TWI729272B - Color material dispersion liquid for color filter, dispersant, photosensitive color resin composition for color filter, color filter, and display device - Google Patents

Abstract

Provided is a color material dispersion liquid for a color filter, comprising a color material, a dispersant and a solvent, wherein the dispersant is a block copolymer comprising a block A including a constitutional unit represented by the following general formula (I) and a block B including at least one selected from a constitutional unit represented by the following general formula (B1) and a constitutional unit represented by the following general formula (B2): (the symbols in the general formulae (I), (B1) and (B2) are as described in the specification.)

Description

Color material dispersion liquid for color filter, dispersant, photosensitive colored resin composition for color filter, color filter, display device

The present invention relates to a color material dispersion liquid for color filters, a dispersant, a photosensitive colored resin composition for color filters, 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 has increased. The penetration rate of mobile displays (mobile phones, smart phones, and tablet personal computers (PC, Personal Computer)) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, organic light-emitting display devices such as organic electroluminescence (EL, Electroluminescence) displays, which are highly visible by self-luminescence, are also attracting attention as next-generation image display devices. In the performance of these image display devices, there is a strong desire for further enhancement of image quality, such as improvement of contrast and color reproducibility, or reduction of power consumption.

Color filters are used in these liquid crystal display devices or organic light emitting display devices. For example, the formation of a color image in a liquid crystal display device directly colors the light passing through the color filter into the color of each pixel constituting the color filter, and synthesizes the light of these colors to form a color image. As the light source at this time, in addition to the conventional cold-cathode tube, there are cases of using white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements. In addition, in organic light-emitting display devices, color filters are used for color adjustment and the like. Under such circumstances, expectations for color filters, such as higher brightness or higher contrast, and improved color reproducibility, have also increased.

Here, in general, the color filter has: a transparent substrate; a coloring layer formed on the transparent substrate and including coloring patterns of the three primary colors of red, green, and blue; and a light-shielding portion that divides the coloring patterns The method is formed on a transparent substrate.

As a method of forming pixels in a color filter, among the viewpoints of spectral characteristics, durability, pattern shape and accuracy, the most widely used pigment dispersion method with excellent characteristics on average is used. In a color filter with pixels formed using a pigment dispersion method, in order to achieve high brightness or high contrast, the miniaturization of pigments is studied. It is believed that by miniaturizing the pigment, the scattering of light that passes through the color filter caused by the pigment particles can be reduced, thereby achieving high brightness or high contrast. However, since the micronized pigment particles tend to agglomerate, there is a problem of reduced dispersibility or dispersion stability.

As a method for improving the dispersibility of a finely divided pigment, it is known that the use of a dispersant is effective. For example, in Patent Document 1, in order to satisfy the initial dispersibility and time-dependent dispersion stability of the dispersant of the finely divided pigment, and to meet the requirements of high contrast, high brightness, and high developability of liquid crystal display elements, it is disclosed There is a coloring composition for color filters, which uses a block copolymer having an A block and a B block as a pigment dispersant. The A block contains a specific repeating unit having an amine group or an ammonium salt group. The B block contains specific repeating units containing oxygen-containing saturated heterocyclic groups or alkenyl groups in the alcohol-derived portion of the carboxylic acid ester. In addition, in Patent Document 2, in order to provide a coloring composition for a color filter that can form a colored layer with excellent chromaticity characteristics and heat resistance and has good dispersibility and storage stability, a coloring composition for a color filter is disclosed It uses the following copolymer as a pigment dispersant. The copolymer contains a specific repeating unit with an amine group and a repeating unit with a crosslinkable functional group, and the amine value is 80~250mgKOH/g.

In addition, Patent Document 3 and Patent Document 4 describe the use of a specific photosensitive color resin composition in order to obtain a photosensitive colored resin composition that is excellent in color material dispersion stability, suppresses the generation of development residues, and is excellent in development adhesion and solvent resolubility Dispersant. As a specific dispersant, a block copolymer is described in Patent Document 3, which includes a structure having an amide group and a nitrogen site corresponding to the end of the amine group or a structure in which the nitrogen site forms a salt with a specific compound A specific structural unit has a specific amine value and a specific glass transition temperature; Patent Document 4 describes a block copolymer containing: A block, which contains a nitrogen site corresponding to the end of the amine group Or the nitrogen site and the specific compound form a specific structural unit of the structure of the salt; and the B block, which contains the structural unit derived from the carboxyl group-containing monomer; the block copolymer further has a specific acid value and a specific glass Transfer temperature.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2012/063435

