (A2) have reactive groups, and the reactive groups are bonded to each other in the process of forming the colored layer. Since the crosslinked structure is formed, it is believed that the crosslinked structure suppresses the penetration of oxygen into the colored layer, thereby further suppressing the decomposition or oxidation of the binder component. In addition, it is believed that the crosslinked structure suppresses the movement of the coloring material in the colored layer, thereby suppressing the decomposition or oxidation of the coloring material. Thus, by using the specific silicon-containing compound, the decomposition or oxidation of the binder component and the decomposition or oxidation of the coloring material are suppressed, so it is considered that a highly bright colored layer can be formed. .
Further, the compound represented by the general formula (A1) and the compound represented by the general formula (A2) contain a silicon atom, so that an electronegative Since there is a difference in degree and the polarity is biased, it is considered that the ionic alkali, which is also biased in polarity, is likely to be adsorbed and has good alkali developability. Furthermore, it is believed that the compound represented by the general formula (A1) has a high affinity for water in the Si—O bond in the main chain, and thus is more likely to have improved alkali developability.

The photosensitive colored resin composition of the present invention contains at least a silicon-containing compound (A), a photopolymerizable compound (B), and a photoinitiator (C) as a binder component, and further as a coloring component, It contains a coloring material (D), and may further contain other components within a range that does not impair the effects of the present invention.
Each component of the photosensitive colored resin composition of the present invention will be described in detail below.

The photosensitive colored resin composition of the present invention contains, as a binder component, a silicon-containing compound (A), a photopolymerizable compound (B), and a photoinitiator (C), thereby improving film-forming properties and coating properties. Adhesion to the coated surface can be imparted, and a pattern can be easily formed by photolithography using existing processes.

<Silicon-containing compound (A)>
In the photosensitive colored resin composition of the present invention, the silicon-containing compound (A) is at least one selected from compounds represented by the following general formula (A1) and compounds represented by the following general formula (A2). , contains a silicon-containing compound having a reactive group. The compound represented by the following general formula (A1) and the compound represented by the following general formula (A2) can each be used singly or in combination of two or more.

（一般式（Ａ１）において、Ｒは、水素原子、酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基、又は反応性基を有する基であり、複数あるＲはそれぞれ同一でも異なっていてもよく、全てのＲのうち少なくとも一部が反応性基を有する基である。Ｌは直接結合又は－Ｏ－結合であり、ｎは２以上３０以下の整数を表す。
一般式（Ａ２）において、Ｒ’は、水素原子、酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基、又は反応性基を有する基であり、複数あるＲ’はそれぞれ同一でも異なっていてもよく、全てのＲ’のうち少なくとも一部が反応性基を有する基である。Ｒ”は、炭素数１以上３以下のアルキレン基であり、複数あるＲ”は同一でも異なっていてもよく、Ｌ’は直接結合又は炭素数１以上３以下のアルキレン基であり、ｎ’は２以上３０以下の整数を表す。）

(In the general formula (A1), R is a hydrocarbon group which may have a hydrogen atom or an oxygen atom and has 1 to 10 carbon atoms and does not have a reactive group, or a group having a reactive group. , a plurality of R may be the same or different, at least a portion of all R is a group having a reactive group.L is a direct bond or -O- bond, n is 2 or more and 30 or less represents an integer of
In general formula (A2), R' is a hydrocarbon group which may have a hydrogen atom or an oxygen atom and has 1 to 10 carbon atoms and does not have a reactive group, or a group having a reactive group. , a plurality of R' may be the same or different, and at least a portion of all R' is a group having a reactive group. R ″ is an alkylene group having 1 to 3 carbon atoms, a plurality of R ″ may be the same or different, L′ is a direct bond or an alkylene group having 1 to 3 carbon atoms, and n′ is represents an integer of 2 or more and 30 or less. )

The reactive groups in R in the general formula (A1) and R' in the general formula (A2) are groups capable of forming a crosslinked structure by light irradiation or heating, i.e., they react with each other by light irradiation or heating. It is a group capable of forming a crosslinked structure by bonding, and is preferably a group capable of forming a crosslinked structure by reacting and bonding between reactive groups of the same kind.
Light irradiation or heating conditions for the reactive groups to react with each other and bond to each other are appropriately selected depending on the type of the reactive groups, and are not particularly limited, but the reactive groups react with each other by light irradiation. In the case of bonding, for example, in a color filter described later, the reactive groups can be bonded to each other by exposure during formation of the colored layer. For the exposure, for example, ultraviolet light emitted from a light source such as an ultra-high pressure mercury lamp or a high pressure mercury lamp can be preferably used. The exposure dose is preferably 30 mJ/cm ² or more and 200 mJ/cm ² or less, more preferably 40 mJ/cm ² or more and 150 mJ/cm ² or less, and even more preferably 50 mJ/cm ² or more and 100 mJ/cm ² or less. When the reactive groups react and bond with each other by heating, for example, in a color filter described later, after exposure for forming a colored layer, the temperature is preferably 80° C. or higher and 250° C. or lower, more preferably 100° C. or higher. By heating at 240° C. or lower, more preferably 180° C. or higher and 230° C. or lower, and most preferably 200° C. or higher and 230° C. or lower, the reactive groups can be bonded to each other. The heating time is preferably 10 minutes or more and 180 minutes or less, more preferably 20 minutes or more and 150 minutes or less.

The reactive group is preferably at least one selected from ethylenically unsaturated bonds, thiol groups and epoxy groups. The group having a reactive group is preferably a group having a (meth)acryloyl group from the viewpoint of improving the brightness of the colored layer, and has an epoxy group from the viewpoint of improving developability. It is preferably a group.
In addition, the reactive group may react and bond with a different reactive group or another functional group as long as the reactive groups of the same type can react and bond with each other. .

When the reactive group contains a thiol group, it is preferable from the point of being able to reduce the post-baking temperature when forming a colored layer using the photosensitive colored resin composition of the present invention. In this case, the post-baking temperature can be, for example, 70° C. or higher and 150° C. or lower, and more preferably 80° C. or higher and 120° C. or lower. Moreover, when the reactive group contains a thiol group, the time for the post-baking heat treatment is preferably 10 minutes or more and 120 minutes or less.
Further, from the viewpoint of reducing the post-baking temperature, the proportion of thiol groups in the total amount of 100 mol% of the reactive groups is preferably 10 mol% or more, more preferably 15 mol% or more. Preferably, it is more preferably 50 mol % or more, and it is particularly preferable that the reactive group is a thiol group.

In R in the general formula (A1) and R' in the general formula (A2), the group having a reactive group is a monovalent group having the reactive group, and has at least one reactive group. It is a monovalent group. The group having a reactive group includes, for example, at least one divalent linking group selected from a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (-CO-). monovalent groups in which at least one methyl group is replaced with a thiol group, a (meth)acryloyl group, a vinyl group or an epoxy group in a linear or branched alkyl group which may be substituted. The number of carbon atoms in the alkyl group may be 1 or more, but the crosslinked structure formed by the reactive group suppresses thermal movement of the colorant, improves heat resistance, and suppresses a decrease in luminance. From the viewpoint of high effect, it is preferably 20 or less, more preferably 17 or less, further preferably 10 or less, further preferably 6 or less, further preferably 4 or less, Furthermore, it is preferably 3 or less. When the alkyl group is a linear alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and even more preferably 1 or more and 3 or less. When the alkyl group is a branched alkyl group, the number of carbon atoms is preferably 3 or more and 20 or less, more preferably 4 or more and 17 or less. In addition, when the alkyl group is linear, it is preferable from the viewpoint of being less susceptible to structural change due to oxidation, and when it is branched, it has a plurality of terminals. It is preferable in that a crosslinked structure can be easily formed, the crosslink density can be easily increased, and vibration of the crosslinked structure due to heat can be suppressed.

Examples of groups having reactive groups include glycidoxyalkyl groups such as 3-glycidoxypropyl groups, (meth)acryloyloxyalkyl groups such as 3-(meth)acryloyloxypropyl groups, and 3-mercaptopropyl. A mercaptoalkyl group such as a group, a 2-(meth)acryloyloxyethoxy group, a (meth)acryloyloxyalkoxy group such as a 1-(meth)acryloyloxy-3-(meth)acryloyloxy-2-propoxy group, 2-mercapto Ethoxy group, mercaptoalkoxy group such as mercaptomethoxy group, glycidyloxy group, glycidyl group, (meth)acryloyl group, allyl group, 2-(3,4-epoxycyclohexyl)ethyl group, pentaerythritol tetrakis (mercaptoacetate) At least one divalent linkage selected from thioether bond (-S-), ether bond (-O-) and carbonyl bond (-CO-), such as a group obtained by removing one hydrogen atom from terminal -SH Those having the reactive group at the end of a linear or branched alkyl group which may contain a group can be preferably used.
Further, the group having the reactive group may be a group composed of the reactive group such as a thiol group. A group composed of the reactive group is preferable because it can form a high-density crosslinked structure, thereby easily improving the heat resistance of the colored layer.
Further, the group having a reactive group for R′ in the general formula (A2) includes a group represented by the formula: —(CH ₂ ) _a —SiA ₂ H (a is an integer of 1 or more and 3 or less, A represents a (meth)acryloyloxyalkoxy group, a mercaptoalkoxy group or a glycidyloxy group) is also preferred. In the above formula, a is more preferably 1 or 2.
As the group having a reactive group, among them, a group having a (meth)acryloyl group, a glycidyl group or a thiol group is preferable from the viewpoint of brightness and developability.

In the compound represented by the general formula (A1), at least a portion of all Rs in the general formula (A1) is a group having the reactive group. The reactive group equivalent of the compound is preferably 100 g/mol or more, more preferably 105 g/mol or more, and 110 g/mol or more in terms of easily suppressing a decrease in luminance due to heating. On the other hand, from the viewpoint of developability, it is preferably 300 g/mol or less, more preferably 250 g/mol or less, and even more preferably 200 g/mol or less.
In the compound represented by the general formula (A2), at least a portion of all R' in the general formula (A2) is a group having the reactive group. The reactive group equivalent of the represented compound is preferably 100 g/mol or more, more preferably 105 g/mol or more, more preferably 110 g/mol or more, from the viewpoint of easily suppressing a decrease in luminance due to heating. On the other hand, from the viewpoint of developability, it is preferably 300 g/mol or less, more preferably 250 g/mol or less, and even more preferably 200 g/mol or less.
Here, the reactive group equivalent of the silicon-containing compound is represented by the following formula (1).
Formula (1)
Reactive group equivalent (g/mol) = W _(A) (g)/M _(A) (mol)
(In formula (1), W _(A) represents the mass (g) of the silicon-containing compound, M _(A) is the sum of all reactive groups contained in the silicon-containing compound W _(A) (g) represents the number of moles (mol).)

As the hydrocarbon group optionally having an oxygen atom in R in the general formula (A1) and R' in the general formula (A2) and having 1 to 10 carbon atoms and not having a reactive group, It may be any of a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be linear, branched or cyclic. Cyclic alkyl groups are preferred. Examples of the hydrocarbon group having an oxygen atom include a hydrocarbon group containing an ether bond (--O--), typically an alkoxy group. R in the general formula (A1) and R' in the general formula (A2) may have an oxygen atom, and the number of carbon atoms in the hydrocarbon group having no reactive group is, among others, 1 or more and 4 It is preferably 1 or more, and more preferably 1 or more and 3 or less.

As the alkylene group having 1 to 3 carbon atoms in R″ in the general formula (A2), an ethylene group is particularly preferable from the viewpoint of the balance between storage stability and reactivity and heat resistance.

L in the general formula (A1) is a direct bond or -O- bond, preferably -O- bond.
L' in the general formula (A2) is a direct bond or an alkylene group having 1 to 3 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, preferably an ethylene group. more preferred.
In addition, that L or L' is a direct bond means that silicon atoms are directly bonded to each other.

n in the general formula (A1) and n' in the general formula (A2) are not particularly limited as long as they are 2 or more and 30 or less; is preferably 6 or more, and on the other hand, from the viewpoint of developability and compatibility, it is preferably 27 or less, more preferably 25 or less, and further preferably 20 or less, Furthermore, it is preferably 10 or less.

Further, from the viewpoint of developability, the molecular weight of the compound represented by the general formula (A1) is preferably 300 or more and 5000 or less, more preferably 500 or more and 4000 or less, and 1000 or more and 3000 or less. More preferably, the molecular weight of the compound represented by the general formula (A2) is preferably 300 or more and 5000 or less, more preferably 500 or more and 4000 or less, and 1000 or more and 3000 or less. Even more preferred.

As the compound represented by the general formula (A1), among others, a structural unit having a terminal structure represented by the following general formula (A1-1) and further represented by the following general formula (A1-2) more preferably a silicon-containing compound having a partial structure in which three or more constitutional units represented by the following general formula (A1-2) are bonded. The preferred silicon-containing compound may further have a structural unit represented by general formula (A1-3) below. The preferred silicon-containing compound includes a terminal structure represented by the following general formula (A1-1), a partial structure in which three or more structural units represented by the following general formula (A1-2) are bonded, and the terminal A silicon-containing compound comprising a structure and an —O— bond connecting a structural unit represented by general formula (A1-2) below is particularly preferred. Here, the terminal structure refers to the structure of both terminals of the main chain of the compound represented by the general formula (A1).

（一般式（Ａ１－１）において、Ｒ^ｉは、水素原子、酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基、又は反応性基を有する基である。
一般式（Ａ１－２）において、Ｒ^ｉｉは、反応性基を有する基である。
一般式（Ａ１－３）において、Ｒ^ｉｉｉは、水素原子、又は酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基である。）

(In the general formula (A1-1), R ⁱ may have a hydrogen atom or an oxygen atom, a hydrocarbon group having 1 to 10 carbon atoms that does not have a reactive group, or a reactive group is the base.
In general formula (A1-2), R ⁱⁱ is a group having a reactive group.
In general formula (A1-3), R ⁱⁱⁱ is a hydrocarbon group optionally having a hydrogen atom or an oxygen atom and having 1 to 10 carbon atoms and having no reactive group. )

In general formula (A1-1), a plurality of R ⁱ may be the same or different, but are preferably the same ^. In the terminal structure, R ⁱ is preferably the same.
In general formula (A1-2), a plurality of R ⁱⁱ may be the same or different, but are preferably the same. Although R ⁱⁱ may be different in each structural unit, it is preferable that R ⁱⁱ be the same in all structural units represented by the general formula (A1-2) from the viewpoint of easy formation of a crosslinked structure. .
In general formula (A1-3), a plurality of R ⁱⁱⁱ may be the same or different, but are preferably the same. R ⁱⁱⁱ may be the same or different in each structural unit.

Having a group having a reactive group in the general formula (A1-1) and the general formula (A1-2), and an oxygen atom in the general formula (A1-1) and the general formula (A1-3) The hydrocarbon group having 1 to 10 carbon atoms and not having a reactive group is the same as in the general formula (A1), and those preferable in the general formula (A1) are preferably used in the same manner. be able to. As the group having a reactive group in the general formula (A1-1) and the general formula (A1-2), among others, a linear alkoxy group having 1 to 6 carbon atoms or a linear alkoxy group having 1 to 6 carbon atoms at the end of the alkyl group, via or without a divalent linking group that is a -O- bond, -O-(C=O)- bond, an alkylene group having 1 to 3 carbon atoms, or a combination thereof, A group having the reactive group is preferable, and among them, a (meth)acryloyloxyalkyl group, a mercaptoalkyl group, a glycidoxyalkyl group, a (meth)acryloyloxyalkoxy group, a mercaptoalkoxy group or a glycidyloxy group is more preferable. Specifically, 3-glycidoxypropyl group, 3-(meth)acryloyloxypropyl group, 3-mercaptopropyl group, 2-(meth)acryloyloxyethoxy group, 2-mercaptoethoxy group, mercaptomethoxy group or glycidyl Oxy groups are preferred. Among these, further, at the end of a linear alkoxy group having 1 to 6 carbon atoms, -O-bond, -O-(C=O)-bond, alkylene group having 1 to 3 carbon atoms, or a combination thereof A group having the reactive group with or without a certain divalent linking group is preferred, and among them, a (meth)acryloyloxyalkoxy group, a mercaptoalkoxy group or a glycidyloxy group is more preferred, and more specifically , 2-(meth)acryloyloxyethoxy group, 2-mercaptoethoxy group or glycidyloxy group are preferred.
R ⁱ in the general formula (A1-1) is preferably a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom and does not have a reactive group. It is more preferably an alkoxy group of 1 or more and 4 or less.
When R ⁱ in general formula (A1-1) is a group having a reactive group, the reactive group possessed by R ⁱ is the reactive group possessed by R ⁱⁱ in general formula (A1-2). Although they may be the same or different, they are preferably the same from the viewpoint of easy formation of a crosslinked structure.

Among the total amount of structural units possessed by the silicon-containing compound represented by the preferred general formula (A1), the content ratio of the structural units represented by the general formula (A1-2) and the general formula (A1-3) ) is preferably adjusted appropriately so that the amount of reactive groups contained in the silicon-containing compound is within the preferred range.

The compound represented by the general formula (A1) contains, for example, a cyclic siloxane represented by the following general formula (a2) in the presence of a disiloxane represented by the following general formula (a1); can be produced by ring-opening polymerization of a mixture of cyclic siloxanes containing cyclic siloxanes represented by the following general formula (a3).

（一般式（ａ１）中のＲ^ｉは、前記一般式（Ａ１－１）と同様であり、一般式（ａ２）中のＲ^ｉｉは、前記一般式（Ａ１－２）と同様であり、一般式（ａ２）中のＲ^ｉｉｉは前記一般式（Ａ１－３）と同様である。ｎ１及びｎ２はそれぞれ独立に、３又は４である。）

(R ⁱ in the general formula (a1) is the same as the general formula (A1-1), R ⁱⁱ in the general formula (a2) is the same as the general formula (A1-2), and general R ⁱⁱⁱ in formula (a2) is the same as in general formula (A1-3).n1 and n2 are each independently 3 or 4.)

The content of the cyclic siloxane represented by the general formula (a2) in the mixture of cyclic siloxanes may be appropriately adjusted so that the amount of reactive groups contained in the silicon-containing compound is within the preferred range. Although not particularly limited, it is preferably 50 mol % or more, more preferably 70 mol % or more, in 100 mol % of the total cyclic siloxane.

Further, in the presence of the disiloxane represented by the general formula (a1), the cyclic siloxane represented by the general formula (a2) is contained, and if necessary, the general formula (a3) is present. When a mixture of cyclic siloxanes containing cyclic siloxanes is subjected to ring-opening polymerization, the total amount of the cyclic siloxanes is preferably 1 mol or more and 10 mol or less, preferably 2 mol or more, relative to 1 mol of the disiloxane. It is more preferable to make it 8 mol or less.

The conditions for the ring-opening polymerization reaction are appropriately selected according to the type of material to be used, and are not particularly limited. For example, the mixture containing the disiloxane and the cyclic siloxane is It can be carried out by heating to a temperature and keeping it for 8 hours or more and 24 hours or less.
A catalyst is preferably used in the ring-opening polymerization reaction. As the catalyst, a known catalyst can be used without any particular limitation, and either a basic catalyst or a strongly acidic catalyst can be used. The catalyst can be removed by neutralizing or washing the product obtained by ring-opening polymerization. A solvent may be used as necessary in the ring-opening polymerization reaction.

The compound represented by the general formula (A1) can also be produced by reacting a polysiloxane represented by the following general formula (a4) with tetraalkoxysilane.

（一般式（ａ４）中、Ｒ^ｉｉは前記一般式（Ａ１－２）と同様である。ｎ３は２以上３０以下の整数を表す。）

(In general formula (a4), R ⁱⁱ is the same as in general formula (A1-2). n3 represents an integer of 2 or more and 30 or less.)

n3 in the general formula (a4) is preferably 5 or more.
Among the tetraalkoxysilanes, it is preferable that the number of carbon atoms in the alkoxy group of the tetraalkoxysilane is 1 or more and 4 or less. Among them, tetramethoxysilane is particularly preferred.

When the polysiloxane represented by the general formula (a4) is reacted with tetraalkoxysilane, 0.5 of the polysiloxane represented by the general formula (a4) is added to 1.0 mol of the tetraalkoxysilane. It is preferably 0.6 mol or more and 2.0 mol or less, more preferably 0.6 mol or more and 2.0 mol or less.

The reaction conditions of the polysiloxane represented by the general formula (a4) and the tetraalkoxysilane are appropriately adjusted and are not particularly limited, but the reaction should be carried out at a reaction temperature of 50° C. or higher and 140° C. for 1 hour or longer and 10 hours or shorter. is preferred. Moreover, in the reaction between the polysiloxane represented by the general formula (a4) and the tetraalkoxysilane, an acidic or basic catalyst may be used, or a solvent may be used, if necessary. The amount of the catalyst added is preferably 100 ppm or less with respect to the total amount of the polysiloxane represented by the general formula (a4) and the tetraalkoxysilane. Moreover, it is preferable to carry out the reaction while removing the by-produced alcohol under reduced pressure or under a nitrogen stream.

The compound represented by the general formula (A2), among others, has a terminal structure represented by the following general formula (A2-1), and further has a structural unit represented by the following general formula (A2-2). Silicon-containing compounds are preferred. The preferred silicon-containing compound may further have a structural unit represented by general formula (A2-3) below. Preferred silicon-containing compounds include, among others, a terminal structure represented by general formula (A2-1) below, a structural unit represented by general formula (A2-2) below, and general formula (A2-3) below. and the structural unit represented by the terminal structure and the structural unit represented by the general formula (A2-2) or the structural unit represented by the general formula (A2-3). Silicon-containing compounds consisting of the following alkylene groups are particularly preferred. Here, the terminal structure refers to the structure of both terminals of the main chain of the compound represented by the general formula (A2).

（一般式（Ａ２－１）において、Ｒ^ｉｖは、水素原子、酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基、又は反応性基を有する基である。
一般式（Ａ２－２）において、Ｒ^ｖは、反応性基を有する基、水素原子、又は酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基であり、少なくとも１つのＲ^ｖは反応性基を有する基であり、Ｒ”は、炭素数１以上３以下のアルキレン基である。
一般式（Ａ２－３）において、Ｒ^ｖｉは、水素原子、又は酸素原子を有していてもよく、反応性基を有しない炭素数１以上１０以下の炭化水素基であり、Ｒ”は、炭素数１以上３以下のアルキレン基である。）

(In the general formula (A2-1), R ^iv may have a hydrogen atom or an oxygen atom, a hydrocarbon group having 1 to 10 carbon atoms without a reactive group, or a reactive group is the base.
In general formula (A2-2), R ^v is a group having a reactive group, a hydrogen atom, or a hydrocarbon group which may have an oxygen atom and has 1 to 10 carbon atoms and which does not have a reactive group. and at least one R ^v is a group having a reactive group, and R″ is an alkylene group having 1 to 3 carbon atoms.
In general formula (A2-3), R ^vi is a hydrocarbon group optionally having a hydrogen atom or an oxygen atom and having 1 to 10 carbon atoms and having no reactive group; It is an alkylene group having 1 or more and 3 or less carbon atoms.)

A group having a reactive group in the general formula (A2-1) and the general formula (A2-2), and the general formula (A2-1), the general formula (A2-2) and the general formula (A2) -3), the hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom and does not have a reactive group is the same as in the general formula (A2), and the general formula (A2 ) can likewise be preferably used.
In general formula (A2-1), a plurality of R ^iv may be the same or different, but one R ^iv is a hydrogen atom and the remaining two R ^iv are groups having a reactive group. is preferred. Examples of groups having reactive groups in R ^iv include, among others, -O-bonds, -O-(C=O)-bonds, and 1 to 3 carbon atoms at the ends of linear alkoxy groups having 1 to 6 carbon atoms. Via or without the following alkylene groups or a combination of these divalent linking groups, a group having the reactive group is preferable, and a (meth)acryloyloxyalkoxy group, a mercaptoalkoxy group or a glycidyloxy group is more Preferred are 2-(meth)acryloyloxyethoxy group, 2-mercaptoethoxy group, mercaptomethoxy group and glycidyloxy group, more specifically.
In general formula (A2-2), a plurality of R ^v may be the same or different, but are preferably the same, and preferably a group having a reactive group. The group having a reactive group in R ^v includes, among others, a group represented by the above formula: —(CH ₂ ) _a —SiA ₂ H (a is an integer of 1 or more and 3 or less, and A is (meta) represents an acryloyloxyalkoxy group, a mercaptoalkoxy group or a glycidyloxy group). A in the above formula is preferably a 2-(meth)acryloyloxyethoxy group, a 2-mercaptoethoxy group, a mercaptomethoxy group or a glycidyloxy group.
In general formula (A2-3), a plurality of R ^vi may be the same or different, but are preferably the same, and are preferably hydrogen atoms.

Among the total amount of structural units possessed by the silicon-containing compound represented by the preferred general formula (A2), the content ratio of the structural units represented by the general formula (A2-2) and the general formula (A2-3) ) is preferably adjusted appropriately so that the amount of reactive groups contained in the silicon-containing compound is within the preferred range.

The compound represented by the general formula (A2) is obtained, for example, by adding a monochlorosilane represented by the following general formula (a5) to a polyfunctional vinyl compound represented by the following general formula (a6), followed by reduction. It can be manufactured by

（一般式（ａ５）中のＲ^ｉｖは反応性基を有する基であり、一般式（ａ６）中のＲ”は、炭素数１以上３以下のアルキレン基である。）

(R ^iv in general formula (a5) is a group having a reactive group, and R″ in general formula (a6) is an alkylene group having 1 to 3 carbon atoms.)

R ^iv in general formula (a5) is the same as the group having a reactive group for R ^iv in general formula (A2-1).

Examples of the method for adding the monochlorosilane represented by the general formula (a5) to the polyfunctional vinyl compound represented by the general formula (a6) include a method using a Pt compound. After that, it can be reduced by using a reducing agent. Here, the addition reaction using the Pt compound can be carried out according to known methods and conditions. Also, as the reducing agent, for example, LiAlH ₄ or the like can be used. The said reduction reaction can also be performed by a well-known method and conditions.

The total content of the compound represented by the general formula (A1) and the compound represented by the general formula (A2) is 10.0 parts by mass with respect to 100 parts by mass of the photopolymerizable compound (B) described later. Although it is not particularly limited as long as it exceeds, it is preferably 20 parts by mass or more, more preferably 50 parts by mass or more with respect to 100 parts by mass of the photopolymerizable compound (B) from the viewpoint of improving the brightness. , It is more preferably 75 parts by mass or more, and from the viewpoint of compatibility, it is preferably 300 parts by mass or less, and 200 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound (B). more preferred.

The photosensitive colored resin composition of the present invention, as the silicon-containing compound (A), within a range that does not impair the effects of the present invention, represented by the compound represented by the general formula (A1) and the general formula (A2) may contain other silicon-containing compounds different from the Examples of the other silicon-containing compounds include copolymers containing a partial structure in which the main chain is a C—C bond and a partial structure having a siloxane skeleton.
Among them, the total content of the compound represented by the general formula (A1) and the compound represented by the general formula (A2) is, from the viewpoint of brightness, based on 100 parts by mass of the total amount of the silicon-containing compound (A). , is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and even more preferably 95 parts by mass or more.

In addition, the content of the silicon-containing compound (A) in the photosensitive colored resin composition is preferably 10% by mass or more and 80% by mass or less in 100% by mass of the total solid content of the photosensitive colored resin composition. , 15% by mass or more and 50% by mass or less. When the content of the silicon-containing compound (A) is at least the lower limit, it is easy to suppress a decrease in brightness and a change in color due to heating during post-baking, and it is easy to improve the brightness of the colored layer. Also tend to be good. When the content of the silicon-containing compound (A) is equal to or less than the upper limit, the concentration of the coloring material can be increased, and the effects of combined use with other components can be sufficiently exhibited.
In the present invention, the solid content refers to all substances other than the solvent, including monomers and the like dissolved in the solvent.

<Photopolymerizable compound (B)>
The photopolymerizable compound (B) contained in the photosensitive colored resin composition of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator described later. For example, in the molecule, ethylene Among them, compounds having two or more ethylenically unsaturated bonds in the molecule are preferable, and in particular, polyfunctional (meth)acryloyl groups in the molecule having two or more ( Meth)acrylates are preferred.
As such a polyfunctional (meth)acrylate, it may be appropriately selected and used from conventionally known ones. Specific examples include those described in JP-A-2013-029832.

One of these polyfunctional (meth)acrylates may be used alone, or two or more thereof may be used in combination. Further, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional monomer has three polymerizable double bonds (trifunctional) or more. is preferred, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and dicarboxylic acid-modified products thereof are preferred. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate Succinic acid-modified products, dipentaerythritol hexa(meth)acrylate and the like are preferred.

The content of the photopolymerizable compound (B) in the photosensitive colored resin composition suppresses poor curing and prevents the exposed portion from eluting during development, so the solid content of the photosensitive colored resin composition It is preferably 10% by mass or more, more preferably 15% by mass or more, in 100% by mass of the total amount. On the other hand, the content of the photopolymerizable compound (B) is determined from the viewpoints of suppressing poor development, improving brightness, suppressing heat shrinkage, and making it difficult for fine wrinkles to occur on the entire surface of the colored layer. In 100% by mass of the total solid content of the colored resin composition, it is preferably 80% by mass or less, more preferably 70% by mass or less, more preferably 55% by mass or less, and further 40% by mass. % or less, may be 30 mass % or less, or may be 25 mass % or less.

<Photoinitiator (C)>
The photoinitiator (C) contained in the photosensitive colored resin composition of the present invention is not particularly limited, and can be used alone or in combination of two or more of conventionally known various photoinitiators. can be done. The photoinitiator used in the colored resin composition of the present invention includes a chain transfer agent in addition to the photopolymerization initiator.
In the present invention, the photoinitiator (C) includes an oxime ester photoinitiator, an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto-based chain transfer agent, etc., can be suitably used, and among them, an oxime ester-based photoinitiator is included from the viewpoint of improving the sensitivity and easily improving the brightness of the colored layer when combined with the silicon-containing compound. is preferred. In addition, by using an oxime ester photoinitiator, in-plane variations in line width can be easily suppressed when a fine line pattern is formed. Further, the use of an oxime ester photoinitiator tends to improve development resistance and enhance the effect of suppressing the occurrence of water stains. The term "water stain" means that when a component that enhances alkali developability is used, after alkali development and rinsing with pure water, water stain marks are produced. Such water stains disappear after post-baking, so there is no problem with the product. occur. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the visual inspection, the yield of the final color filter product will be lowered, resulting in a problem.

In the present invention, the photoinitiator (C) preferably contains an oxime ester compound represented by the following general formula (C1) as an oxime ester photoinitiator.

（一般式（Ｃ１）において、Ｘは、チオエーテル結合（－Ｓ－）、エーテル結合（－Ｏ－）又は－Ｃ（Ｒ^ａ）（Ｒ^ｂ）－で表される２価の基であり、Ｒ^ａ及びＲ^ｂはそれぞれ独立に、水素原子又はアルキル基であり、Ｘがチオエーテル結合（－Ｓ－）又はエーテル結合（－Ｏ－）の場合は、Ｙは無結合であり、Ｘが－Ｃ（Ｒ^ａ）（Ｒ^ｂ）－で表される２価の基の場合は、Ｙは直接結合である。Ｒ^ｃは、チオエーテル結合（－Ｓ－）、エーテル結合（－Ｏ－）及びカルボニル結合（－ＣＯ－）から選択される少なくとも１種の２価の連結基を含んでいてもよい炭化水素基であり、Ｚは、水素原子又は－（Ｃ＝Ｏ）Ｒ^ｄであり、Ｒ^ｄは酸素原子及び硫黄原子から選択される少なくとも１種を含んでいてもよい炭化水素基、又は、窒素原子を含まず、酸素原子及び硫黄原子から選択される少なくとも１種を含む複素環基であり、Ｒ^ｅは、炭素数１以上１０以下の炭化水素基である。）

(In the general formula (C1), X is a thioether bond (-S-), an ether bond (-O-) or a divalent group represented by -C(R ^a )(R ^b )-, and R ^a and R ^b are each independently a hydrogen atom or an alkyl group, and when X is a thioether bond (—S—) or an ether bond (—O—), Y is no bond, and X is —C ( In the case of a divalent group represented by R ^a )(R ^b )-, Y is a direct bond.R ^c is a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond ( —CO—) is a hydrocarbon group optionally containing at least one divalent linking group selected from Z is a hydrogen atom or —(C═O)R ^d , where R ^d is oxygen A hydrocarbon group optionally containing at least one selected from atoms and sulfur atoms, or a heterocyclic group containing no nitrogen atoms and containing at least one selected from oxygen atoms and sulfur atoms, ^e is a hydrocarbon group having 1 to 10 carbon atoms.)

When a photoinitiator with higher sensitivity is used, after radical generation, the radicals move to the unexposed area, and the shape of the unexposed area inside the exposed area is maintained, and the surroundings of the unexposed area are smoothed. difficult to form. Therefore, if a highly sensitive photoinitiator capable of forming a fine line pattern is used, it may be difficult to form micropores in the fine line pattern even if the fine line pattern has good linearity. If a photoinitiator with relatively low sensitivity is used, even if micropores can be formed, there is a problem that the residual film rate is lowered. On the other hand, by using the oxime ester compound represented by the general formula (C1), it is possible to form micropores in the fine line pattern while suppressing the decrease in the residual film ratio.
Further, by using the oxime ester compound represented by the general formula (C1), it is possible to improve the linearity when forming a fine line pattern. Here, "improved linearity" means that the colored layer formed in the development step after applying the coloring composition has less unevenness at the end and is formed in a linear or substantially linear shape. .

In the general formula (C1), X and Y are, among others, X is a thioether bond (-S-) and Y is no bond, or X is -C(R ^a )(R ^b )- It is preferably a divalent group represented and Y is a direct bond.
R ^a and R ^b are each independently a hydrogen atom or an alkyl group, and the alkyl group may be a linear, branched, cyclic, or a combination of these alkyl groups, for example, an ethyl group , n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, cyclopentyl group, methylcyclopentyl group, cyclopentylmethyl group, cyclohexyl group and the like. Among them, an alkyl group having 2 to 6 carbon atoms is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and a linear alkyl group having 2 to 4 carbon atoms is further preferable. is.

In the general formula (C1), R ^c contains at least one divalent linking group selected from a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (-CO-). is a hydrocarbon group that may be
Examples of the hydrocarbon group for ^Rc include an alkyl group, an alkenyl group, an aryl group, an aralkyl group and the like. The alkyl group may be linear, branched, cyclic, or a combination thereof. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group and n-dodecyl. group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, cyclopentylethyl group, cyclohexylethyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group, and the like. can. The alkenyl group may be linear, branched or cyclic, and examples thereof include vinyl, allyl and propenyl groups. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and the like. The hydrocarbon group for R ^c is preferably a hydrocarbon group having 1 to 14 carbon atoms, such as an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and 6 carbon atoms. An aryl group having at least 10 carbon atoms is more preferable, and an alkyl group having from 1 to 10 carbon atoms is even more preferable. Further, it is preferable that the hydrocarbon group in R ^c has 2 or more carbon atoms from the viewpoint of improving developability. The hydrocarbon group in R ^c preferably has a structure containing a cyclic or linear alkyl group such as a cyclopentylmethyl group or a cyclohexylmethyl group from the viewpoint of solvent solubility and compatibility.
Further, in R ^c , the hydrocarbon group contains the divalent linking group, so that solvent solubility and compatibility can be improved. The divalent linking group is preferably a thioether bond (--S--) or an ether bond (--O--) from the viewpoint of improving solvent solubility. In R ^c , when the hydrocarbon group contains the divalent linking group, the hydrocarbon group may be bonded to the carbon atom of the oxime ester group via the divalent linking group, A carbon atom of the hydrocarbon group may be directly bonded to a carbon atom of the oxime ester group. In the R ^c , when the hydrocarbon group contains the divalent linking group and the carbon atom of the hydrocarbon group is directly bonded to the carbon atom of the oxime ester group, for example, R ^c The case where it is the group which couple|bonded the hydrogen groups by the said divalent coupling group is mentioned. Examples of the group in which hydrocarbon groups are bonded to each other with the divalent linking group include, for example, a structure containing a thioether bond (-S-) such as an alkylthioalkyl group such as a methylthiomethyl group and an arylthioalkyl group; a methoxymethyl group; Structures containing an ether bond (--O--) such as a methoxycyclohexyl group, an alkoxyalkyl group, and an aryloxyalkyl group; structures containing a carbonyl bond (--CO--) such as an acetylmethyl group, a benzoylmethyl group, and an acylalkyl group ; and the like.