Patent Document 2: Japanese Patent Laid-Open No. 2013-88695

Patent Document 3: Japanese Patent Laid-Open No. 2016-122073

Patent Document 4: Japanese Patent Laid-Open No. 2016-122169

However, in recent color filters, further enhancement of brightness and improvement of various tolerances have been sought. In addition, in general, a color filter is formed on a colored layer to form an indium tin oxide (ITO) (Indium Tin Oxide) film as a transparent electrode. However, in the conventional color filter, there is also the following problem: the ITO film formed adjacent to the colored layer is prone to cracks, and the cracks generated on the ITO film cause current not to flow and display poor display. The present invention was completed in view of the above-mentioned actual situation, and its object is to provide a color material dispersion that can form a high-brightness coloring layer and can suppress cracks in an ITO film formed adjacent to the coloring layer. In addition, an object of the present invention is to provide a dispersant for the color material dispersion liquid that can form a high-brightness coloring layer and can suppress cracks in the ITO film formed adjacent to the coloring layer. In addition, an object of the present invention is to provide a photosensitive colored resin composition for a color filter that can form a high-brightness colored layer and can suppress cracks in an ITO film formed adjacent to the colored layer. In addition, an object of the present invention is to provide a color filter formed using the photosensitive colored resin composition for a color filter. In addition, an object of the present invention is to provide a display device with excellent display characteristics by using the color filter.

The color material dispersion liquid for color filters of the present invention contains a color material, a dispersant, and a solvent, and the dispersant contains a block copolymer of the A block and the B block, and the A block contains the following general The structural unit represented by the formula (I), the B block contains at least one selected from the structural unit represented by the following general formula (B1) and the structural unit represented by the following general formula (B2).

[化1]

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ² and R ³ can be They are bonded to each other to form a ring structure.)

(In the general formula (B1), A ¹ represents a divalent linking group, R ¹¹ represents a two-, three- or four-valent aliphatic hydrocarbon group or a carbon atom that may contain an oxygen atom, and R ¹⁰ and R ¹² each independently represent a hydrogen atom or Methyl; n is 1, 2 or 3.)

[化3]

(In the general formula (B2), A ² represents a divalent linking group, A ³ and A ⁴ each independently represent a divalent, trivalent or tetravalent linking group, and R ¹³ represents that it may contain at least one selected from the group consisting of oxygen atoms and nitrogen atoms A divalent hydrocarbon group, R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group that may contain an oxygen atom, and R ¹⁰ , R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or a methyl group; n ¹ represents 0, 1, 2 or 3, n ² represents 0 or 1, n ³ represents 0, 1 or 2, n ¹ + n ² is 1, 2 or 3, n ¹ + n ² + n ³ is 1, 2 or 3; m ¹ represents 1, 2 or 3, m ² represents 0, 1 or 2, and m ¹ + m ² is 1, 2 or 3.)

The dispersant of the present invention contains a block copolymer of A block and B block, the A block contains the structural unit represented by the above general formula (I), and the B block contains selected from the above general formula (B1) At least one of the structural unit represented and the structural unit represented by the general formula (B2).

The photosensitive colored resin composition for a color filter of the present invention contains the color material dispersion of the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.

The color filter of the present invention is provided with at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a cured product of the photosensitive coloring resin composition for a color filter of the present invention.

The display device of the present invention has the above-mentioned color filter of the present invention.

According to the present invention, it is possible to provide a color material dispersion liquid that can form a high-brightness coloring layer and can suppress cracks in an ITO film formed adjacent to the coloring layer. Furthermore, according to the present invention, it is possible to provide a dispersant for the color material dispersion liquid that can form a high-brightness coloring layer and can suppress cracks in the ITO film formed adjacent to the coloring layer. Furthermore, according to the present invention, it is possible to provide a photosensitive colored resin composition for a color filter that can form a high-brightness colored layer and can suppress cracks in an ITO film formed adjacent to the colored layer. Furthermore, according to the present invention, it is possible to provide a color filter formed using the photosensitive colored resin composition for a color filter. Furthermore, according to the present invention, it is possible to provide a display device having excellent display characteristics by using the color filter.

1‧‧‧Substrate

2‧‧‧Shading part

3‧‧‧Coloring layer

10‧‧‧Color filter

20‧‧‧Opposite substrate

30‧‧‧Liquid crystal layer

40‧‧‧LCD device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧hole injection layer

73‧‧‧Hole Transmission Layer

74‧‧‧Light-emitting layer

75‧‧‧Electron injection layer

76‧‧‧Cathode

80‧‧‧Organic luminous body

100‧‧‧Organic light emitting display device

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 liquid crystal display device of the present invention.

FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention.

Hereinafter, the color material dispersion liquid for color filters, the dispersant, the photosensitive colored resin composition for color filters, the color filter, and the display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and further includes radiation, which includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less. In the present invention, the so-called (meth)acryloyl group means each of an acrylic acid group and a methacryloyl group, and the so-called (meth)acrylic group means each of an acrylic group and a methacrylic group, and the so-called (meth)acryloyl group means each of an acrylic acid group and a methacrylic acid group. Acrylate means each of acrylate and methacrylate. In this manual, unless otherwise specified, the chromaticity coordinates x and y are those of the XYZ color system of JIS Z8701: 1999 for color measurement using C light source.

1. Color material dispersion liquid for color filter

The color material dispersion liquid for color filters of the present invention contains a color material, a dispersant, and a solvent, and the dispersant contains a block copolymer of the A block and the B block, and the A block contains the following general The structural unit represented by the formula (I), the B block contains at least one selected from the structural unit represented by the following general formula (B1) and the structural unit represented by the following general formula (B2).

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ² and R ³ can be They are bonded to each other to form a ring structure.)

[化5]

(In the general formula (B1), A ¹ represents a divalent linking group, R ¹¹ represents a two-, three- or four-valent aliphatic hydrocarbon group or a carbon atom that may contain an oxygen atom, and R ¹⁰ and R ¹² each independently represent a hydrogen atom or Methyl; n is 1, 2 or 3.)

(In the general formula (B2), A ² represents a divalent linking group, A ³ and A ⁴ each independently represent a divalent, trivalent or tetravalent linking group, and R ¹³ represents that it may contain at least one selected from the group consisting of oxygen atoms and nitrogen atoms A divalent hydrocarbon group, R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group that may contain an oxygen atom, and R ¹⁰ , R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or a methyl group; n ¹ represents 0, 1, 2 or 3, n ² represents 0 or 1, n ³ represents 0, 1 or 2, n ¹ + n ² is 1, 2 or 3, n ¹ + n ² + n ³ is 1, 2 or 3; m ¹ represents 1, 2 or 3, m ² represents 0, 1 or 2, and m ¹ + m ² is 1, 2 or 3.)

Since the color material dispersion of the present invention uses a block copolymer containing the above-mentioned specific A block and the above-mentioned specific B block as a dispersant, a photosensitive colored resin for color filters prepared by using the color material dispersion The composition can form a high-brightness coloring layer, and can suppress the cracking of the ITO film formed adjacent to the coloring layer. Although it is unclear as to the effect of exerting this effect, it is estimated as follows. It is believed that the above-mentioned specific block copolymer is easily adsorbed to the color material by the A block, thereby improving the dispersibility and dispersion stability of the color material. The B block has a composition selected from the above-mentioned general formula (B1). Among the units and at least one of the structural units represented by the general formula (B2), the (meth)acrylic acid is easily crosslinked with other crosslinkable groups when forming the colored layer. When it is a conventional dispersant, the crosslinking density near the color material is insufficient, and it is easy to swell due to the solvent. Therefore, it is considered that after the ITO film is formed adjacent to the colored layer, the solvent such as NMP (N-methyl-2-pyrrolidone) contained in the coating solution applied on the ITO film in the next step , Causing the coloring layer under the ITO film to swell, so it is easy to crack in the ITO film, which is an inorganic substance. On the contrary, it is considered that the dispersant used in the present invention is composed of at least one selected from the structural unit represented by the above general formula (B1) and the structural unit represented by the above general formula (B2) possessed by the B block. The (meth)acrylic acid group is cross-linked with other cross-linkable groups, especially the intermolecular of the dispersant adsorbed to the color material is easily cross-linked, which can increase the cross-linking density near the color material in the color layer , Reduce the part where the cross-linking density becomes thinner, thereby increasing the strength of the film. Therefore, in the present invention, the colored layer in the vicinity of the color material can also ensure the cross-linking density, reducing the part where the cross-linking density becomes sparse, and thereby suppressing the swelling caused by the solvent. Therefore, it is inferred that the colored layer has excellent solvent resistance. The ITO film formed adjacent to the colored layer will not be cracked (crack), so that the color filter can be easily formed. In addition, since the color material in the color layer is covered by a cured film with a higher crosslinking density, the thermal movement of the color material molecules during baking is reduced, and the deterioration of the color material is suppressed, thereby suppressing the decrease in the brightness of the color layer. , So it is inferred that a high-brightness colored layer can be formed. In addition, it is considered that a (meth)acryloyl group having at least one selected from the structural unit represented by the above general formula (B1) and the structural unit represented by the above general formula (B2) in the side chain is more than an oxygen heterocyclic ring Other cross-linking groups such as butyl have excellent photopolymerization when combined with a radical polymerization initiator. Therefore, when the colored layer is formed, it can react sufficiently by exposure to increase the cross-linking density and post-baking When the crosslinking density is higher, the effect of suppressing the decrease in brightness can be obtained, and the brightness of the formed coloring layer is further improved. In addition, it is believed that compared with other crosslinkable groups such as oxetanyl group, (meth)acrylic acid has excellent storage stability under acid or alkalinity, so it coexists with the acidic group of the resin or the basic group of the dispersant. The stability below is excellent, so the viscosity stability is further improved. In addition, in the manufacturing process of the color filter, the colored material sublimates or precipitates and adheres to the colored layer, which may cause foreign matter defects. If the color material is sublimated from the coloring layer of the color filter, there will be the following problems: not only the hue of the colored layer changes, but the hue of other colored layers is also changed due to adhesion to other colored layers, resulting in a decrease in brightness, or Produce pollution in the heating device. In contrast, in the present invention, by using the above-mentioned specific block copolymer as a dispersant, the color material in coloring becomes a state covered by a cured film with a higher crosslinking density, thereby suppressing the sublimation and precipitation of the color material.