In the general formula (C1), Z is a hydrogen atom or -(C=O)R ^d , where R ^d is a hydrocarbon group optionally containing at least one selected from an oxygen atom and a sulfur atom, Alternatively, it is a heterocyclic group containing no nitrogen atom and containing at least one selected from an oxygen atom and a sulfur atom. Examples of the hydrocarbon group optionally containing at least one selected from an oxygen atom and a sulfur atom in R ^d include the hydrocarbon group described in R ^c above and the hydrocarbon group described in R ^c above. , ether bond (-O-), carbonyl bond (-CO-) at least one linking group selected from linking groups containing oxygen atoms and sulfur atoms such as thioether bond (-S-) Among them, it is preferably a hydrocarbon group having 1 to 14 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and 6 carbon atoms An aryl group having 10 or less carbon atoms is more preferable, and an aryl group having 6 or more and 10 or less carbon atoms is even more preferable. In addition, the heterocyclic ring in the heterocyclic group containing at least one selected from an oxygen atom and a sulfur atom without containing a nitrogen atom includes, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a thienothiophene ring, Examples include a furofuran ring and a thienofuran ring. From the viewpoint of developability, the hydrocarbon group or heterocyclic group in R ^d preferably has 1 or more and 10 or less carbon atoms.
Above all, Z is preferably a hydrogen atom from the viewpoint of developability and brightness. On the other hand, when Z is —(C═O)R ^d , solvent solubility and compatibility can be improved.

In the general formula (C1), R ^e is a hydrocarbon group having 1 or more and 10 or less carbon atoms.
Examples of the hydrocarbon group having 1 or more and 10 or less carbon atoms include those having 1 or more and 10 or less carbon atoms among the hydrocarbon groups described above for ^Rc . Among them, R ^e is preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of improving sensitivity. An alkyl group of 1 to 4 is more preferred, and a methyl group is particularly preferred.

Although the molecular weight of the oxime ester compound represented by the general formula (C1) is not particularly limited, it is preferably 1,000 or less, more preferably 800 or less from the viewpoint of reducing the photoinitiator content. is preferred. Moreover, the lower limit of the molecular weight of the oxime ester compound represented by the general formula (C1) is not particularly limited, but can be, for example, 300 or more.

Among the oxime ester compounds represented by the general formula (C1), a divalent group represented by —C(R ^a )(R ^b )— in the general formula (C1), and Y is directly As the oxime ester compound which is a bond, for example, both R ^a and R ^b are alkyl groups having 1 to 4 carbon atoms, R ^c is an alkyl group having 1 to 4 carbon atoms, and Z is a hydrogen atom. and R ^e is an alkyl group having 1 to 4 carbon atoms; both R ^a and R ^b are alkyl groups having 1 to 6 carbon atoms, and R ^c is a linear alkyl group and a cyclic alkyl group; a combined alkyl group having 4 to 10 carbon atoms, Z is a hydrogen atom, and R ^e is an alkyl group having 1 to 4 carbon atoms; both R ^a and R ^b are hydrogen atoms or 1 carbon atom; R ^c is an alkyl group having 1 to 4 carbon atoms, Z is —(C═O)R ^d , and R ^d is an aryl group having 6 to 10 carbon atoms. and a compound in which R ^e is an alkyl group having 1 to 4 carbon atoms; but not limited thereto.

Among the oxime ester compounds represented by the general formula (C1), a divalent group represented by —C(R ^a )(R ^b )— in the general formula (C1), and Y is directly As the oxime ester compound which is a bond, at least one selected from the following compounds (C1-1) to (C1-4) is more preferable.

Among the oxime ester compounds represented by the general formula (C1), a divalent group represented by —C(R ^a )(R ^b )— in the general formula (C1), and Y is directly For the oxime ester compound that is a bond, for example, refer to Japanese Patent Application Publication No. 2012-526185, use fluorene or a derivative thereof instead of diphenyl sulfide or a derivative thereof, and use a solvent, reaction temperature, and reaction time depending on the material used. , purification method, etc. can be appropriately selected.

Among the oxime ester compounds represented by the general formula (C1), examples of the oxime ester compound in which X in the general formula (C1) is a thioether bond (-S-) and Y is no bond include , R ^c is an alkyl group having 6 to 10 carbon atoms in which a linear alkyl group and a cyclic alkyl group are combined, Z is a hydrogen atom, and R ^e is an alkyl group having 1 to 4 carbon atoms. ; R ^c is an alkyl group having 6 to 10 carbon atoms in which a linear alkyl group and a cyclic alkyl group are combined, Z is —(C═O)R ^d , and the R ^d contains a nitrogen atom; First, a compound which is a heterocyclic group containing a sulfur atom and R ^e is an alkyl group having 1 to 4 carbon atoms;

Among the oxime ester compounds represented by the general formula (C1), the oxime ester compounds in which X in the general formula (C1) is a thioether bond (-S-) and Y is no bond include the following: At least one selected from compound (C1-5) and compound (C1-6) below is more preferred.

Among the oxime ester compounds represented by the general formula (C1), the oxime ester compounds in which X in the general formula (C1) is a thioether bond (-S-) and Y is no bond are, for example, Synthesis can be performed with reference to JP-T-2012-526185.

As the oxime ester compound represented by the general formula (C1), among others, an oxime ester compound in which X in the general formula (C1) is a thioether bond (-S-) and Y is no bond, The combination with the silicon-containing compound (A) is preferable because the brightness of the colored layer can be easily improved.

Further, in the photosensitive colored resin composition of the present invention, the photoinitiator (C) contains two or more oxime ester compounds having no carbazole skeleton, so that a colored layer with improved brightness can be formed. It is preferable from the viewpoint of good sensitivity and easy adjustment of the line width during pattern formation. In the oxime ester compound having no carbazole skeleton, the reaction residue is unlikely to cause coloration, and thus reduction in brightness of the colored layer can be suppressed. Among them, by appropriately selecting and combining two or more kinds of oxime ester compounds having different sensitivities including the oxime ester compound represented by the general formula (C1), it is possible to maintain good sensitivity while forming a pattern. Line width can be adjusted. When the colored resin composition of the present invention contains two or more oxime ester compounds having no carbazole skeleton, it preferably contains at least one oxime ester compound represented by the general formula (C1). Two or more oxime ester compounds represented by (C1) may be included, and the oxime ester compound represented by the general formula (C1) is different from the oxime ester compound represented by the general formula (C1). An oxime ester compound having no carbazole skeleton may be included in combination.

In the photosensitive colored resin composition of the present invention, among others, the photoinitiator (C) is an oxime ester compound represented by the general formula (C1), wherein X in the general formula (C1) is -C ( In the oxime ester compound represented by R ^a ) (R ^b )—, a divalent group represented by — and Y being a direct bond, and the oxime ester compound represented by the general formula (C1), the general formula (C1 ) in combination with an oxime ester compound in which X is a thioether bond (-S-) and Y is a non-bond, it is possible to form a colored layer with improved brightness, and a line during pattern formation It is preferable because the width can be easily adjusted, and linearity can be further improved and rippling can be suppressed when forming a thin line pattern. When forming desired micropores in the colored layer at the same time as patterning the colored layer, the rims of the micropores are particularly susceptible to rippling, but the rippling of the rims of the micropores can also be suppressed.

Further, in the photosensitive colored resin composition of the present invention, the photoinitiator (C) contains an oxime ester compound represented by the general formula (C1), and further includes an α-aminoketone photoinitiator, a vinyl Containing at least one selected from imidazole-based photoinitiators, thioxanthone-based photoinitiators, acylphosphine oxide-based photoinitiators, and mercapto-based chain transfer agents improves brightness and forms a fine line pattern. In this case, the linearity is further improved, and the ability to form a fine line pattern as designed for the mask line width is improved.
Among them, it is preferable to use an acylphosphine oxide-based photoinitiator further in combination, from the viewpoint of suppressing the stickiness during pattern formation. Since the acylphosphine oxide photoinitiator has a higher thermal decomposition temperature than other initiators, it is thought that side reactions caused by heating during prebaking are less likely to occur, thereby suppressing tingling.

Further, from the viewpoint of further improving the linearity when forming a fine line pattern, the oxime ester compound represented by the general formula (C1) is added with an α-aminoketone photoinitiator, a biimidazole photoinitiator, It is preferable to use in combination with at least one selected from thioxanthone-based photoinitiators, acylphosphine oxide-based photoinitiators, and mercapto-based chain transfer agents. Among them, the oxime ester represented by the general formula (C1) As the compound, it is preferable to contain an oxime ester compound in which X in the general formula (C1) is a thioether bond (-S-) and Y is no bond, and α-aminoketone-based photoinitiators, biimidazole-based At least one selected from photoinitiators, thioxanthone-based photoinitiators, acylphosphine oxide-based photoinitiators, and mercapto-based chain transfer agents preferably contains a mercapto-based chain transfer agent. It is more preferred to use a combination of inhibitors.

The α-aminoketone-based photoinitiator has the property of curing the coating film from the surface to the middle, and is easy to suppress the deep part curability of the coating film, so when combined with the oxime ester compound represented by the general formula (C1), It is preferable because it tends to improve deep-part curability of the coating film.
Examples of α-aminoketone photoinitiators include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (eg Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino)-1-(4-morpholinophenyl)-1-butanone (eg Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF) and the like. The α-aminoketone-based photoinitiator may be used alone or in combination of two or more. 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone is preferable from the viewpoint of improving the film retention rate, and 2-methyl-1-(4-methylthiophenyl)-2 -Morpholinopropan-1-one is more preferable from the point of suppressing the stickiness.

The biimidazole-based photoinitiator has the property of curing the deep part of the coating film, and it is easy to suppress the coating film surface curability. It is preferable because it tends to improve the properties.
Biimidazole-based photoinitiators include, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl )-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl- 1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,2,2'-bis(2,4-dibromophenyl)-4,4', 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4,6-tribromophenyl)-4,4′,5,5′-tetraphenyl-1,2 '-Biimidazole and the like can be mentioned. The biimidazole-based photoinitiator may be used alone or in combination of two or more. Among them, it is preferable to use it in combination with a mercapto-based chain transfer agent from the viewpoint of improving the coating film curability.

Thioxanthone photoinitiators include, for example, 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2,4-dichlorothioxanthone. As the thioxanthone-based photoinitiator, it may be used alone or in combination of two or more. Among them, 2,4-isopropylthioxanthone and 2,4-diethylthioxanthone are used from the viewpoint of improving the transfer of radical generation. preferable.

Acylphosphine oxide-based photoinitiators have the property of less yellowing due to heat, and are therefore suitable for improving brightness, but generally have low sensitivity and may not provide sufficient curability. However, when combined with the oxime ester compound represented by the general formula (C1), the overall curability of the coating film is improved, and when the pattern is formed, the splintering of the edges is suppressed, and the dimensional accuracy tends to be improved. preferable.
Examples of acylphosphine oxide photoinitiators include benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 3, 4-dimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2 ,4,4-trimethyl-pentylphosphine oxide, bis(2,6-dimethylbenzoyl)-ethylphosphine oxide and the like. The acylphosphine oxide photoinitiator may be used alone or in combination of two or more. Among them, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is used to is preferable in terms of improvement.

Mercapto-based chain transfer agents have the property of accepting radicals from slow-reacting radicals, speeding up the reaction, and improving curability. preferable. A mercapto-based chain transfer agent is also preferable from the viewpoint of improving the effect of suppressing the occurrence of water stains. When the oxime ester photoinitiator represented by the general formula (C1) and the mercapto chain transfer agent are contained in combination, the developability is improved, the effect of suppressing the occurrence of water stains is further improved, and It is preferable in terms of improving the linearity when forming a fine line pattern and improving the ability to form a fine line pattern according to the design of the mask line width.
Mercapto chain transfer agents include, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3- Mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3- mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercapto butyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate). The mercapto-based chain transfer agent may be used alone or in combination of two or more. Among them, those having two or more mercapto groups in one molecule are preferred from the viewpoint of improving the effect of suppressing water staining. In addition, from the viewpoint that a good effect of suppressing water staining is easily maintained even when stored for a long period of time, it is preferable to have a secondary mercapto group in which the carbon atom to which the mercapto group is bonded is a secondary carbon atom. Those having two or more higher-grade mercapto groups in one molecule are more preferable.

The content of the photoinitiator (C) in the photosensitive colored resin composition is preferably 0.1% by mass or more and 15% by mass or less in 100% by mass of the total solid content of the photosensitive colored resin composition. , 1.0% by mass or more and 10% by mass or less. When the content of the photoinitiator (C) is at least the above lower limit, radical polymerization can be sufficiently promoted and poor curing can be suppressed, and the content of the photoinitiator (C) is at most the above upper limit. As a result, side reactions can be suppressed, and a decrease in stability over time can be suppressed.

The photoinitiator (C) is an oxime ester compound represented by the general formula (C1), wherein X in the general formula (C1) is -C(R ^a )(R ^b )- 2 an oxime ester compound (hereinafter referred to as oxime ester compound 1) in which Y is a direct bond and an oxime ester compound represented by the general formula (C1), wherein When X is a thioether bond (-S-) and Y is a non-bonded oxime ester compound (hereinafter referred to as oxime ester compound 2), the combination of the oxime ester compound 1 and the oxime ester compound 2 The ratio is preferably 10 parts by mass or more and 150 parts by mass or less of the oxime ester compound 2 with respect to 100 parts by mass of the oxime ester compound 1, and more preferably 15 parts by mass or more and 120 parts by mass or less. This is preferable in terms of brightness and sensitivity.
Further, when the photoinitiator (C) contains another photoinitiator different from the oxime ester compound 1 and the oxime ester compound 2, the total content of the oxime ester compound 1 and the oxime ester compound 2 The amount is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and even more preferably 50 parts by mass or more, based on a total of 100 parts by mass of the photoinitiator (C). On the other hand, it is preferably 95 parts by mass or less, more preferably 85 parts by mass or less, from the viewpoint of sufficiently exhibiting the effect of combined use with the other photoinitiators.

In addition, the photoinitiator (C) further comprises an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent. When at least one selected is contained, the total content of these is 0.1% by mass or more and 4.0% by mass or less, and further 0.5% by mass with respect to the total solid content of the photosensitive colored resin composition It is preferable that the content is in the range of 2.0% by mass or more from the viewpoint of sufficiently exhibiting the combined effect with these photoinitiators.
From the viewpoint of improving the effect of suppressing water staining by using a mercapto-based chain transfer agent as the photoinitiator (C), the content of the mercapto-based chain transfer agent with respect to the total solid content of the photosensitive colored resin composition is It is preferably 0.2% by mass or more and 4.0% by mass or less, more preferably 0.5% by mass or more and 2.0% by mass or less.

<Colorant (D)>
The coloring material contained in the photosensitive colored resin composition of the present invention is not particularly limited as long as the desired color development is possible when forming the colored layer of the color filter, and various organic pigments and inorganic pigments. , dispersible dyes can be used singly or in combination of two or more. Among them, organic pigments are preferably used because of their high color developability and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists).
Further, as the dispersible dye, various substituents are added to the dye, or a dye that is made dispersible by making it insoluble in a solvent using a known lake formation (chlorination) technique, or a dye with low solubility Dyes that become dispersible when used in combination with a solvent are included. By using such a dispersible dye in combination with the dispersant, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
As a guideline, if the amount of dye dissolved in 10 g of the solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

When red pixels are formed using the photosensitive colored resin composition of the present invention, the coloring material (D) used in the present invention is not particularly limited, and examples include diketopyrrolopyrrole pigments and naphthol azo pigments. and other red colorants such as azo pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, perinone pigments, perylene pigments, and thioindigo pigments. The red colorant used in the present invention, among others, has a high coloring power, and the P/V ratio ((colorant component mass in the composition) / (solid content mass other than the colorant component in the composition) ratio) is From the point of being able to suppress, it is preferable to contain at least one selected from the group consisting of diketopyrrolopyrrole-based pigments, naphthol-based azo pigments, anthraquinone-based pigments, and perylene-based pigments. From the viewpoint of easy formation and high brightness, it preferably contains at least one selected from the group consisting of diketopyrrolopyrrole pigments and anthraquinone pigments, and more preferably contains a diketopyrrolopyrrole pigment.

As the diketopyrrolopyrrole-based pigment, for example, one represented by the following general formula (D1) can be preferably used.

（一般式（Ｄ１）中、Ａ^３及びＡ^４は、それぞれ独立に、ハロゲン原子、メチル基、エチル基、ｔｅｒｔ－ブチル基、フェニル基、Ｎ，Ｎ－ジメチルアミノ基、トリフルオロメチル基、又はシアノ基を表し、ｋ及びｋ’はそれぞれ独立に０以上５以下の整数を表し、ｋ及びｋ’がそれぞれ２以上の整数の場合、複数のＡ^３及びＡ^４は、それぞれ同一でも異なっていてもよい。）

(In general formula (D1), A ³ and A ⁴ are each independently a halogen atom, a methyl group, an ethyl group, a tert-butyl group, a phenyl group, an N,N-dimethylamino group, a trifluoromethyl group, or represents a cyano group, k and k' each independently represent an integer of 0 or more and 5 or less, and when k and k' are each an integer of 2 or more, a plurality of A ³ and A ⁴ may be the same or different; is also good.)

Specific examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 270, C.I. I. Pigment Red 272, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73, and a diketopyrrolopyrrole pigment (BrDPP) represented by the following chemical formula (D1-1), among which C.I. I. Pigment Red 254 is preferred.

Examples of the naphthol-based azo pigment include C.I. I. Pigment Red 144, C.I. I. Pigment Red 166, C.I. I. Pigment Red 214, C.I. I. Pigment Red 242, C.I. I. Pigment Red 21, C.I. I. Pigment Red 2, C.I. I. Pigment Red 112, C.I. I. Pigment Red 114, C.I. I. Pigment Red 5, C.I. I. Pigment Red 146, C.I. I. Pigment Red 170, C.I. I. Pigment Orange 38, C.I. I. Pigment Red 187, C.I. I. Pigment Red 150, C.I. I. Pigment Red 185 and the like.
Other azo pigments include C.I. I. Pigment Red 38, C.I. I. Pigment Red 41 and the like.
Examples of the anthraquinone pigment include C.I. I. Pigment Red 177, C.I. I. Pigment Red 168, C.I. I. Pigment Orange 51 and the like.
Examples of the perylene pigment include C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 190, C.I. I. Pigment Red 224 and the like.