The color material dispersion liquid of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. Hereinafter, each component of the color material dispersion liquid of the present invention will be described in detail sequentially starting from the dispersant of the present invention.

<Dispersant>

In the present invention, a block copolymer containing an A block and a B block is used as a dispersant. The A block contains the structural unit represented by the above general formula (I), and the B block contains selected from the above general formula. At least one of the structural unit represented by (B1) and the structural unit represented by the above general formula (B2). The block copolymer may also be formed from at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons (hereinafter Sometimes called salt block copolymer). First, the self-block copolymer will be described.

{A block}

(Constituted unit represented by general formula (I))

The structural unit represented by the above general formula (I) contained in the A block has basicity and functions as an adsorption site for the color material. In the general formula (I), A is a divalent linking group. As the divalent linking group, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and 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, in terms of dispersibility, A in the general formula (I) is preferably a divalent linking group including a -CONH- group or a -COO- group.

Examples of the hydrocarbon group in the hydrocarbon group that may contain a hetero atom in R ² and R ^{3 include an alkyl group, an aralkyl group, and an aryl group.} Examples of alkyl groups include methyl, ethyl, propyl, butyl, isopropyl, tertiary butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc. The number of carbon atoms in the alkyl group is relatively high. Preferably it is 1-18, and more preferably is methyl or ethyl. As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, for example. The number of carbon atoms of the aralkyl group is preferably 7-20, and more preferably 7-14. Moreover, as an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. The number of carbon atoms of the aryl group is preferably 6-24, and more preferably 6-12. Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent. The heteroatom-containing hydrocarbon group has a structure in which the carbon atoms in the above-mentioned hydrocarbon group are substituted by heteroatoms. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. In addition, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, and a bromine atom.

啉環等。 The phrase that R ² and R ³ may be bonded to each other to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. The ring structure formed by R ² and R ^{3 may contain heteroatoms.} The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring,

Morpholino ring etc.

啉環。 In the present invention, it is preferred that 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 or a piperidine ring ,

Morpholino ring.

Examples of monomers that derive the constituent units represented by the above general formula (I) include: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and dimethyamine (meth)acrylate. Ethylaminoethyl, diethylaminopropyl (meth)acrylate, etc. (meth)acrylates containing alkyl substituted amino groups, etc., dimethylaminoethyl (meth)acrylamide, dimethylamine Alkylpropyl (meth)acrylamide, etc., containing alkyl-substituted amino group (meth)acrylamide, etc. Among them, in terms of improving dispersibility and dispersion stability, it is preferable to use dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate ( (Meth)acrylamide. The structural unit represented by the general formula (I) may be composed of one type, or may be composed of two or more types of structural units.

In the A block containing the structural unit represented by the general formula (I), the structural unit represented by the general formula (I) preferably contains 3 or more. Among them, in terms of improving dispersibility and dispersion stability, it is preferable to include 3 to 100, more preferably 3 to 50, and even more preferably 3 to 30.