When forming a red pixel using the photosensitive colored resin composition of the present invention, as the colorant (D) used in the present invention, the red colorant may be used in combination with another colorant. . As the other colorant used in combination with the red colorant, at least one selected from, for example, a yellow colorant and an orange colorant not included in the red colorant can be suitably used.
Other coloring materials used in combination with the red coloring material specifically include C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 40, 43, 46, 49, 51, 61, 63, 64, and other orange colorants; C.I. I. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, yellow colorants such as 155, 156, 166, 167, 168, 175, 180, and 185;

When forming a red pixel using the photosensitive colored resin composition of the present invention, the content ratio of the red colorant relative to the entire colorant (D) may be appropriately adjusted according to the desired chromaticity, Although not particularly limited, from the viewpoint of brightness and contrast, the content of the red colorant is preferably 35% by mass or more and 99% by mass or less, and 40% by mass or more with respect to the total amount of the colorant 100% by mass. It is more preferably 98% by mass or less, and even more preferably 45% by mass or more and 97% by mass or less.

When green pixels are formed using the photosensitive colored resin composition of the present invention, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 and the like. Among them, C.I. I. Pigment Green 59 is preferred.

When forming a green pixel using the photosensitive colored resin composition of the present invention, C.I. I. Pigment Green 59 and C.I. I. Pigment Yellow 150 and its derivative pigments are preferably used in combination with at least one yellow colorant from the viewpoint of improving the brightness and contrast of the colored layer.
C. I. pigment green 59, C.I. I. Pigment Yellow 150 and at least one yellow colorant selected from derivative pigments thereof include, among others, an azo compound represented by the following general formula (D2) and an azo compound having a tautomeric structure thereof mono-, di-, tri- and At least one anion selected from the group consisting of tetraanions and at least two metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn and a compound represented by the following general formula (D3) (hereinafter referred to as yellow colorant (a)) is preferable from the viewpoint of improving luminance and contrast. The yellow colorant (a) contains two or more of the specific metal ions to suppress the crystal growth of the colorant, so that the colorant is easily atomized in the resin composition, so that the brightness and contrast is presumed to improve In addition, since the yellow colorant (a) has excellent coloring power, a colored layer with a high color density can be produced even if the P/V ratio is suppressed. In addition, since the total content of the coloring material components in the colored resin composition can be suppressed, the content of the binder component can be relatively increased, improving the plate-making properties and improving the adhesion to the substrate. It becomes possible to form a colored layer with higher color.

（一般式（Ｄ２）中、Ｒ^ｆはそれぞれ独立して、－ＯＨ、－ＮＨ_２、－ＮＨ－ＣＮ、アシルアミノ、アルキルアミノ又はアリールアミノであり、Ｒ^ｇはそれぞれ独立して、－ＯＨ又は－ＮＨ_２である。）

(In general formula (D2), each R ^f is independently —OH, —NH ₂ , —NH—CN, acylamino, alkylamino or arylamino, and each R ^g is independently —OH or — _NH2 .)

（一般式（Ｄ３）中、Ｒ^ｈはそれぞれ独立して、水素原子又はアルキル基である。）

(In general formula (D3), each R ^h is independently a hydrogen atom or an alkyl group.)

The acyl group in the acylamino group in general formula (D2) includes, for example, an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, a carbamoyl group optionally substituted with alkyl, phenyl, or naphthyl, an alkyl , a sulfamoyl group optionally substituted with phenyl or naphthyl, a guanyl group optionally substituted with alkyl, phenyl or naphthyl, and the like. The alkyl group preferably has 1 to 6 carbon atoms. In addition, the alkyl group may be substituted with halogen such as F, Cl, and Br, —OH, —CN, —NH ₂ , and/or an alkoxy group having 1 to 6 carbon atoms. The phenyl group and naphthyl group are, for example, halogens such as F, Cl, and Br, —OH, —CN, —NH ₂ , —NO ₂ , alkyl groups having 1 to 6 carbon atoms, and/or It may be substituted with 6 or less alkoxy groups.
The alkyl group in the alkylamino group in general formula (D2) preferably has 1 or more and 6 or less carbon atoms. The alkyl group may be substituted with, for example, halogen such as F, Cl, Br, --OH, --CN, --NH ₂ and/or an alkoxy group having 1 to 6 carbon atoms.
Examples of the aryl group in the arylamino group in the general formula (D2) include a phenyl group and a naphthyl group, and these aryl groups are, for example, halogens such as F, Cl, and Br, —OH, and 1 to 6 carbon atoms. , an alkoxy group having 1 to 6 carbon atoms, —NH ₂ , —NO ₂ and —CN.

In the azo compound represented by the general formula (D2) and the azo compound having a tautomeric structure thereof, each R ^f is independently —OH, —NH , —NH _— CN, or alkylamino. is preferable from the point of view of a reddish hue, and the two R ^f 's may be the same or different.
In the general formula (D2), the two R ^f are, from the viewpoint of hue, when both are —OH, when both are —NH—CN, or when one is —OH and one is —NH— More preferred is CN, and even more preferred is both --OH.

Further, in the azo compound represented by the general formula (D2) and the azo compound having the tautomeric structure thereof, R ^g is more preferably —OH in terms of hue.

At least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn are, among others, metals that become divalent or trivalent cations. It preferably contains at least one, preferably at least one selected from the group consisting of Ni, Cu, and Zn, and more preferably contains at least Ni.
Among them, it preferably contains Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn. Furthermore, it preferably contains at least one metal selected from the group consisting of Zn, Cu, Al and Fe. Above all, the at least two metals are preferably Ni and Zn or Ni and Cu.

The content ratio of at least two kinds of metals in the yellow colorant (a) may be appropriately adjusted. The content ratio of the at least one metal selected from the group consisting of Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn is Ni: the at least one other metal of 97:3 to It is preferably included in a molar ratio of 10:90.
When the other at least one metal contains Zn, it is preferable that Ni and Zn are contained in a molar ratio of Ni:Zn of 95:5 to 10:90, from the viewpoint of hue, and 90: It is more preferably included in a molar ratio of 10 to 10:90, even more preferably in a molar ratio of 80:20 to 20:80.
When the at least one other metal contains Cu, it is preferable that Ni and Cu are contained in a molar ratio of 97:3 to 10:90 in terms of hue, and 96: More preferably, it is contained in a molar ratio of 4-20:80.

The yellow colorant (a) may further contain metal ions different from the specific metal ions, such as Li, Cs, Mg, Na, K, Ca, Sr, Ba, Ce, of at least one metal selected from the group consisting of Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Ti, Zr, V, Nb, Mo and La It may contain ions. When the yellow colorant (a) contains three or more metal ions, at least one selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn The two metal ions include Ni and Zn metal ions, and Li, Cs, Mg, Na, K, Ca, Sr, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy , Ho, Er, Tm, Yb, Sc, Y, Ti, Zr, V, Nb, Mo and La ions, preferably La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, Mn, Cd, and Pb at least one metal ion selected from the group, more preferably at least one metal ion selected from the group consisting of La, Ce, Pr, Nd, Sm, Tb, Ho and Sr , the brightness and contrast can be improved, and the P/V ratio can be suppressed.

The yellow colorant (a) contains Ni and Zn as ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn. Li, Cs, Mg, Na, K, Ca, Sr, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y , Ti, Zr, V, Nb, Mo and La, the total amount of Ni and Zn is 75 mol% with respect to 100 mol% of all metals. It is preferably 99.5 mol % or more, and more preferably 80 mol % or more and 99 mol % or less. In addition, Li, Cs, Mg, Na, K, Ca, Sr, Ba, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb with respect to 100 mol% of all metals , Sc, Y, Ti, Zr, V, Nb, Mo and La. It is more preferably mol % or more and 20 mol % or less.

Also, C.I. I. pigment green 59, C.I. I. As at least one yellow colorant selected from Pigment Yellow 150 and derivative pigments thereof, mono-, di-, tri- and tetra-anions of the azo compound represented by the general formula (D2) and the azo compounds having tautomeric structures thereof At least one anion selected from the group consisting of Zn or Ni metal ions and La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, V, Nb, Cr, Mo, Mn, Cd, and at least two metal ions selected from the group consisting of Pb, and represented by the general formula (D3) A yellow colorant (hereinafter referred to as a yellow colorant (b)) containing a compound having a colorant such as a yellow colorant is also preferable from the viewpoint of improving brightness.

Examples of the embodiment in which the yellow colorant contains ions of at least two kinds of metals include the case where ions of at least two kinds of metals are contained in a common crystal lattice, and the case where ions of at least two kinds of metals are contained in separate crystal lattices. For example, crystals containing ions are aggregated. Among them, the case where at least two kinds of metal ions are contained in a common crystal lattice is preferable from the viewpoint of further improving the contrast. It should be noted that whether the crystal lattice contains ions of at least two kinds of metals in a common crystal lattice or the crystals each containing ions of one kind of metal in separate crystal lattices is agglomerated, For example, with reference to JP-A-2014-12838, it can be appropriately determined using an X-ray diffraction method.

The yellow colorant (a) and the yellow colorant (b) are a metal composed of an anion of the azo compound represented by the general formula (D2) and an azo compound having a tautomeric structure thereof and a specific metal ion It includes a composite molecule of a complex and the compound represented by the general formula (D3). Bonds between these molecules can be formed, for example, by intermolecular interactions, by Lewis acid-base interactions, or by coordinate bonds. Moreover, it may have a structure such as an inclusion compound in which the guest molecule is incorporated into the lattice that constitutes the host molecule. Alternatively, the two materials may form a co-crystal, forming a mixed permutation crystal in which the atoms of the second component are located in the regular lattice positions of the first component.

The alkyl group for R ^h in the general formula (D3) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be substituted with an --OH group.
Among them, R ^h is preferably a hydrogen atom.

The content of the compound represented by the general formula (D3) is generally It is 5 mol or more and 300 mol or less, preferably 10 mol or more and 250 mol or less, and more preferably 100 mol or more and 200 mol or less.

In addition, the yellow colorant (a) and the yellow colorant (b) further include urea and substituted ureas such as phenylurea and dodecylurea, and polycondensates thereof with aldehydes, particularly formaldehyde; For example barbituric acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2- hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, It may contain cyanuric acid or the like.
Further, the yellow colorant (a) and the yellow colorant (b) may further include a water-soluble polymer such as ethylene-propylene oxide-block polymer, polyvinyl alcohol, poly(meth)acrylic acid, carboxymethylcellulose, hydroxy Modified celluloses such as ethyl cellulose, hydroxypropyl cellulose, methyl- and ethylhydroxyethyl cellulose, and the like may also be included.

The yellow colorant (a) and the yellow colorant (b) can be prepared, for example, by referring to JP-A-2014-12838 and JP-A-2017-171912.

The average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as the coloring layer of the color filter can develop a desired color, and varies depending on the type of coloring material used. is preferably in the range of 10 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm or less. Since the average primary particle size of the colorant is within the above range, the display device equipped with the color filter produced using the photosensitive colored resin composition of the present invention has high contrast and high quality. can be done.

Further, the average dispersed particle size of the colorant in the colorant dispersion obtained by dispersing the colorant (D) in a solvent is preferably in the range of 10 nm to 100 nm, although it varies depending on the type of colorant used. , 15 nm or more and 60 nm or less.
The average dispersed particle size of the colorant in the colorant dispersion is the dispersed particle size of the colorant particles dispersed in the dispersion medium containing at least the solvent, and is measured by a laser light scattering particle size distribution meter. is. As for the measurement of the particle size by the laser light scattering particle size distribution meter, the solvent used in the colorant dispersion liquid is appropriately diluted to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times etc.), and can be measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (for example, Nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is the volume average particle size.

The content of the coloring material (D) in the photosensitive colored resin composition is preferably 5% by mass or more and 60% by mass or less in 100% by mass of the total solid content of the photosensitive colored resin composition, and 25% by mass % or more and 55 mass % or less. When the content of the coloring material (D) is at least the lower limit value, good optical properties can be obtained, and the desired function can be expressed. is 1.0 μm or more and 5.0 μm or less), the colored layer has a sufficient color density. When the content of the coloring material (D) is at most the above upper limit, poor curing is suppressed, the formation of the colored layer is facilitated, and the colored layer has excellent storage stability and adhesion to the substrate. can be obtained.
Especially when forming a coating film or a colored layer having a high colorant concentration, the content of the colorant (D) in the photosensitive colored resin composition is the total solid content of the photosensitive colored resin composition 100% by mass. Furthermore, it is preferably 15% by mass or more and 60% by mass or less, more preferably 25% by mass or more and 55% by mass or less.

<Dispersant (E)>
In the photosensitive colored resin composition of the present invention, the coloring material (D) is preferably used by dispersing it in a solvent described later with a dispersant. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants, and can be used singly or in combination of two or more. As the dispersing agent, for example, a cationic, anionic, nonionic, amphoteric, silicone or fluorine surfactant can be used. Among surfactants, polymer dispersants are preferred because they can be uniformly and finely dispersed.

Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkyleneimine) with free carboxy group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and free carboxy (a reaction product obtained by reacting one or more compounds selected from three compounds: polyesters, polyamides, or cocondensates of esters and amides (polyesteramides) having groups), and the like.

As the polymeric dispersant, among others, a polymeric dispersant containing a nitrogen atom in the main chain or side chain and having an amine value can suitably disperse the coloring material (D) and has good dispersion stability. Among them, a polymer dispersant composed of a polymer containing a repeating unit having a tertiary amine is preferred because it has good dispersibility, does not deposit foreign matter during coating film formation, and improves brightness and contrast. preferable. A repeating unit having a tertiary amine is a site having an affinity for the colorant (D). A polymeric dispersant comprising a polymer containing a repeating unit having a tertiary amine usually contains a repeating unit that serves as a site having affinity with a solvent. As the polymer containing a repeating unit having a tertiary amine, among others, a block copolymer having a block portion composed of a repeating unit having a tertiary amine and a block portion having solvent affinity is preferred for heat resistance. It is preferable in that it is possible to form a coating film that is excellent in brightness and has high brightness.

The repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may constitute the main chain. Among them, a repeating unit having a tertiary amine in the side chain is preferable, and among them, the structure represented by the following general formula (I) is preferable because the main chain skeleton is difficult to thermally decompose and has high heat resistance. is more preferred.

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａは、２価の連結基、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２及びＲ^３が互いに結合して環構造を形成してもよい。）

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom, or a hydrocarbon optionally containing a hetero atom. group, and R ² and R ³ may combine with each other to form a ring structure.)

In the general formula (I), A is a divalent linking group. The divalent linking group for A includes, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, an ether group having 1 to 10 carbon atoms (-R'-OR "-: R' and R" are each independently an alkylene group) and combinations thereof.
Among them, from the viewpoint of dispersibility, A in the general formula (I) is preferably a -CONH- group or a divalent linking group containing a -COO- group.

In the general formula (I), examples of the hydrocarbon group in the hydrocarbon group which may contain a heteroatom in R ² and R ³ include an alkyl group, an aralkyl group and an aryl group.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1. More than or equal to 18 or less is preferable, and among them, a methyl group or an ethyl group is more preferable.
The aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 14 or less.
Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less. In addition, the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.
A hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom. Examples of the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
Moreover, the hydrogen atom in the hydrocarbon group may be substituted with an alkyl group having 1 to 5 carbon atoms, or a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

That R ² and R ³ are bonded to each other to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. A heteroatom may be included in the ring structure formed by R ² and R ³ . Although the ring structure is not particularly limited, examples thereof include pyrrolidine ring, piperidine ring, morpholine ring and the like.

In the present invention, among others, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ² and R ³ are bonded to form a pyrrolidine ring, It is preferable to form a piperidine ring or a morpholine ring, in which at least one of R ² and R ³ is an alkyl group having 1 to 5 carbon atoms or a phenyl group, or R ² and R ³ are bonded preferably form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

Examples of structural units represented by the general formula (I) include alkyl group-substituted amino groups such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate and diethylaminopropyl (meth)acrylate. Examples thereof include group-containing (meth)acrylates and alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide. Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
The structural unit represented by the general formula (I) may consist of one type, or may contain two or more types of structural units.

From the viewpoint of improving the dispersibility, the polymer having the structural unit represented by the general formula (I) preferably further contains a site having solvent affinity. As the solvent affinity portion, a monomer having an ethylenically unsaturated bond polymerizable with the monomer deriving the structural unit represented by the general formula (I) is selected depending on the solvent so as to have solvent affinity. It is preferable to select and use them as appropriate. As a guideline, it is preferable to introduce a solvent affinity site so that the solubility of the polymer at 23° C. in the solvent used in combination is 50 (g/100 g solvent) or more.
As the polymer dispersant used in the present invention, it is possible to improve the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition, and to form a colored layer with high brightness and high contrast. Polymers or graft copolymers are preferred, block copolymers being particularly preferred. A particularly preferred block copolymer will be described in detail below.

(Block copolymer)
When the block containing the structural unit represented by the general formula (I) is referred to as the A block, the A block has a basic structural unit represented by the general formula (I), and is an adsorption site for the coloring material. function as On the other hand, the B block that does not contain the structural unit represented by the general formula (I) functions as a block having solvent affinity. In the present invention, the arrangement of each block in the block copolymer is not particularly limited, and examples thereof include AB block copolymers, ABA block copolymers, and BAB block copolymers. Among them, an AB block copolymer or an ABA block copolymer is preferable because of its excellent dispersibility.

Examples of the structural unit constituting the B block include a monomer having an unsaturated double bond that is copolymerizable with the monomer from which the structural unit represented by the general formula (I) is derived. Structural units of formula (II) are preferred.

（一般式（ＩＩ）中、Ａ’は、直接結合又は２価の連結基、Ｒ^４は、水素原子又はメチル基、Ｒ^５は、炭化水素基、－［ＣＨ（Ｒ^６）－ＣＨ（Ｒ^７）－Ｏ］_ｘ－Ｒ^８又は－［（ＣＨ_２）_ｙ－Ｏ］_ｚ－Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ_２ＣＨＯ、又は－ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素数１以上５以下のアルキル基である。
前記炭化水素基は、置換基を有していてもよい。
ｘは１以上１８以下の整数、ｙは１以上５以下の整数、ｚは１以上１８以下の整数を示す。）

(In general formula (II), A′ is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, —[CH(R ⁶ )—CH(R ⁷ ) a monovalent group represented by —O] _x —R ⁸ or —[(CH ₂ ) _y —O] _z —R ^8. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group; and R ⁸ is a hydrogen atom, a hydrocarbon group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ and is a monovalent group represented by —CH 2 COOR 9 , and R ⁹ is a hydrogen atom or a It is an alkyl group.
The hydrocarbon group may have a substituent.
x is an integer of 1 or more and 18 or less, y is an integer of 1 or more and 5 or less, and z is an integer of 1 or more and 18 or less. )

The divalent linking group A' in general formula (II) can be the same as A in general formula (I). Among them, A' is preferably a direct bond or a divalent linking group containing a -CONH- or -COO- group, from the viewpoint of solubility in organic solvents. In view of the heat resistance of the obtained polymer, the solubility in propylene glycol monomethyl ether acetate (PGMEA), which is suitably used as a solvent, and the fact that it is a relatively inexpensive material, A' is a -COO- group. preferable.