The A block may have a structural unit other than the structural unit represented by the general formula (I) within the scope of achieving the purpose of the invention, as long as it is a structural unit that can be copolymerized with the structural unit represented by the general formula (I) May contain. For example, as a structural unit other than the structural unit represented by the general formula (I) that may be contained in the A block, the "other structural units" listed in the following B block can be used. Specifically, for example, the following The structural units represented by the general formula (II), etc. are described. In the A block in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is preferably 50-100% by mass relative to the total mass of the total structural unit of the A block , More preferably 80-100% by mass, most preferably 100% by mass. The reason is that the higher the ratio of the constituent units represented by the general formula (I), the higher the adsorption force to the color material, and the better the dispersibility and dispersion stability of the block copolymer. In addition, the content ratio of the above-mentioned structural unit is calculated from the feed mass when synthesizing the A block having the structural unit represented by the general formula (I).

Moreover, in terms of improving dispersibility and dispersion stability, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is preferably relative to the block copolymer The total mass of the total constituent units is 5-60% by mass, more preferably 10-50% by mass. In addition, the content ratio of each constituent unit in the above-mentioned block copolymer is calculated from the feed mass at the time of synthesizing the block copolymer before formation of the salt. Furthermore, the structural unit represented by the general formula (I) only needs to have affinity with the color material, and may be composed of one type, or may include two or more types of structural units.

{B block}

The B block does not contain the structural unit represented by the general formula (I), but contains at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) Blocks, and may further contain blocks of other constituent units within a range that does not impair the effects of the present invention. As the B block, in terms of dispersibility and dispersion stability, it is preferable to use a monomer having an unsaturated double bond that can be copolymerized with a monomer that derives the constituent unit represented by the general formula (I) The block is appropriately selected according to the solvent so as to have a solvophilic property. As a standard, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. becomes 20 (g/100g solvent) or more with respect to the solvent used in combination.

(At least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2))

The B block contains at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2). As the ^{bivalent linking group in A 1} of the above general formula (B1) and A ² , A ³ and A ⁴ of the above general formula (B2), the trivalent or tetravalent linking group in A ³ and A ^{4, for example} Represents aliphatic hydrocarbon groups, aromatic groups, -CONH- groups, -COO- groups, and combinations of these, and can contain O (oxygen atom), S (sulfur atom), N (nitrogen atom) in the carbon chain, and also May have substituents. As the above-mentioned tetravalent linking group, it may be a carbon atom. The aliphatic hydrocarbon groups in A ¹ , A ² , A ³ and A ⁴ may be linear, branched, or cyclic, saturated or unsaturated, may have substituents, and may also have O, S, N and other heteroatoms. For example, an ether group, a thioether group, a carbonyl group, an oxycarbonyl group, an amide group, etc. may be contained in the carbon chain. Moreover, as the above-mentioned substituent, a halogen atom, an alkoxy group, a phenoxy group, etc. are mentioned. The aromatic group in A ¹ , A ² , A ³ and A ⁴ may be a monocyclic or polycyclic aromatic group, which may have a substituent, and may also be a heterocyclic ring containing O, S, and N. The aromatic group includes, for example, a group containing a benzene ring and a naphthalene ring, and among these, a group containing a benzene ring is preferred. As a substituent, the same thing as mentioned above can be mentioned. Examples of the combination of aliphatic hydrocarbon groups and aromatic groups in A ¹ , A ² , A ³ and A ⁴ include a structure in which the above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic group are directly bonded, or the above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic group. The structure is connected with a heteroatom-containing linking group such as the above-mentioned ether group. Examples of the formula (B1) of the general formula A ¹ and (B2) of A ² in the divalent linking group, which is preferably a divalent group with the number of carbon atoms -COO- extending alkyl group having 1 to 10 of the The linking group is more preferably a divalent linking group that is a combination of a -COO- group and an alkylene group having 1 to 10 carbon atoms. ^{As the divalent linking group in A 3} and A ⁴ of the general formula (B2), among them, an alkylene group having 1 to 10 carbon atoms is preferred. ^{The A 1 of the} above general formula (B1) ^{and the alkylenes of A 2} , A ³ and A ⁴ of the above general formula (B2) may be linear, branched, or cyclic, preferably It is linear. In addition, the alkylene group may have a substituent, and may contain heteroatoms such as O, S, and N in the carbon chain. ^{As the trivalent linking group in A 3} and A ⁴ of the above general formula (B2), the group of atoms remaining after removing 3 hydrogen atoms from a saturated aliphatic hydrocarbon with 1 to 10 carbon atoms is preferred, and more preferred is The group of atoms remaining after removing 3 hydrogen atoms from saturated aliphatic hydrocarbons with 1 to 5 carbon atoms. These aliphatic saturated hydrocarbon groups may have substituents, and may contain heteroatoms such as O, S, and N in the carbon chain. ^{As the tetravalent linking group in A 3} and A ⁴ of the above general formula (B2), the atom group or carbon atom remaining after removing 4 hydrogen atoms from the aliphatic saturated hydrocarbon with 1 to 10 carbon atoms is preferred, More preferably, it is the atom group or carbon atom remaining after 4 hydrogen atoms are removed from the aliphatic saturated hydrocarbon with 1 to 5 carbon atoms. These aliphatic saturated hydrocarbon groups may have substituents, and may contain heteroatoms such as O, S, and N in the carbon chain.