The hydrocarbon group for R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and 2-ethylhexyl. group, 2-ethoxyethyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, adamantyl group, and lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of the reactivity of the resulting polymer.
A nitro group, a halogen atom, etc. can be mentioned as a substituent of aliphatic hydrocarbons, such as an alkyl group and an alkenyl group.

The aryl group includes phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group and the like, and may further have a substituent. The number of carbon atoms in the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.
Moreover, the aralkyl group includes a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 14 or less.
Examples of aromatic ring substituents such as aryl groups and aralkyl groups include linear or branched alkyl groups having 1 to 4 carbon atoms, alkenyl groups, nitro groups, and halogen atoms.
In addition, the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.

In R ⁵ , x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably 1 to 4. is an integer of, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less.

The hydrocarbon group for R ⁸ can be the same as those shown for R ⁵ above.
R9 is a hydrogen atom or an alkyl group having ¹ to 5 carbon atoms, and may be linear, branched or cyclic.
Moreover, R ⁵ in the structural unit represented by the general formula (II) may be the same as or different from each other.

Among them, R ⁵ is preferably selected so as to have excellent compatibility with the solvent described later. Specifically, for example, the solvent is generally used as a solvent for a photosensitive colored resin composition. When the glycol ether acetate-based, ether-based, and ester-based solvents used in the above are used, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group and the like are preferable.

Furthermore, the R ⁵ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, or an isocyanate group within a range that does not interfere with the dispersibility of the block copolymer. After synthesizing the polymer, the substituent may be added by reacting with the compound having the substituent.

In the present invention, the glass transition temperature (Tg) of the solvent-affinity block portion of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-affinitive block portion is preferably 80° C. or higher, more preferably 100° C. or higher.
The glass transition temperature (Tg) of the solvent affinity block portion in the present invention can be calculated by the following formula. Similarly, the glass transition temperature of the colorant-affinity block portion and the block copolymer can also be calculated.
1/Tg=Σ(Xi/Tgi)
Here, it is assumed that n monomer components from i=1 to n are copolymerized in the solvent affinity block portion. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ takes the sum from i=1 to n. In addition, the value of the homopolymer glass transition temperature (Tgi) of each monomer can adopt the value of Polymer Handbook (3rd Edition) (J. Brandrup, EH Immergut (Wiley-Interscience, 1989)). can.

The number of structural units constituting the solvent-affinity block portion may be appropriately adjusted within a range in which the coloring material dispersibility is improved. Among them, the solvent affinity portion and the colorant affinity portion act effectively to improve the dispersibility of the colorant, so the number of structural units constituting the solvent affinity block portion is 10 or more and 200 or less. It is preferably 10 or more and 100 or less, and further preferably 10 or more and 70 or less.

The solvent affinity block portion may be selected so as to function as a solvent affinity portion, and the repeating units constituting the solvent affinity block portion may consist of one type or two or more types. may contain a repeating unit of

In addition, among others, the dispersant in the present invention preferably contains a polymer having a structure represented by the general formula (II) and an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less. It is preferable from the viewpoint of improving brightness and contrast without depositing foreign matter during coating film formation.
When the amine value is within the above range, the viscosity stability over time and heat resistance are excellent, and alkali developability and solvent re-solubility are also excellent. In the present invention, the amine value of the dispersant is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, the amine value of the dispersant is preferably 110 mgKOH/g or less, more preferably 105 mgKOH/g or less, from the viewpoint of solvent resolubility.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so the block copolymer itself used as the dispersant can be measured.

The lower limit of the acid value of the dispersant used in the present invention is preferably 1 mgKOH/g or more from the viewpoint of the effect of suppressing development residue. Among them, it is more preferable that the acid value of the dispersant is 2 mgKOH/g or more because the effect of suppressing development residue is more excellent. Further, the upper limit of the acid value of the dispersant used in the present invention is 18 mgKOH/g or less from the viewpoint of preventing deterioration of development adhesion and deterioration of solvent resolubility. preferable. Above all, the acid value of the dispersant is more preferably 16 mgKOH/g or less, and even more preferably 14 mgKOH/g or less, from the viewpoint of good development adhesion and solvent re-solubility.
In the dispersant used in the present invention, the block copolymer before salt formation preferably has an acid value of 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. This is because the effect of suppressing development residue is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 16 mgKOH/g or less, and even more preferably 14 mgKOH/g or less. . This is because development adhesion and solvent re-solubility are improved.
Incidentally, in the present invention, the acid value can be measured according to JIS K 0070.

Moreover, in the present invention, the glass transition temperature of the dispersant is preferably 30° C. or higher from the viewpoint of improving adhesion to development. That is, the glass transition temperature of the dispersant is preferably 30° C. or higher, regardless of whether the dispersant is a pre-salt block copolymer or a salt-type block copolymer. If the glass transition temperature of the dispersing agent is low, it is particularly close to the temperature of the developer (usually about 23° C.), and there is a possibility that the development adhesion may be lowered. It is presumed that this is because when the glass transition temperature approaches the developer temperature, the movement of the dispersant increases during development, and as a result, the development adhesion deteriorates. When the glass transition temperature is 30° C. or higher, the molecular movement of the dispersant during development is suppressed, so it is presumed that the decrease in development adhesion is suppressed.
The glass transition temperature of the dispersant is preferably 32° C. or higher, more preferably 35° C. or higher, from the viewpoint of development adhesion. On the other hand, the temperature is preferably 200° C. or less from the viewpoint of operability during use, such as facilitating accurate weighing.
The glass transition temperature of the dispersant in the invention can be obtained by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

When the concentration of the coloring material is increased and the content of the dispersant is increased, the amount of the binder is relatively decreased, so that the colored resin layer is easily peeled off from the underlying substrate during development. The dispersant contains a B block containing a structural unit derived from a carboxyl group-containing monomer, and has the above-mentioned specific acid value and glass transition temperature, thereby improving development adhesion. If the acid value is too high, the developability will be excellent, but the polarity will be too high, and it is presumed that peeling will rather easily occur during development.

From the above, the dispersant in the present invention is a polymer containing the structure represented by the general formula (I) and having an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less, and an acid value of 1 mgKOH / g or more and 18 mgKOH / g or less and a glass transition temperature of 30 ° C. or more have excellent colorant dispersion stability, improve contrast, and suppress the generation of development residues when used as a colored resin composition. However, it is preferable from the viewpoint of being excellent in solvent re-solubility and having high development adhesion.

As the carboxy group-containing monomer, a monomer containing an unsaturated double bond and a carboxy group, which is copolymerizable with the monomer having the structural unit represented by the general formula (I), can be used. Examples of such monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimers. Also, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used. Acid anhydride group-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as a precursor of the carboxy group. Among them, (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, glass transition temperature, and the like.

When the structural unit derived from the carboxy group-containing monomer is contained, the content ratio of the structural unit derived from the carboxy group-containing monomer in the block copolymer before salt formation is such that the acid value of the block copolymer is above the specific acid value. It may be set appropriately so as to fall within the range, and is not particularly limited. It is more preferably 0.07% by mass or more and 3.7% by mass or less.
When the content ratio of the structural unit derived from the carboxy group-containing monomer is at least the lower limit value, the effect of suppressing development residue is exhibited, and when it is at most the upper limit value, development adhesion is deteriorated and solvent resolubility is reduced. It can prevent deterioration.
The structural unit derived from the carboxy group-containing monomer may have the specific acid value, and may consist of one type or may contain two or more types of structural units.

Further, the glass transition temperature of the dispersant used in the present invention is set to a specific value or higher, and the development adhesiveness is improved, so the glass transition temperature value (Tgi) of the homopolymer of the monomer is 10 ° C. or higher. is preferably 75% by mass or more, more preferably 85% by mass or more, in the B block in total.

In the block copolymer, the ratio m/n between the number m of the constituent units of the A block and the number n of the constituent units of the B block is in the range of 0.05 or more and 1.5 or less. It is more preferably in the range of 0.1 or more and 1.0 or less from the viewpoint of dispersibility and dispersion stability of the colorant.

Although the weight average molecular weight Mw of the block copolymer is not particularly limited, it is preferably 1000 or more and 20000 or less, and 2000 or more and 15000 or less from the viewpoint of improving the colorant dispersibility and dispersion stability. is more preferably 3000 or more and 12000 or less.
Here, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC), converted to standard polystyrene, using THF as an eluent, Shodex GPC System-21H (Shodex GPC System-21H). can be measured. Note that macromonomers, salt-type block copolymers, and graft copolymers, which are raw materials for block copolymers, are also processed under the above conditions.

The method for producing the block copolymer is not particularly limited. A block copolymer can be produced by a known method, but is preferably produced by a living polymerization method. This is because chain transfer and deactivation are unlikely to occur, a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include a living radical polymerization method, a living anion polymerization method such as a group transfer polymerization method, a living cationic polymerization method, and the like. A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, a block copolymer can be produced by first producing the A block and then polymerizing the structural units constituting the B block onto the A block. Also, the order of polymerization of the A block and the B block can be reversed in the above production method. It is also possible to prepare the A and B blocks separately and then couple the A and B blocks.

Specific examples of the block copolymer having a block portion containing a structural unit represented by the general formula (I) and a block portion having solvent affinity are described in Japanese Patent No. 4911253. Block copolymers may be mentioned as suitable.

In the present invention, from the viewpoint of the dispersibility and dispersion stability of the coloring material, at least a portion of the amino groups in the polymer containing the structural unit represented by the general formula (I), an organic acid compound or It is also preferable to use a dispersant formed by forming a salt with a halogenated hydrocarbon (such a polymer is hereinafter sometimes referred to as a salt-type polymer).
Among them, the polymer containing a repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. and excellent dispersion stability. Specific examples of the organic acid compound used in such a dispersant include, for example, the organic acid compounds described in JP-A-2012-236882 as suitable ones.
Further, the halogenated hydrocarbon is preferably at least one selected from allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

The content of the dispersant (E) in the photosensitive colored resin composition is appropriately selected according to the type of coloring material used and the solid content concentration in the photosensitive colored resin composition, and is not particularly limited. In 100% by mass of the total solid content of the photosensitive colored resin composition, it is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 30% by mass or less, 3% by mass or more and 25% by mass. % or less is even more preferable. When the content of the dispersant (E) is at least the lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition is excellent. Moreover, if it is below the said upper limit, developability will become favorable.
Especially when forming a colored layer with a high colorant concentration, the content of the dispersant (E) in the photosensitive colored resin composition is 2 in the total solid content of the photosensitive colored resin composition 100% by mass. It is preferably from 3% by mass to 25% by mass, more preferably from 3% by mass to 20% by mass.

<Solvent (F)>
The photosensitive colored resin composition of the present invention may further contain a solvent, if necessary. The solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive colored resin composition and is capable of dissolving or dispersing them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, i-propyl alcohol and methoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate and methoxypropione. Ester solvents such as methyl acid, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, clohexanol acetate; acetone, Ketone solvents such as methyl ethyl ketone, cyclohexanone and 2-heptanone; glycol ether acetates such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl Glycol ether solvents such as ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; N,N-dimethyl Aprotic amide solvents such as formamide, N,N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated carbonization such as benzene, toluene, xylene and naphthalene. Hydrogen-based solvents; saturated hydrocarbon-based solvents such as N-heptane, N-hexane and N-octane; and organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used in terms of solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl carbitol acetate (BCA), 3-methoxy -1 or more selected from the group consisting of 3-methyl-1-butyl acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate, dispersibility or solubility of other components It is preferable from the viewpoint of the properties and coating suitability.

From the viewpoint of developability, solvent re-solubility, etc., it is also preferable to use a mixed solvent containing two or more kinds of solvents.
When a mixed solvent is used, the first solvent is the above-described glycol ether acetate-based solvent because of its high safety, moderate volatility, and good dispersibility due to its moderate solubility. Solvents are preferably used. Among them, 2-methoxyethyl acetate or propylene glycol monomethyl ether acetate having a boiling point (meaning the boiling point at atmospheric pressure; the same shall apply hereinafter) of less than 150° C. is more preferred, and propylene glycol monomethyl ether acetate (PGMEA) is particularly preferred. preferable.

As the second solvent, which is a solvent other than the first solvent, a solvent having an alcoholic hydroxyl group or a solvent having a boiling point of 150° C. or higher is preferable. A 2nd solvent may be used individually by 1 type, and may mix and use 2 or more types.
When a solvent having an alcoholic hydroxyl group is used as the second solvent, dispersibility is improved and solvent re-solubility tends to be improved.
Examples of the solvent having an alcoholic hydroxyl group include the alcohol solvent, the carbitol solvent, and the glycol ether solvent. Specific examples include propylene glycol monomethyl ether (boiling point 121° C.), 3-methoxy- 3-methyl-1-butanol (boiling point 174° C.) and the like.

When a mixed solvent is used, the content of the solvent having an alcoholic hydroxyl group is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less in the total solvent. Moreover, 0.1 mass % or more is preferable, 0.3 mass % or more is more preferable, and 1 mass % or more is still more preferable.
Within the above range, the solubility of the dispersant tends to be good, and the dissolution of the dispersant in the first solvent is not hindered, so the dispersion stability tends to be good.

When the first solvent is a solvent with a boiling point of less than 150 ° C., if a solvent with a boiling point of 150 ° C. or higher is used as the second solvent, uneven drying is less likely to occur, foreign matter is less likely to occur, and solvent re-solubility is likely to be improved. .
Examples of solvents having a boiling point of 150° C. or higher include diethylene glycol ethyl methyl ether (boiling point 179° C.), 3-methoxy-3-methyl-1-butyl acetate (boiling point 188° C.), and diethylene glycol ethyl methyl ether (boiling point 179° C.). , 3-methoxybutyl acetate (boiling point 172° C.) and the like.

When a mixed solvent is used, the content of the solvent having a boiling point of 150° C. or higher is preferably 40% by mass or less, more preferably 30% by mass or less, in the total solvent. Moreover, it is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more.
Within the above range, drying unevenness is less likely to occur, and the drying time does not become too long, and productivity tends to be good.

The boiling point of the "solvent having a boiling point of 150° C. or higher" is preferably 240° C. or lower, particularly preferably 200° C. or lower, in order to prevent excessive drying time.

When the photosensitive colored resin composition of the present invention contains a solvent (F), the content of the solvent (F) is not particularly limited, but improves the coatability and improves the dispersibility or solubility of other components. From the viewpoint of easy improvement, it is usually preferably in the range of 55% by mass or more and 95% by mass or less with respect to the total amount of the photosensitive colored resin composition containing the solvent (F), and among them 60% by mass or more and 90% by mass. % or less.

<Antioxidant (G)>
The photosensitive colored resin composition of the present invention may further contain an antioxidant. By containing an antioxidant, the photosensitive colored resin composition of the present invention can improve the heat resistance and suppress the decrease in luminance after exposure and post-baking, thereby improving the luminance. Among others, the photosensitive colored resin composition of the present invention preferably contains an antioxidant in combination with the oxime ester compound represented by the general formula (1).

The antioxidant used in the present invention is not particularly limited, and can be appropriately selected from conventionally known ones and used alone or in combination of two or more. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. From this point of view, it is preferable to use a hindered phenol-based antioxidant.

A hindered phenol-based antioxidant contains at least one phenol structure, and has a structure in which at least one of the 2- and 6-positions of the hydroxyl group of the phenol structure is substituted with a substituent having 4 or more carbon atoms. means antioxidant.
Specific examples of hindered phenol antioxidants include dibutylhydroxytoluene (BHT), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4 ,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl)mesitylene (trade name: Irganox 1330, manufactured by BASF), 6-(4-hydroxy-3,5-di-tert-butylanilino )-2,4-bis(octylthio)-1,3,5-triazine (trade name: Irganox 565, manufactured by BASF), 2,2′-thiodiethylbis[3-(3,5-di-tert -Butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1035, manufactured by BASF), 1,2-bis[3-(4-hydroxy-3,5-di-tert-butylphenyl)propionyl]hydrazine (trade name: Irganox MD1024, manufactured by BASF), octyl 3-(4-hydroxy-3,5-diisopropylphenyl)propionate (trade name: Irganox 1135, manufactured by BASF), 4,6-bis(octyl) thiomethyl)-o-cresol (trade name: Irganox 1520L, manufactured by BASF), N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] (trade name: Irganox 1098, manufactured by BASF), 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 259, BASF) company), 1-dimethyl-2-[(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5.5]undecane ( Trade name: ADK STABAO-80, manufactured by Adeka), bis(3-tert-butyl-4-hydroxy-5-methylbenzenepropionic acid) ethylene bis(oxyethylene) (trade name: Irganox 245, manufactured by BASF), 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Irganox 1790, manufactured by BASF), 2,2′-methylenebis(6-tert-butyl-4- methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6′-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3, Diethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert- Butyl-5-methylbenzyl)phenyl (trade name: Sumilizer GM, manufactured by Sumitomo Chemical), 4,4′-thiobis(6-tert-butyl-m-cresol) (trade name: Sumilizer WX-R, manufactured by Sumitomo Chemical) , 6,6′-di-tert-butyl-4,4′-butylidenedi-m-cresol (trade name: ADEKA STAB AO-40, manufactured by ADEKA). In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

Moreover, in the present invention, a latent antioxidant may be used as the antioxidant. In the present invention, the latent antioxidant is a compound having a protective group that can be removed by heating, and a compound that exhibits an antioxidant function when the protective group is removed. Among them, those from which the protecting group is easily eliminated by heating at 150° C. or higher are preferable. Since the latent antioxidant does not have an antioxidant function during exposure, it does not deactivate the radicals generated from the photoinitiator, suppresses the decrease in sensitivity, suppresses the narrowing of the line width, and reduces the residual film rate. easy to improve. On the other hand, in the heating step performed after the exposure, the protective group is eliminated and the antioxidant effect is exhibited, so that the fading of the coloring material and the like is suppressed, and a colored layer with high brightness can be obtained.
From the viewpoint of heat resistance and compatibility, the latent antioxidant preferably used in the present invention is a latent antioxidant obtained by protecting the phenolic hydroxyl group of a hindered phenolic antioxidant with a protecting group that can be removed by heating. Examples include chemically hindered phenol-based antioxidants, and specific examples thereof include those represented by the following chemical formulas (a) to (c), but are not limited to these.