^{As the divalent hydrocarbon group in R 13} of the above general formula (B2), which may contain at least one selected from an oxygen atom and a nitrogen atom, it may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. For example, it may contain Linear, branched or cyclic alkylene, alkenylene, arylene, and combinations of at least one of oxygen atom and nitrogen atom may also contain -CONH- group in the carbon chain, -COO- group, ether group, etc.

Examples of the divalent aliphatic hydrocarbon groups that may contain oxygen atoms in R ¹¹ of the above general formula (B1) and R ¹⁴ , R ¹⁶ , R ¹⁸ and R ^{19 of the above general formula (B2) include straight chain and branched chain} Or cyclic alkylene and alkenylene groups, and may also contain ether groups in the carbon chain. Among them, an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom is preferred. ^{Furthermore, when there are several R 14} , R ¹⁶ , R ¹⁸ or R ¹⁹ in the above general formula (B2), several R ¹⁴ , several R ¹⁶ , several R ¹⁸ and several R ¹⁹ can be respectively The same may be different. ^{In addition, as the trivalent or tetravalent aliphatic hydrocarbon group in R 11} of the above general formula (B1) that may contain an oxygen atom, for example, aliphatic saturated hydrocarbons or aliphatic non-linear, branched, or cyclic aliphatic hydrocarbon groups may be included. The remaining aliphatic hydrocarbon groups or carbon atoms after the removal of 3 or 4 hydrogen atoms in saturated hydrocarbons may also contain ether groups in the carbon chain. Among them, it is preferably the aliphatic saturated hydrocarbon group or carbon atom remaining after removing 3 or 4 hydrogen atoms from linear, branched or cyclic aliphatic saturated hydrocarbons with 1 to 10 carbon atoms that may contain oxygen atoms .

As R ¹⁰ and R ¹² of the above general formula (B1) and R ¹⁰ , R ¹⁵ and R ^{17 of the} above general formula (B2), among them, the reactivity is higher, the film strength is improved, the brightness of the colored layer and the ITO are improved In terms of the crack resistance of the film, a hydrogen atom is preferred. ^{Furthermore, in the case where there are several R 12} in the above general formula (B1) and in the case where there are several R ¹⁵ or R ¹⁷ in the above general formula (B2), several R ¹² , several R ¹⁵ and The plurality of R ¹⁷ may be the same or different.

In the above general formula (B2), it is preferable in terms of the hydroxy value of the dispersant easily becomes appropriate, in terms of solvent resolubility and development adhesion, and in terms of brightness and crack resistance of the ITO film. It is n ¹ +n ² >n ³ , and preferably m ¹ >m ² .

The number of (meth)acrylic groups having at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) in the side chain is not particularly limited, as long as In terms of improving the crack resistance of the ITO film, two or more are preferred. On the other hand, in terms of dispersion stability, it is preferably 6 or less, more preferably 3 or less, or 1 or 2.

At least one selected from the structural unit represented by the above-mentioned general formula (B1) and the structural unit represented by the above-mentioned general formula (B2) can be used, for example, by using a single unit having the structural unit represented by the general formula (I). Monomer copolymerized unsaturated double bonds and hydroxyl monomers (hereinafter referred to as "hydroxyl-containing monomers"), introducing structural units having hydroxyl groups to make compounds having isocyanate groups and (meth)acrylic groups ( Hereinafter, the isocyanate group referred to as "isocyanate group-containing (meth)acrylate") reacts with the hydroxyl group in the above-mentioned structural unit to be introduced. In addition, the structural unit represented by the above-mentioned general formula (B2) may be used, for example, by using a hydroxyl-containing monomer to introduce a structural unit having a hydroxyl group, so that an isocyanate group of the diisocyanate compound can react with the hydroxyl group in the above-mentioned structural unit. , The other isocyanate group of the diisocyanate compound is introduced by reacting with the hydroxyl group of the compound having a hydroxyl group and a (meth)acryloyl group. Furthermore, the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon. The reactivity of the hydroxyl group and the isocyanate group is high, and the reaction temperature can be reduced to about 70~90°C without the use of an amine catalyst. Therefore, the composition selected from the general formula (B1) is introduced by the above method At least one of the unit and the structural unit represented by the above general formula (B2) can inhibit yellowing caused by heating or catalyst during the reaction, so it can also inhibit the yellowing of the colored layer and improve the brightness of the colored layer . In addition, in the above-mentioned introduction method, the hydroxyl value can be easily adjusted, so that the solvent resolubility can be improved by making the hydroxyl value an appropriate value.