The method for producing the latent antioxidant is not particularly limited. 2004-501128, with an acid anhydride, an acid chloride, a Boc reagent, an alkyl halide compound, a silyl chloride compound, an allyl ether compound, etc. can be done. Moreover, you may use a commercial item.
Examples of the protecting group that can be removed by heating include reaction residues of acid anhydrides, acid chlorides, Boc conversion reagents, alkyl halide compounds, silyl chloride compounds, or allyl ether compounds, typically , t-butoxycarbonyl group.

When the photosensitive colored resin composition of the present invention contains an antioxidant (G), the content of the antioxidant (G) in the photosensitive colored resin composition is not particularly limited, but after exposure and post-baking From the viewpoint of suppressing the decrease in brightness of the colored layer and improving the brightness of the colored layer, the total solid content of 100% by mass of the photosensitive colored resin composition is preferably 0.1% by mass or more and 20% by mass or less, and 0 0.2% by mass or more and 10% by mass or less, and even more preferably 0.3% by mass or more and 5% by mass or less.

In addition, the content of the antioxidant is 10 parts by mass or more with respect to a total of 100 parts by mass of the photoinitiator (C) from the viewpoint of sufficiently exhibiting the combined effect with the photoinitiator. is preferred, 20 parts by mass or more is more preferred, and 30 parts by mass or more is even more preferred. On the other hand, from the viewpoint of maintaining appropriate sensitivity, the amount is preferably 300 parts by mass or less, more preferably 200 parts by mass or less with respect to the total 100 parts by mass of the photoinitiator (C).

<Alkali-soluble resin>
The photosensitive colored resin composition of the present invention may further contain an alkali-soluble resin.
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder component and are soluble in an alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
A preferable alkali-soluble resin in the present invention is a polymer having an acidic group, usually a carboxy group. polymer, epoxy (meth)acrylate polymer having a carboxyl group, and the like. Among these, particularly preferred are those having a carboxyl group in the side chain and a photopolymerizable functional group such as an ethylenically unsaturated bond in the side chain. By containing a photopolymerizable functional group in the side chain of the alkali-soluble resin, in the step of curing the resin composition during the production of a color filter, the alkali-soluble resins themselves, or the alkali-soluble resin is combined with the silicon-containing compound or By reacting with the ethylenically unsaturated bond of the photopolymerizable compound to form a crosslinked bond, a decrease in brightness is suppressed, the film strength of the cured film is further improved, and the development resistance is improved. The thermal shrinkage of the cured film is suppressed, and the adhesiveness to the substrate is excellent.

Acrylic polymers such as acrylic copolymers having a structural unit having a carboxyl group and styrene-acrylic copolymers having a carboxyl group are, for example, carboxyl group-containing monomers, and optionally other copolymerizable monomers. is a (co)polymer obtained by (co)polymerizing the monomers of the above by a known method.
As the carboxyl group-containing monomer, for example, the same as those described in the dispersing agent (E) can be mentioned. is preferred.

A method for introducing an ethylenically unsaturated bond into an alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of adding a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, to the carboxyl group of the alkali-soluble resin to introduce an ethylenically unsaturated bond into the side chain. Alternatively, a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenically unsaturated bond is added to the molecule, and an ethylenically unsaturated bond is introduced into the side chain. etc.

The alkali-soluble resin used in the present invention preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. Examples of the hydrocarbon ring include an optionally substituted aliphatic hydrocarbon ring, an optionally substituted aromatic hydrocarbon ring, and combinations thereof.
Specific examples of the hydrocarbon ring include aliphatic hydrocarbon rings such as cyclohexane, norbornane, and adamantane; aromatic hydrocarbon rings such as benzene and naphthalene; chain polycyclic rings such as biphenyl; 9-diarylfluorene) and the like.
Examples of the substituent that the hydrocarbon ring may have include an alkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, and a halogen atom.
The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher group.

In the alkali-soluble resin used in the present invention, using an acrylic copolymer having a structural unit having a hydrocarbon ring separately from a structural unit having a carboxy group makes it easy to adjust the amount of each structural unit. It is preferable from the viewpoint that the amount of structural units having a hydrocarbon ring can be increased to easily improve the functions of the structural units.
The acrylic copolymer having a structural unit having a carboxyl group and the hydrocarbon ring can be prepared by using a monomer having a hydrocarbon ring as the aforementioned "other copolymerizable monomer".

Examples of monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl (meth)acrylate. , styrene, etc., and from the point that the effect of maintaining the cross-sectional shape of the colored layer after development is large even in heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, At least one selected from benzyl (meth)acrylate and styrene is preferably used.

The alkali-soluble resin used in the present invention may further contain other structural units such as structural units having an ester group such as methyl (meth)acrylate and ethyl (meth)acrylate. The structural unit having an ester group functions not only as a component that suppresses alkali solubility of the photosensitive colored resin composition, but also as a component that improves solvent solubility and solvent re-solubility.
The alkali-soluble resin can be made into an alkali-soluble resin having desired performance by appropriately adjusting the charged amount of each structural unit.

The weight average molecular weight Mw of the alkali-soluble resin used in the present invention is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be significantly deteriorated, and if it exceeds 50,000, pattern formation may become difficult during development with an alkaline developer.

The alkali-soluble resin used in the present invention preferably has an acid value of 50 mgKOH/g or more from the viewpoint of developability (solubility) in an alkaline aqueous solution used in the developer. The alkali-soluble resin preferably has an acid value of 70 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of developability (solubility) in an alkaline aqueous solution used in the developer and adhesion to a substrate. It is preferably 80 mgKOH/g or more and 280 mgKOH/g or less.

When the side chain of the alkali-soluble resin has an ethylenically unsaturated bond, the ethylenically unsaturated bond equivalent improves the film strength of the cured film, improves the development resistance, and achieves the effect of excellent adhesion to the substrate. From this point of view, it is preferably in the range of 100 g/mol or more and 2000 g/mol or less, and particularly preferably in the range of 140 g/mol or more and 1500 g/mol or less. When the ethylenically unsaturated bond equivalent is 100 g/mol or more, the development resistance and adhesion are excellent. In addition, if it is 2000 g / mol or less, the proportion of other structural units such as the structural unit having a carboxy group and the structural unit having a hydrocarbon ring can be relatively increased, so that the developability and heat resistance are improved. Are better.
Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (2).
Formula (2)
Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In formula (2), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g).)

The ethylenically unsaturated bond equivalent is, for example, according to the iodine value test method described in JIS K 0070: 1992, by measuring the number of ethylenically unsaturated bonds contained per 1 g of the alkali-soluble resin. can be calculated.

In the present invention, the alkali-soluble resin may be used singly or in combination of two or more. If the photosensitive colored resin composition of the present invention contains an alkali-soluble resin, the content is not particularly limited, relative to the total solid content of the photosensitive colored resin composition, the effect of improving the alkali developability It is preferably 1% by mass or more, more preferably 2% by mass or more, because it is easy to obtain, and it is 10% by mass or less because the silicon-containing compound (A) is sufficiently contained. is preferred.
In the photosensitive colored resin composition of the present invention, the content of the alkali-soluble resin is preferably 25 parts by mass or less, more preferably 22 parts by mass or less, relative to 100 parts by mass of the silicon-containing compound (A). It is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

<Optional Addition Ingredients>
The photosensitive colored resin composition of the present invention may optionally contain various additives.
Additives include, for example, antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like. mentioned.
Specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.

Examples of silane coupling agents include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like. Among them, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 having a methacrylic group or an acrylic group are preferable from the viewpoint of adhesion to SiN substrates.

As the content of the silane coupling agent, the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the total solid content in the colored resin composition. .1 mass parts or more and 5.0 mass parts or less are more preferable. If it is more than the said lower limit and below the said upper limit, it will be excellent in the adhesiveness of SiN.

In the photosensitive colored resin composition of the present invention, the P/V ratio ((coloring material component mass in the composition)/(solid content mass other than the coloring material component in the composition) ratio) is controlled by degassing and heat. From the viewpoint of shrinkage, it is preferably 0.1 or more, more preferably 0.2 or more. From the standpoint of superiority, it is preferably 0.8 or less, more preferably 0.7 or less, and from the standpoints of development residue and development adhesion, it is even more preferably 0.6 or less.

<Method for producing a photosensitive colored resin composition>
The method for producing the photosensitive colored resin composition of the present invention is not particularly limited. A silicon-containing compound (A), a photopolymerizable compound (B), a photoinitiator (C), and, if necessary, other components such as a dispersion-assisting resin are added to the colorant dispersion. , can be obtained by mixing using a known mixing means. When the colorant (D) contains two or more colorants, a dispersant is used as necessary to prepare a colorant dispersion for each colorant, and each colorant dispersion and a silicon-containing compound are prepared. (A), a photopolymerizable compound (B), a photoinitiator (C), and, if necessary, other components such as a dispersion-assisting resin can be mixed using a known mixing means. can.
Examples of the dispersion-assisting resin include the alkali-soluble resins. The steric hindrance of the alkali-soluble resin may make it difficult for the colorant particles to come into contact with each other, and may have the effect of stabilizing the dispersion and reducing the amount of the dispersant due to the effect of stabilizing the dispersion.
In addition, the colorant dispersion may optionally contain, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, and an antifoaming agent, as long as the effects of the present invention are not impaired. Additives such as agents, anti-cratering agents, antioxidants, anti-aggregating agents, and UV absorbers may be contained.
Although the method for producing the colorant dispersion is not particularly limited, it is preferable to use, for example, one of the following two production methods.

A first method for producing the colorant dispersion comprises the steps of preparing the dispersant and dispersing the colorant in a solvent in the presence of the dispersant. Two or more colorants may be co-dispersed in a solvent in the presence of the dispersant, or one or more colorants may be dispersed or co-dispersed and then two or more colorant dispersions may be mixed. You may obtain the said coloring material dispersion liquid by carrying out.

The second method for producing the colorant dispersion is a method using the dispersant that is the salt-type block copolymer, and the solvent, the block copolymer, the organic acid compound, and the halogenated hydrocarbon , by mixing with a coloring material to form a salt of at least part of the terminal nitrogen portion of the structural unit represented by the general formula (I) and the organic acid compound or halogenated hydrocarbon, while color and dispersing the material. Even in the case of dispersing the colorant while forming such a salt, two or more colorants may be co-dispersed, or one or more colorants may be dispersed or co-dispersed before two or more colorants are dispersed. The coloring material dispersion may be obtained by mixing the material dispersions.

In the first production method and the second production method, the colorant can be dispersed using a conventionally known disperser.
Specific examples of the disperser include roll mills such as two-roll and three-roll roll mills, ball mills such as ball mills and vibrating ball mills, bead mills such as paint conditioners, continuous disk-type bead mills, and continuous annular-type bead mills. As preferable dispersion conditions for the bead mill, the diameter of the beads used is preferably 0.03 mm or more and 3.0 mm or less, more preferably 0.05 mm or more and 2.0 mm or less.

[Cured product]
The cured product according to the present invention is a cured product of the photosensitive colored resin composition according to the present invention.
The cured product according to the present invention is suitably used as a colored layer of a color filter, and since it is a cured product of the photosensitive colored resin composition according to the present invention, the decrease in luminance is suppressed. .
The cured product according to the present invention, for example, forms a coating film of the photosensitive colored resin composition according to the present invention, and after drying the coating film, is exposed, if necessary in the silicon-containing compound It can be obtained by heating for reacting and bonding the reactive groups and, if necessary, developing. The method of forming, exposing, heating, and developing the coating film may be, for example, the same method as that used in the formation of the colored layer provided in the color filter according to the present invention, which will be described later.

[Color filter]
The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive colored resin composition according to the present invention. It is a cured product.

Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light shielding portion 2 and a colored layer 3. As shown in FIG.

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition according to the present invention, that is, a colored layer formed by curing the colored resin composition.
The colored layer is usually formed in the opening of the light shielding part on the substrate, which will be described later, and is usually composed of colored patterns of three or more colors.
Moreover, the arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type. Moreover, the width, area, etc. of the colored layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, solid content concentration and viscosity of the photosensitive colored resin composition, and is preferably in the range of 1 μm to 5 μm.

The colored layer can be formed, for example, by the following method.
First, the photosensitive colored resin composition of the present invention described above is applied onto a substrate described later using a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. to form a wet coating. Among them, the spin coating method and the die coating method can be preferably used.
Next, after drying the wet coating film using a hot plate or an oven, it is exposed through a mask of a predetermined pattern to photopolymerize the polymer and the photopolymerizable compound, etc. to cure the coating. membrane. For exposure, for example, ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, electron beams usually taken out from 20 to 2000 kV particle accelerators, α Rays, β rays, γ rays, etc. can be used. The amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
After the exposure, heat treatment (post-baking) may be performed in order to further accelerate the polymerization reaction and to react and bond the reactive groups in the silicon-containing compound. The heating conditions for post-baking are appropriately selected depending on the mixing ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, the type of reactive group, etc., and are not particularly limited, but the heating after exposure The temperature in the treatment is preferably 80° C. or higher and 250° C. or lower, more preferably 100° C. or higher and 240° C. or lower, still more preferably 180° C. or higher and 230° C. or lower, and most preferably 200° C. or higher and 230° C. or lower. The time is preferably 10 minutes or more and 180 minutes or less, more preferably 20 minutes or more and 150 minutes or less. When the silicon-containing compound (A) contains a thiol group as a reactive group, the temperature in the heat treatment after exposure can be 70° C. or higher and 150° C. or lower. °C or less. Moreover, when the silicon-containing compound (A) contains a thiol group as a reactive group, the heat treatment time after exposure is preferably 10 minutes or more and 120 minutes or less.

Next, a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as the developing method.
After the development processing, the developing solution is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after development processing. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

(Light shielding part)
The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as those used as light-shielding portions in general color filters.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like. The light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like can be used. be.

The film thickness of the light-shielding portion is set to about 0.2 μm or more and 0.4 μm or less in the case of a metal thin film, and about 0.5 μm or more to 2 μm or less in the case of a black pigment dispersed or dissolved in a binder resin. is set by

(substrate)
As the substrate, a transparent substrate or a silicon substrate, which will be described later, or a substrate obtained by forming a thin film of aluminum, silver, silver/copper/palladium alloy, or the like on the substrate is used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates. In the photosensitive colored resin composition of the present invention, when the reactive group of the silicon-containing compound (A) contains a thiol group, since the post-baking temperature can be reduced, the substrate can be a transparent resin film, an optical A substrate that is easily deformed at high temperatures, such as a resin plate for the substrate, a silicon substrate, or the like, can be preferably used.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material.
Although the thickness of the transparent substrate is not particularly limited, a thickness of about 100 μm or more and 1 mm or less can be used depending on the application of the color filter of the present invention.
The color filter of the present invention is formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, alignment projections, columnar spacers, etc., in addition to the substrate, the light shielding portion and the colored layer. good too.

[Display device]
A display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device and an organic light emitting display device.

<Liquid crystal display device>
A liquid crystal display device of the present invention includes the above-described color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram showing an example of the display device of the present invention, and is a schematic diagram showing an example of a liquid crystal display device. As illustrated in FIG. 2, a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a known configuration as a liquid crystal display device generally using color filters.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, IPS method, OCB method, and MVA method. Any of these methods can be suitably used in the present invention.
Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

<Organic Light Emitting Display Device>
An organic light-emitting display device according to the present invention is characterized by having the above-described color filter according to the present invention and an organic light-emitting material.
The organic light-emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing another example of the display device of the present invention, and is a schematic diagram showing an example of an organic light-emitting display device. As illustrated in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. As shown in FIG. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80 .

As a method of stacking the organic light emitter 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. method, and a method of bonding the organic light emitter 80 formed on another substrate onto the inorganic oxide film 60, and the like. As for the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other structures in the organic light emitter 80, known structures can be appropriately used. The organic light-emitting display device 100 manufactured in this way can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
Note that the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a known configuration as an organic light-emitting display device generally using color filters.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the invention.
In the following, the structures of the synthesized silicon-containing compounds were analyzed by GC/MS and 1H-NMR.
In the following, the weight average molecular weight Mw is measured by GPC (gel permeation chromatography) using a Shodex GPC system-21H (Shodex GPC System-21H) using polystyrene as a standard substance and THF as an eluent. bottom.

(Synthesis Example 1: Synthesis of Si-containing compound A)
A 500 ml glass flask equipped with an ester adapter, condenser, and thermometer was charged with 165.4 g (0.1 mol) of α,ω-dihydroxydiacryloethoxysiloxane and 15.2 g (0.1 mol) of tetramethoxysilane, The reaction was carried out at 120° C. for 3 hours under a nitrogen atmosphere. Distillation of methanol due to the demethanolation reaction was observed in the ester adapter. After completion of the reaction, analysis revealed that the molar equivalent of the reactive group (ethylenically unsaturated bond) of the obtained compound was 159 g/mol, the molecular weight was 1,904, and in the following general formula (i), A is a Si-containing compound A having a 2-acryloyloxyethoxy group (-O-(CH ₂ ) ₂ -O-C(=O)-CH=CH ₂ ).

(Synthesis Example 2: Synthesis of Si-containing compound B)
98.4 g (0.4 mol) of bis(trivinylsilyl)ethane and divinyltetramethyldisiloxane complex of chloroplatinic acid were placed in a 1,000 ml four-necked flask equipped with a stirrer, thermometer, Dimroth, and dropping funnel. 1.0 g of a toluene solution (concentration in terms of Pt: 0.5% by mass) was charged, and the temperature was raised to 90° C. while stirring. Then, 598.5 g (2.64 mol) of diacryloethoxychlorosilane was added dropwise from a dropping funnel at 90°C to 100°C over 2 hours, followed by aging at 90°C to 100°C for 3 hours. After cooling, it was distilled under reduced pressure.
Next, 150 g of toluene and 30.1 g (0.79 mol) of LiAlH ₄ were charged into a 1,000 ml four-necked flask equipped with a stirrer, a thermometer, a Dimroth, and a dropping funnel, and 300 g of THF was dropped from the dropping funnel while stirring. After that, a mixture of 596 g (0.35 mol) of a fraction obtained by distillation under reduced pressure and 500 g of toluene was added dropwise using a dropping funnel. After aging at 30°C or lower for 2 hours, 80 g of ethyl acetate was added dropwise from a dropping funnel, then the reactant was added to 3 L of 1N hydrochloric acid, washed with water, and only the upper layer was taken out by liquid separation. Distilled under reduced pressure. Analysis revealed that the molar equivalent of the reactive group (ethylenically unsaturated bond) of the obtained compound was 148 g/mol, the molecular weight was 1,779, and in the following general formula (ii), A' is 2- It was confirmed to be a Si-containing compound B having an acryloyloxyethoxy group (-O-(CH ₂ ) ₂ -O-C(=O)-CH=CH ₂ ).