The hydroxyl-containing monomer is not particularly limited as long as it has an unsaturated double bond that can be copolymerized with the monomer deriving the structural unit represented by the general formula (I) and a monomer having at least one hydroxyl group. For example, Examples: 2-hydroxyethyl (meth)acrylate, 2(or 3)-hydroxypropyl (meth)acrylate, 2(or 3 or 4)-hydroxybutyl (meth)acrylate, cyclohexane dimethanol Hydroxyalkyl (meth)acrylates such as mono(meth)acrylate, alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, 2-hydroxy-3-(meth)acrylate Phenoxypropyl ester and other hydroxyaryloxyalkyl (meth)acrylate, hydroxyalkoxyalkyl (meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol mono(meth) Acrylate, ε-caprolactone 1 mol adduct of 2-hydroxyethyl (meth)acrylate and other (meth)acrylate monomers with hydroxyl groups; N-(2-hydroxyethyl)(former N-(hydroxyalkyl)(methyl)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, etc. ) (Meth)acrylamide monomers having hydroxyl groups such as acrylamide; 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, 2-(or 3- or 4-) Hydroxyalkyl vinyl ethers and other vinyl ether monomers such as hydroxybutyl vinyl ether; 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, 2-(or 3- Or 4-) Allyl ether monomers having hydroxyl groups such as hydroxyalkyl allyl ethers such as hydroxybutyl allyl ether, etc. Among them, (meth)acrylate monomers having hydroxyl groups are preferred to improve developability In terms of it, having a primary hydroxyl group is better than having a secondary hydroxyl group. Furthermore, the so-called primary hydroxyl group refers to a hydroxyl group whose carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the so-called secondary hydroxyl group refers to a hydroxyl group whose carbon atom to which the hydroxyl group is bonded is a secondary carbon atom. Moreover, in terms of improving the adhesiveness of development, among them, it is preferable to use the value of the glass transition temperature (Tgi) of the homopolymer of each monomer to be a hydroxyl-containing monomer of 0°C or higher, and it is more preferable to use it as Hydroxyl-containing monomers above 10°C. The (meth)acrylate monomer having a hydroxyl group is more preferably selected from hydroxyalkyl (meth)acrylate, hydroxyarylalkyl (meth)acrylate, and hydroxyalkoxy (meth)acrylate At least one of alkyl ester and hydroxyaryloxyalkyl (meth)acrylate, and more preferably selected from hydroxyalkyl (meth)acrylate and hydroxyaryloxyalkyl (meth)acrylate At least one of them, particularly preferably selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate More than one species in the group.

Examples of the above-mentioned isocyanate group-containing (meth)acrylate used when introducing the structural unit represented by the above-mentioned general formula (B1) include: 2-isocyanatoethyl (meth)acrylate, (former) Base) 3-isocyanatopropyl acrylate, 2-isocyanato-1-methyl ethyl (meth)acrylate, 2-isocyanato-1,1-dimethyl (meth)acrylate Ethyl, 4-isocyanatocyclohexyl (meth)acrylate, 2-(2-isocyanatoethoxy)ethyl (meth)acrylate, 1,1-(bisacrylic acid) isocyanate (Oxymethyl) ethyl ester and their derivatives. Examples of the above-mentioned derivatives include compounds having an isocyanate group and at least one (meth)acryloyl group blocked by a blocking agent, such as 2-[(3,5-dimethylpyridine methacrylate). Azolyl)carbonylamino]ethyl, 2-(0-[1'-methylpropyleneamino]carboxyamino)ethyl methacrylate and the like. Examples of these commercially available products include: Karenz AOI (registered trademark), Karenz MOI (registered trademark), AOI-VM (registered trademark), Karenz MOI-EG (registered trademark), Karenz BEI (registered trademark), Karenz MOI-BP (registered trademark), Karenz MOI-BM (registered trademark) (the above are made by Showa Denko Co., Ltd.), etc.