(Synthesis Example 3: Synthesis of Si-containing compound C)
Synthesis Example 1 was carried out in the same manner as in Synthesis Example 1, except that an equimolar amount of α,ω-dihydroxydiethoxythiosiloxane was used instead of α,ω-dihydroxydiacryloethoxysiloxane. Analysis revealed that the molar equivalent of the reactive group (thiol group) of the obtained compound was 127 g/mol, the molecular weight was 1,525, and in the general formula (i), A was a 2-mercaptoethoxy group (- It was confirmed to be Si-containing compound C, which is O--(CH ₂ ) ₂ --SH).

(Synthesis Example 4: Synthesis of Si-containing compound D)
Synthesis Example 2 was carried out in the same manner as in Synthesis Example 2, except that an equimolar amount of dimethoxythiochlorosilane was used in place of diacryloethoxychlorosilane. Analysis showed that the molar equivalent of the reactive group (thiol group) of the obtained compound was 122 g/mol, the molecular weight was 1,468, and in the general formula (ii), A' is a mercaptomethoxy group (- It was confirmed to be Si-containing compound D, which is O—CH ₂ —SH).

(Synthesis Example 5: Synthesis of Si-containing compound E)
Synthesis Example 1 was carried out in the same manner as in Synthesis Example 1, except that an equimolar amount of α,ω-dihydroxydiglycidyloxysiloxane was used instead of α,ω-dihydroxydiacryloethoxysiloxane. Analysis revealed that the obtained compound had a reactive group (epoxy group) molar equivalent of 117 g/mol, a molecular weight of 1,400, and a Si-containing compound in which A was a glycidyloxy group in the general formula (i). It was confirmed to be Compound E.

(Synthesis Example 6: Synthesis of Si-containing compound F)
Synthesis Example 2 was carried out in the same manner as in Synthesis Example 2, except that an equimolar amount of diglycidyloxychlorosilane was used instead of diacryloethoxychlorosilane. According to analysis, the obtained compound has a reactive group (epoxy group) molar equivalent of 118 g/mol, a molecular weight of 1,419, and in the general formula (ii), A' is a glycidyloxy group. It was confirmed to be Si-containing compound F.

(Synthesis Example 7: Synthesis of initiator a)
(1) Synthesis of Intermediate A1 0.60 mol of fluorene, 2.4 mol of potassium hydroxide and 0.06 mol of potassium iodide are dissolved in 500 ml of anhydrous dimethylsulfoxide under a nitrogen atmosphere and maintained at 15° C., and 1.33 mol of bromobutane is added. The reaction was stirred at 15° C. for 1 hour with slow addition over 2 hours. After that, 2 L of distilled water was added to the reactant and stirred for about 30 minutes, the product was extracted with 2 L of dichloromethane, and the extracted organic layer was washed twice with 2 L of distilled water. Next, the collected organic layer was dried over anhydrous _MgSO4 , and the product obtained by distilling the solvent under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1:20). The following intermediate A1 was obtained.

(2) Synthesis of Intermediate A2 Intermediate A1 (0.11 mol) was dissolved in 500 ml of dichloromethane, cooled to -5°C, and then slowly added with 0.13 mol of AlCl3 _, the temperature of the reactant did not rise. A solution consisting of 15 ml of dichloromethane and 0.13 mol of cyclohexylpropionyl chloride was slowly added dropwise over 1 hour, and the mixture was stirred at -5°C for 1 hour. Then, the reactant was gradually poured into 500 ml of ice water, stirred for 30 minutes, and then the organic layer was washed with 200 ml of distilled water. Next, the product obtained by distilling the collected organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane=1:4) to obtain Intermediate A2 below.

(3) Synthesis of Intermediate A3 Intermediate A2 (0.042 mol) was dissolved in 200 ml of tetrahydrofuran (THF), and 25 ml of 4N HCl dissolved in 1,4-dioxane and 0.063 mol of isobutyl nitrite were sequentially added to react. The material was stirred at 25° C. for 6 hours. Then, 200 ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes to separate the organic layer, which was washed with 200 ml of distilled water. Next, the collected organic layer was dried over anhydrous MgSO4, and the product obtained by distilling the solvent under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane=1: ₄ ). Intermediate A3 below was obtained.

(4) Synthesis of initiator a The intermediate A3 (0.056 mol) was dissolved in 200 ml of N-methyl-2-pyrrolidinone (NMP) under a nitrogen atmosphere and maintained at -5°C, and 0.068 mol of triethylamine was added. The reaction solution was stirred for 30 minutes. Then, a solution of 0.068 mol of acetyl chloride and 10 ml of N-methyl-2-pyrrolidinone was gradually added over 30 minutes, and the reaction mixture was stirred for 30 minutes so as not to raise the temperature. After that, 200 ml of distilled water was slowly added to the reactant and stirred for 30 minutes to separate the organic layer. Then, the recovered organic layer was dried over anhydrous MgSO4, and the product obtained by distilling the solvent under reduced pressure was recrystallized using ₁ L of ethanol and dried to obtain the following initiator a.

(Synthesis Example 8: Synthesis of initiator b)
(1) Synthesis of Intermediate B1 0.030 mol of 9H-fluoren-2-yl-(phenyl)methanone was dissolved in 45 ml of dichloromethane, cooled to −5° C., added with 0.033 mol of anhydrous AlCl ₃ , and then 9 ml of dichloromethane. and 0.033 mol of propionyl chloride was slowly added over 1 hour and stirred at -5°C for 1 hour so as not to raise the temperature of the reactant. After that, the reactant was slowly poured into 250 g of ice water and stirred for 30 minutes, and then the organic layer was separated and washed with 100 ml of distilled water. Subsequently, the product obtained by distilling the recovered organic layer under reduced pressure was recrystallized with 20 ml of a mixed solution of toluene:ethyl acetate (5:1) to obtain the following intermediate B1.

(2) Synthesis of Intermediate B2 Intermediate B1 (0.010 mol) was dissolved in 30 ml of tetrahydrofuran (THF), and 4.5 ml of 4N HCl dissolved in 1,4-dioxane and 0.015 mol of isopentyl nitrite were sequentially added. The reaction was stirred at 25° C. for 24 hours. After that, 20 ml of ethyl acetate and 50 ml of distilled water were added to the reaction solution to extract an organic layer. The extracted organic layer is dried over anhydrous MgSO4, and the product obtained by distilling the solvent under reduced pressure is recrystallized using 30 ml of a mixed solvent of ethanol:ethyl acetate ( ₅ :1) and then dried. The following intermediate B2 was obtained.

(3) Synthesis of Initiator b Intermediate B2 (0.006 mol) was dissolved in 25 ml of ethyl acetate under a nitrogen atmosphere, the reaction mixture was maintained at -5°C, and 0.007 mmol of triethylamine was added to dilute the reaction solution to 30°C. After stirring for 30 minutes, a solution of 0.007 mol of acetyl chloride and 5 ml of ethyl acetate was gradually added over 30 minutes so as not to raise the temperature of the reactants, and the mixture was stirred for 30 minutes. After that, 100 ml of distilled water was gradually added to the reactant and stirred for about 30 minutes to separate the organic layer. The recovered organic layer was then dried over anhydrous MgSO ₄ and the solvent was distilled under reduced pressure to obtain the following initiator b.

(Synthesis Example 9: Synthesis of initiator c)
(1) Synthesis of Intermediate C1 In a 500 ml four-necked flask, 0.2 mol of diphenylthioether, 0.22 mol of pulverized AlCl ₃ , and 150 ml of dichloroethane were added and stirred, and the mixture was placed in an ice bath while flowing argon gas. When the temperature was lowered to 0°C by cooling, dropwise addition of a solution of 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was started and added over about 1.5 hours while adjusting the temperature below 10°C. After raising the temperature to 15° C. and continuing stirring for 2 hours, the reaction was discharged. After gradually pouring the reaction solution into diluted hydrochloric acid containing 400 g of ice and 65 ml of concentrated hydrochloric acid while stirring, the lower layer was separated using a separatory funnel, and the upper layer was extracted with 50 ml of dichloroethane. combined with the liquid. After that, it was washed with a _NaHCO3 solution containing 10 g of _NaHCO3 and 200 g of water, further washed with 200 ml of water _three times until the pH value was neutral, and dried with 60 g of anhydrous MgSO4 to remove moisture. Afterwards the dichloroethane was evaporated by rotary evaporation. The solid powder remaining in the rotary evaporator was placed in 200 ml of petroleum ether, subjected to suction filtration, further added to 150 ml of absolute ethanol and heated to reflux. After cooling to room temperature, cooling with ice for 2 hours, suction filtration, and drying in an oven at 50° C. for 2 hours, Intermediate C1 below was obtained.

(2) Synthesis of Intermediate C2 Into a 500 ml four-necked flask, 142 g of Intermediate C, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid, and 24.2 g of isoamyl nitrite were added and stirred at room temperature for 5 hours. After that, the reaction solution was discharged. The reaction mixture was placed in a large beaker, 1000 ml of water was added, and the mixture was stirred and allowed to stand overnight for layer separation to obtain a yellow viscous liquid. The viscous liquid was extracted with dichloroethane, dried by adding 50 g of anhydrous _MgSO4 , suction filtered, and the filtrate was rotary evaporated to remove the solvent to obtain an oily viscous material. Subsequently, the viscous substance was put into 150 ml of petroleum ether, stirred, precipitated, and subjected to suction filtration to obtain a white powdery solid. Then, it was dried at 60° C. for 5 hours to obtain Intermediate C2 below.

(3) Synthesis of initiator c Into a 1000 ml four-necked flask, 34 g of the intermediate C2, 350 ml of dichloroethane, and 12.7 g of triethylamine were charged and stirred, cooled in an ice bath until the temperature reached 0°C. , a solution of 15.7 g of acetic acid chloride and 15 g of dichloroethane began to dropwise and was added over about 1.5 hours. Subsequently, after stirring for 1 hour, 500 ml of cold water was added dropwise, and the layers were separated using a separatory funnel. Wash once with 200ml of 5% _NaHCO3 solution, wash twice with 200ml water until the pH value is neutral, then wash once with dilute hydrochloric acid containing 20g of concentrated hydrochloric acid and 400ml of water, then wash once with 200ml of water. After 3 washes with , it was dried over 100 g of anhydrous MgSO ₄ and the solvent was removed by rotary evaporation to give a viscous liquid. An appropriate amount of methanol was added to the viscous liquid, and the precipitated white solid was filtered and dried to obtain the following initiator c.

(Synthesis Example 10: Preparation of alkali-soluble resin A solution)
A mixture of 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 3 parts by mass of azobisisobutyronitrile (AIBN) was mixed with 150 parts by mass of PGMEA. It was added dropwise over 3 hours at 100° C. under a nitrogen stream into a polymerization tank containing 1 part. After completion of dropping, the mixture was further heated at 100° C. for 3 hours to obtain a polymer solution. The weight average molecular weight Mw of this polymer solution was 7,000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the resulting polymer solution, and heated at 110°C for 10 hours to react. Air was bubbled through the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced using GMA to the main chain formed by copolymerization of BzMA, MMA, and MAA, and the solid content is 42.6 mass. %, an acid value of 74 mgKOH/g, and a weight average molecular weight Mw of 12,000. The acid value was measured according to JIS K 0070.

(Synthesis Example 11: Preparation of Azo derivative 1)
23.1 g of diazobarbituric acid and 19.2 g of barbituric acid were introduced into 550 g of distilled water. Then, it was adjusted to azobarbituric acid (0.3 mol) using an aqueous potassium hydroxide solution and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added dropwise. 38.7 g of melamine were then introduced. A 0.57 mol nickel(II) chloride solution and a 0.03 mol copper chloride solution were then mixed and added and stirred at a temperature of 80° C. for 8 hours. The pigment was isolated by filtration, washed, dried at 120° C. and ground in a mortar to obtain Azo derivative 1 (Ni:Cu=95:5 (molar ratio) azo pigment).

(Synthesis Example 12: Preparation of Azo derivative 2)
In Synthesis Example 11, instead of the 0.57 mol nickel chloride solution and the 0.03 mol copper chloride solution, a 0.39 mol nickel (II) chloride solution and a 0.21 mol zinc (II) chloride solution were used. Azo derivative 2 (azo pigment of Ni:Zn=65:35 (molar ratio)) was obtained in the same manner as in Synthesis Example 11, except that it was used.

(Synthesis Example 13: Preparation of Azo derivative 3)
To 96 g of azobarbituric acid was added 5000 g of distilled water at 82°C. 252.2 g of melamine were then introduced. A mixture of 0.70 mol of 30% nickel(II) chloride solution, 0.05 mol of 30% zinc(II) chloride solution and 0.167 mol of 20% lanthanum(III) chloride solution is then added dropwise. bottom. After 3 hours at 82° C., the pH was adjusted to 5.5 using an aqueous potassium hydroxide solution. It was subsequently diluted with approximately 1000 g of distilled water at 90°C. 113 g of 30% hydrochloric acid were then added dropwise and the mixture was heat treated at 90° C. for 12 hours. The pH was then adjusted to 5 using an aqueous potassium hydroxide solution. The pigment is then isolated on a suction funnel, washed, dried in a vacuum drying cabinet at 80° C., milled in a standard laboratory mill for about 2 minutes, and the Azo derivative 3 (Ni:Zn :La = 81:6:13 (molar ratio) azo pigment).

(Synthesis Example 14: Preparation of dispersant a solution)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed 4-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was sufficiently purged with nitrogen. rice field. After cooling the reaction flask to −60° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. . B block monomers 1-ethoxyethyl methacrylate (EEMA) 3.3 parts by mass, 2-hydroxyethyl methacrylate (HEMA) 18.2 parts by mass, 2-ethylhexyl methacrylate (EHMA) 4.2 parts by mass, methacrylic 7.0 parts by mass of n-butyl acid (BMA), 24.7 parts by mass of benzyl methacrylate (BzMA), and 13.3 parts by mass of methyl methacrylate (MMA) were added dropwise over 60 minutes using an addition funnel. . After 30 minutes, 30.8 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, purified by vacuum drying, and diluted with PGMEA to obtain a solid content 30% by mass solution. 32.5 parts by mass of water was added, the temperature was raised to 100° C., and the mixture was reacted for 7 hours to deprotect the structural units derived from EEMA to obtain structural units derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, filtered, and purified by vacuum drying to obtain a structure derived from the A block containing the structural unit represented by the general formula (I) and the carboxy group-containing monomer. A block copolymer A (acid value: 12 mgKOH/g, Tg: 44°C) containing units and a B block having solvent affinity was obtained. The block copolymer A thus obtained had a weight average molecular weight Mw of 8,100. Moreover, the amine value was 110 mgKOH/g.
29.35 parts by mass of block copolymer A was dissolved in 29.35 parts by mass of PGMEA in a 100 mL round bottom flask, and 1.59 parts by mass of phenylphosphonic acid (manufactured by Tokyo Kasei) (phenylphosphonic acid was block copolymer A 0.1 mol per 1 mol of DMMA unit) and stirred at a reaction temperature of 30 ° C. for 20 hours to obtain a salt-type block copolymer A (dispersant a) solution (solid content 51.3% by mass) Obtained.
The amine value after salt formation can be calculated as 99 mgKOH/g by subtracting the amine value for 0.10 mol of DMMA unit (11 mgKOH/g) from the amine value 110 mgKOH/g before salt formation. The acid value of block copolymer A after salt formation is the same as that of block copolymer A before salt formation. The acid Tg of block copolymer A after salt formation was 46°C.
The acid value of the block copolymer before salt formation is determined according to the method described in JIS K 0070, and the amine value of the block copolymer before salt formation is determined according to the method described in JIS K 7237. method.
The weight average molecular weight Mw of the block copolymer before salt formation was obtained as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the above-described measuring method of the present invention.
The glass transition temperature (Tg) of the block copolymer before and after salt formation was measured by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology) according to the method described in JIS K7121. was measured using

(Example 1)
(1) Production of colorant dispersion liquid R1 6.23 parts by mass of dispersant a solution (solid content: 51.3% by mass) as a dispersant and C.I. I. 13.0 parts by mass of Pigment Red 254 (trade name: Hostaperm Red D2B-COF LV3781, manufactured by Clariant), 14.59 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle and predissolved. Shake for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for crushing, then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and repeat the present solution. Dispersion was carried out for 4 hours using a paint shaker to obtain a colorant dispersion liquid R1 (solid content: 47.9% by mass, colorant concentration: 38.4% by mass).

(2) Production of photosensitive colored resin composition R1 11.29 parts by mass of the colorant dispersion R1 obtained in (1) above, 1.25 parts by mass of Si-containing compound A, obtained in Synthesis Example 10 0.63 parts by mass of alkali-soluble resin A solution (solid content 42.6% by mass), photopolymerizable compound (polyfunctional monomer, trade name Aronix M-403, dipentaerythritol penta and hexaacrylate (DPHA), Toagosei Co., Ltd.), 0.15 parts by mass of the initiator a, and 9.77 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition R1.
(3) Formation of colored layer The photosensitive colored resin composition R1 obtained in (2) above is placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm and a size of 100 mm x 100 mm. was applied using a spin coater. The coating amount was adjusted so that the colored layer after post-baking had a chromaticity of x=0.650. Then, it was dried at 80° C. for 3 minutes using a hot plate to form a coating film. This coating film was irradiated with ultraviolet rays of 60 mJ/ ^cm2 using an ultra-high pressure mercury lamp through a pattern photomask (chrome mask) in which a chrome mask of 20 µm x 20 µm was arranged in an independent fine line with an opening size of 90 µm x 300 µm. Furthermore, the colored layer R1 was formed by post-baking in a clean oven at 230° C. for 30 minutes. The chromaticity (x, y) of the colored layer was measured using a spectroscopic characteristic measurement device LCF-1500M manufactured by Otsuka Electronics Co., Ltd.

(Examples 2 to 14, Comparative Examples 1 to 3)
Examples 2 to 14 and Comparative Examples 1 to 3 use the same colorant dispersion as the colorant dispersion R1 used in Example 1, and the photosensitive colored resin compositions R2 to 14 and RC1 to RC3 are prepared as follows. Manufactured by
In Examples 2 to 6, in place of the Si-containing compound A in (2) of Example 1, the Si-containing compounds shown in Table 1 were used in the amounts shown in Table 1, respectively. Photosensitive colored resin compositions R2 to R6 were obtained in the same manner as in 2).
In Example 7, in (2) of Example 1, the amount of initiator a added was changed to 0.40 parts by mass, 0.40 parts by mass of initiator b was added, and the amount of PGMEA was changed to 11.19 parts by mass. A photosensitive colored resin composition R7 was obtained in the same manner as in (2) of Example 1, except that it was adjusted to be 1 part.
In Example 8, in (2) of Example 1, the photosensitive colored resin composition R8 was prepared in the same manner as in (2) of Example 1, except that the initiator b was used instead of the initiator a. Obtained.
In Example 9, Si-containing compound F was used in the amount shown in Table 1 in place of Si-containing compound A in (2) of Example 1, and initiator c was used in place of initiator a. A photosensitive colored resin composition R9 was obtained in the same manner as in Example 1 (2) except for the above.
In Example 10, in (2) of Example 1, the amount of initiator a added was changed to 0.40 parts by mass, 0.40 parts by mass of initiator c was added, and the amount of PGMEA was changed to 11.19 parts by mass. A photosensitive colored resin composition R10 was obtained in the same manner as in (2) of Example 1, except that it was adjusted to be 1 part.
In Example 11, in (2) of Example 1, the amount of initiator a added was changed to 0.40 parts by mass, and a mercapto-based chain transfer agent (pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Photosensitive coloring in the same manner as in (2) of Example 1, except that 0.30 parts by mass of Karenz MTPE1, manufactured by Showa Denko) was added and the amount of PGMEA was adjusted to 12.05 parts by mass. A resin composition R11 was obtained.
In Example 12, in (2) of Example 1, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name) was added as a hindered phenol antioxidant. A photosensitive colored resin composition R12 was obtained in the same manner as in Example 1 (2) except that 0.30 parts by mass of Irganox 1010, manufactured by BASF) was added.
In Example 13, in (2) of Example 1, OXE-02 (manufactured by BASF) represented by the following chemical formula (d) was used instead of the initiator a. ) to obtain a photosensitive colored resin composition R13.

In Example 14, a photosensitive colored resin composition was prepared in the same manner as in Example 1 (2) except that the amount of Si-containing compound A added was changed to the value shown in Table 1 in Example 1 (2). product R14 was obtained.
In Comparative Example 1, a photosensitive colored resin composition RC1 was obtained in the same manner as in Example 1 (2) except that the Si-containing compound A was not used in Example 1 (2).
In Comparative Example 2, the Si-containing compound A was not used in (2) of Example 1, and OXE-02 (manufactured by BASF) represented by the chemical formula (d) was used instead of the initiator a. A photosensitive colored resin composition RC2 was obtained in the same manner as in Example 1 (2) except for the above.
In Comparative Example 3, the addition amount of the Si-containing compound A was changed to 0.10 parts by mass and the addition amount of the photopolymerizable compound was changed to 2.05 parts by mass in (2) of Example 1. A photosensitive colored resin composition RC3 was obtained in the same manner as in Example 1 (2).

In Examples 2 to 14 and Comparative Examples 1 to 3, in (3) of Example 1, instead of the photosensitive colored resin composition R1, the photosensitive colored resin compositions R2 to R14 and RC1 to RC3 were used, respectively. Colored layers R2 to R14 and RC1 to RC3 were obtained in the same manner as in Example 1 (3) except that

(Example 15)
(1) Production of colorant dispersion liquid G1 13.3 parts by mass of dispersant a solution (solid content: 51.3% by mass) as a dispersant and C.I. I. Pigment Green 59 (trade name: FASTOGEN GREEN C100, manufactured by DIC Corporation) and 11.0 parts by mass of C.I. I. 2.0 parts by mass of Pigment Yellow 150 (trade name: LEVASCREEN YELLOW G01, manufactured by Lanxess Corporation), 63.7 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle and prepared as a reserve. Shake for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for pulverization, then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and repeat the process. Dispersion was carried out for 4 hours using a paint shaker as pulverization to obtain a colorant dispersion liquid G1 (solid content: 22.0% by mass, colorant concentration: 14.4% by mass).

(2) Production of photosensitive colored resin composition G1 287.0 parts by mass of the colorant dispersion G1 obtained in (1), 23.0 parts by mass of Si-containing compound A, obtained in Synthesis Example 10 12.0 parts by mass of alkali-soluble resin A solution (solid content 42.6% by mass), 23.0 parts of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), initiator a and 84.63 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition G1.
(3) Formation of colored layer The photosensitive colored resin composition G1 obtained in (2) above is placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm and a size of 100 mm x 100 mm. was applied using a spin coater. The coating amount was adjusted so that the chromaticity of the colored layer after post-baking was y=0.370. Then, it was dried at 80° C. for 3 minutes using a hot plate to form a coating film. This coating film was irradiated with ultraviolet rays of 60 mJ/ ^cm2 using an ultra-high pressure mercury lamp through a pattern photomask (chrome mask) in which a chrome mask of 20 µm x 20 µm was arranged in an independent fine line with an opening size of 90 µm x 300 µm. Furthermore, the colored layer G1 was formed by post-baking in a clean oven at 230° C. for 30 minutes. The chromaticity (x, y) of the colored layer was measured using a spectroscopic characteristic measurement device LCF-1500M manufactured by Otsuka Electronics Co., Ltd.

(Examples 16-20)
In Examples 16 to 20, the same colorant dispersion as the colorant dispersion G1 used in Example 15 was used, and in (2) of Example 15, instead of the Si-containing compound A, each shown in Table 2. Photosensitive colored resin compositions G2 to G6 were obtained in the same manner as in Example 15 (2) except that the Si-containing compound was used in the amount shown in Table 2. Then, in Example 15 (3), instead of the photosensitive colored resin composition G1, except for using each of the photosensitive colored resin compositions G2 to G6, in the same manner as in Example 15 (3) , to obtain colored layers G2 to G6.

(Example 21)
13.3 parts by mass of dispersant a solution (solid content: 51.3 mass %) as a dispersant, and C.I. I. 11.0 parts by mass of Pigment Green 59 (trade name: FASTOGEN GREEN C100, manufactured by DIC Corporation), 2.0 parts by mass of Azo derivative 1 obtained in Synthesis Example 11, and 63.7 parts by mass of PGMEA , Put 100 parts by mass of zirconia beads with a particle size of 2.0 mm into a mayonnaise bottle, shake for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing, then take out the zirconia beads with a particle size of 2.0 mm, 200 parts by mass of zirconia beads having a particle size of 0.1 mm were added, and dispersion was similarly carried out for 4 hours using a paint shaker as main pulverization to obtain a colorant dispersion liquid G7 (colorant concentration: 14% by mass).
Next, in the same manner as in Example 15 (2), except that the colorant dispersion G7 was used instead of the colorant dispersion G1 in Example 15 (2), a photosensitive colored resin composition was prepared. G7 was obtained.
Then, in (3) of Example 15, instead of the photosensitive colored resin composition G1, except that the photosensitive colored resin composition G7 was used, in the same manner as in (3) of Example 15, colored layer G7 was obtained.

(Example 22)
Colorant dispersion liquid G8 (color A material concentration of 14% by mass) was obtained. Next, in Example 21, a photosensitive colored resin composition G8 and a colored layer G8 were obtained in the same manner as in Example 21, except that the colorant dispersion G8 was used instead of the colorant dispersion G7. .

(Example 23)
Colorant dispersion liquid G9 (color A material concentration of 14% by mass) was obtained. Next, in Example 21, a photosensitive colored resin composition G9 and a colored layer G9 were obtained in the same manner as in Example 21, except that the colorant dispersion G9 was used instead of the colorant dispersion G7. .

(Comparative Examples 4-7)
Comparative colorant dispersions GC1, GC2, GC3 and GC4 were prepared in the same manner as in Examples 15, 21, 22 and 23, respectively, except that Si-containing compound A was not used in Examples 15, 21, 22 and 23. Obtained. Next, in Examples 15, 21, 22 and 23, instead of the colorant dispersions G1, G7, G8 and G9, the comparative colorant dispersions GC1, GC2, GC3 and GC4 were used, respectively. Comparative photosensitive colored resin compositions GC1, GC2, GC3 and GC4 and colored layers GC1, GC2, GC3 and GC4 were obtained in the same manner as in 15, 21, 22 and 23.

[Evaluation method]
<Optical performance evaluation>
The luminance (Y) of the colored layers obtained in Examples and Comparative Examples was measured using a spectroscopic characteristic measurement device LCF-1500M manufactured by Otsuka Electronics Co., Ltd.

<Developability evaluation>
The colored layers obtained in Examples and Comparative Examples were observed with an optical microscope and evaluated for rippling according to the following evaluation criteria.
[Biritsuki]
A: The ten-point average roughness of the periphery of the micropores formed in the colored layer is less than 0.1 B: The ten-point average roughness of the periphery of the micropores formed in the colored layer is 0.1 or more .5 or less C: The ten-point average roughness of the periphery of the micropores formed in the colored layer is greater than 0.5 The ten-point average roughness was measured according to JIS B0601.

[Linearity]
In Examples 1 to 14 and Comparative Examples 1 to 3, the width of the fine line pattern of the colored layer in the portion corresponding to the opening width of 90 μm of the chromium mask used at the time of exposure for forming the colored layer was measured with an optical microscope at five points. The linearity was evaluated based on the variation in width.
A: Variation within ±0.1 μm B: Variation exceeding ±0.1 μm within ±0.3 μm C: Variation exceeding ±0.3 μm

In Examples 1 to 14 and Comparative Examples 1 to 3, the colored layers obtained were observed with an optical microscope, and the development residue was evaluated according to the following evaluation criteria.
[Development residue]
A: Coloring is not observed inside the micropores formed in the colored layer by observation with an optical microscope B: Coloring is observed inside the micropores formed in the colored layer by observation with an optical microscope

<Heat resistance evaluation>
In the examples and comparative examples, when forming the colored layer, the chromaticity of the cured film after exposure and before post-baking (L ₀ , a ₀ , b ₀ ) and the chromaticity of the colored layer after post-baking (L ₁ , a ₁ , b ₁ ) were measured, and the change in chromaticity of the cured film before and after post-baking was evaluated according to the following formula.
ΔEab={(L ₁ −L ₀ ) ² +(a ₁ −a ₀ ) ² +(b ₁ −b ₀ ) ² } ^1/2
The chromaticity (L ₁ , a ₁ , b ₁ ) of the cured film (colored layer) was measured using an Olympus Co., Ltd. "spectroscopic microscope OSP-SP200".

Each abbreviation in the table is as follows.
PR254: C.I. I. Pigment Red 254 Product name: Hostaperm Red D2B-COF LV3781, manufactured by CLARIANT)
PG59: C.I. I. Pigment Green 59 (trade name: FASTOGEN GREEN C100, manufactured by DIC Corporation)
PY150: C.I. I. Pigment Yellow 150 (trade name: LEVASCREEN YELLOW G01, LANXESS Corporation)
Mercapto-based: Mercapto-based chain transfer agent (pentaerythritol tetrakis (3-mercaptobutyrate, trade name: Karenz MTPE1, manufactured by Showa Denko K.K.)
OXE02: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (trade name Irgacure OXE-02, manufactured by BASF)
Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, manufactured by BASF)

[Summary of results]
From the results of the table, at least one specific silicon-containing compound selected from the compound represented by the general formula (A1) and the compound represented by the general formula (A2) was added to 100 parts by mass of the photopolymerizable compound. On the other hand, the photosensitive colored resin compositions of Examples 1 to 23 containing more than 10.0 parts by mass have good developability, while suppressing color change due to heating during post-baking, high brightness It has been clarified that a colored layer can be formed.
Among them, as a photoinitiator, in the oxime ester compound represented by the general formula (C1), X in the general formula (C1) is a divalent compound represented by -C(R ^a )(R ^b )- group and Y is a direct bond, and the oxime ester compound represented by the general formula (C1), wherein X in the general formula (C1) is a thioether bond (-S-), Example 10, in which Y was used in combination with an oxime ester compound having no bond, was excellent in the developability of the photosensitive colored resin composition, and the blistering of the periphery of the microholes formed in the pattern of the colored layer was further suppressed. was
Further, in Examples 15 to 23, C.I. I. Examples 21 to 23 using derivative pigments of Pigment Yellow 150 were able to form particularly bright colored layers.
On the other hand, the photosensitive colored resin compositions of Comparative Examples 1, 2, and 4 to 7 did not contain the specific silicon-containing compound, so the photosensitive colored resin composition of Comparative Example 3 contained the specific silicon Since the amount of the containing compound added was 10 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound, the developability was poor, the change in color due to heating during post-baking was large, and the brightness of the colored layer was poor. rice field.

REFERENCE SIGNS LIST 1 substrate 2 light shielding part 3 colored layer 10 color filter 20 counter substrate 30 liquid crystal layer 40 liquid crystal display device 50 organic protective layer 60 inorganic oxide film 71 transparent anode 72 hole injection layer
73 hole transport layer 74 light emitting layer 75 electron injection layer 76 cathode 80 organic light emitter 100 organic light emitting display

Claims (13)

A silicon-containing compound (A) containing at least one selected from compounds represented by the following general formula (A1) and compounds represented by the following general formula (A2), a photopolymerizable compound (B), and photoinitiation containing an agent (C) and a coloring material (D),
The total content of the compound represented by the general formula (A1) and the compound represented by the general formula (A2) exceeds 10.0 parts by mass with respect to 100 parts by mass of the photopolymerizable compound (B) A photosensitive colored resin composition.

(In the general formula (A1), R is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond (-O-), or a group having a reactive group, and the reaction group having a sexual group, thioether bond (-S-), ether bond (-O-) and carbonyl bond (-CO-) may contain at least one divalent linking group selected from A monovalent group in which at least one methyl group in a linear or branched alkyl group is replaced with at least one reactive group selected from the group consisting of a thiol group, a (meth)acryloyl group, a vinyl group and an epoxy group and a plurality of R may be the same or different, and at least a portion of all R is a group having the reactive group L is a direct bond or -O- bond, n is 2 represents an integer greater than or equal to 30 or less.
In general formula (A2), R′ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an ether bond (—O—), or the formula: —(CH ₂ ) _a —SiA ₂ A group represented by H (a is an integer of 1 or more and 3 or less, and A represents a (meth)acryloyloxyalkoxy group, a mercaptoalkoxy group, or a glycidyloxy group), and a plurality of R' are each the same However, they may be different, and at least part of all R's are groups represented by the above formula: --(CH ₂ ) _a --SiA ₂ H. R ″ is an alkylene group having 1 to 3 carbon atoms, a plurality of R ″ may be the same or different, L′ is a direct bond or an alkylene group having 1 to 3 carbon atoms, and n′ is represents an integer of 2 or more and 30 or less. ) Claim 1, wherein the compound represented by the general formula (A1) and the compound represented by the general formula (A2) have a reactive group equivalent represented by the following formula (1) of 100 g/mol or more. The photosensitive colored resin composition according to .
Formula (1)
Reactive group equivalent (g/mol) = W _(A) (g)/M _(A) (mol)
(In the formula (1), W _(A) represents the mass (g) of the silicon-containing compound, M _(A) is the silicon-containing compound W _(A) (g) contained in the ethylenically unsaturated bond, thiol Represents the total number of moles (mol) of reactive groups that are groups or epoxy groups.) The content of the silicon-containing compound (A) in the total solid content of 100% by mass of the photosensitive colored resin composition is 10% by mass or more and 80% by mass or less,
The photosensitive colored resin composition according to claim 1 or 2, wherein the content of the alkali-soluble resin is 25 parts by mass or less per 100 parts by mass of the silicon-containing compound (A). The photosensitive colored resin composition according to any one of claims 1 to 3, wherein the photoinitiator (C) contains an oxime ester compound represented by the following general formula (C1).

(In the general formula (C1), X is a thioether bond (-S-), an ether bond (-O-) or a divalent group represented by -C(R ^a )(R ^b )-, and R ^a and R ^b are each independently a hydrogen atom or an alkyl group, and when X is a thioether bond (-S-) or an ether bond (-O-), Y is no bond, and X is -C ( In the case of a divalent group represented by R ^a )(R ^b )-, Y is a direct bond, R ^c is a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond ( —CO—) is a hydrocarbon group optionally containing at least one divalent linking group selected from Z is a hydrogen atom or —(C═O)R ^d , where R ^d is oxygen A hydrocarbon group optionally containing at least one selected from an atom and a sulfur atom, or a heterocyclic group containing no nitrogen atom and containing at least one selected from an oxygen atom and a sulfur atom, ^e is a hydrocarbon group having 1 to 10 carbon atoms.) The photosensitive colored resin composition according to claim 4, wherein the photoinitiator (C) contains two or more oxime ester compounds having no carbazole skeleton. The photoinitiator (C) is an oxime ester compound represented by the general formula (C1), wherein X in the general formula (C1) is -C(R ^a )(R ^b )- 2 an oxime ester compound in which Y is a direct bond and the oxime ester compound represented by the general formula (C1), wherein X in the general formula (C1) is a thioether bond (-S-) The photosensitive colored resin composition according to claim 4 or 5, comprising an oxime ester compound in which Y is free. The photoinitiator (C) is further selected from α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents. 7. The photosensitive colored resin composition according to any one of claims 4 to 6, containing at least one. The photosensitive colored resin composition according to any one of claims 1 to 7, further comprising an antioxidant. The antioxidant is a group consisting of a hindered phenol antioxidant and a latent hindered phenol antioxidant in which the phenolic hydroxyl group of the hindered phenol antioxidant is protected with a protecting group that can be removed by heating. The photosensitive colored resin composition according to claim 8, which is at least one selected from. The coloring material (D) is C.I. I. Pigment Green 59 and C.I. I. 10. The photosensitive colored resin composition according to any one of claims 1 to 9, comprising at least one yellow colorant selected from Pigment Yellow 150 and derivative pigments thereof. A cured product of the photosensitive colored resin composition according to any one of claims 1 to 10. 12. A color filter comprising at least a substrate and colored layers provided on the substrate, wherein at least one of the colored layers is the cured product according to claim 11. A display device comprising the color filter according to claim 12 .

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