Examples of the above-mentioned isocyanate group-containing (meth)acrylate used when introducing the structural unit represented by the above-mentioned general formula (B2) include the molar ratio of hydroxyl-containing (meth)acrylate and diisocyanate compound About 1:1 reaction product. Examples of the hydroxyl-containing (meth)acrylate in the above reaction product include the above-mentioned hydroxyl-containing (meth)acrylate monomers that can be used as the above-mentioned hydroxyl-containing monomers, and hydroxyl-containing polyfunctional ( Meth)acrylate. The hydroxyl-containing polyfunctional (meth)acrylate is a compound having at least one hydroxyl group and two or more (meth)acrylic groups, and is not particularly limited, but preferably has 1 to 4 hydroxyl groups and 2 to 5 A (meth)acrylic acid base. Specific examples of hydroxyl-containing polyfunctional (meth)acrylates include, for example, trimethylolpropane di(meth)acrylate, pentaerythritol bis or tri(meth)acrylate, dipentaerythritol bis, Three, four or five (meth)acrylates, etc. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- or 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 3,5,5-isocyanate Trimethyl-3-isocyanatomethylcyclohexyl, meta-or p-xylylene diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, lysine Acid diisocyanate, pyridine diyl isocyanate, etc.

In addition, the isocyanate group-containing (meth)acrylate is 1 equivalent to the hydroxyl group of the hydroxyl-containing monomer, and the isocyanate group is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more In addition, it is easy to make the hydroxyl value an appropriate value when used in a mode of 0.8 equivalent or less, and it is preferable in terms of development adhesiveness and solvent resolubility, and the adhesiveness of the colored resin composition.

In addition, the isocyanate group-containing (meth)acrylate is 1 equivalent to the hydroxyl group of the hydroxyl-containing monomer, and the (meth)acrylic acid group is preferably 0.1 equivalent or more and 3.0 equivalent or less, more preferably The use of 0.15 equivalent or more and 2.5 equivalent or less is preferable in terms of brightness and crack resistance of the ITO film.

In addition, the structural unit represented by the above-mentioned general formula (B2) is to react one of the isocyanate groups of the diisocyanate compound with the hydroxyl group derived from the structural unit of the above-mentioned hydroxyl group-containing monomer, thereby making the hydroxyl group-containing (methyl group) ) In the case of a structural unit introduced by reacting another isocyanate group of an acrylate with a diisocyanate compound, the hydroxyl-containing (meth)acrylate here can be used with the above-mentioned hydroxyl-containing (meth)acrylate and The diisocyanate compound has the same molar ratio as the one described in the reaction product of about 1:1. In this case, one of the isocyanate groups of the diisocyanate compound is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more, based on 1 equivalent of the hydroxyl group of the constituent unit derived from the above-mentioned hydroxyl-containing monomer In addition, the use of the diisocyanate compound in the form of 0.8 equivalents or less makes it easy to make the hydroxyl value an appropriate value, and is preferable in terms of development adhesiveness and solvent resolubility, and adhesiveness of the colored resin composition. Furthermore, it is preferable that the hydroxyl group of the hydroxyl group-containing (meth)acrylate is 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more, based on 1 equivalent of another isocyanate group of the diisocyanate compound. The hydroxyl group-containing (meth)acrylate is used for 0.8 equivalents or less.

In the above-mentioned block copolymer, the content ratio of at least one selected from the constituent unit represented by the general formula (B1) and the constituent unit represented by the general formula (B2) is not particularly limited, and is relative to that of the block copolymer The total mass of the total constituent units is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, on the other hand, it is preferably 35% by mass or less, more preferably 30% by mass Below, it may be 20% by mass or less. By setting the content ratio of at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) to be above the above lower limit, the brightness of the colored layer and the suppression of adjacent coloring The effect of cracking of the ITO film formed on the layer (hereinafter referred to as the crack resistance of the ITO film) is improved, and the plate-making characteristics can be improved by being below the above upper limit. In addition, at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) may be composed of one type, or may include two or more types of structural units.

In addition, in the block copolymer before salt formation, the equivalent weight of the (meth)acrylic acid group contained in the side chain is preferably in the range of 100 to 6000, particularly preferably in the range of 250 to 4500. If the (meth)acrylic equivalent is more than the above lower limit, the brightness of the colored layer and the crack resistance of the ITO film will be further improved, and if it is below the above upper limit, the alkali developability and color material dispersion will be improved. Performance and plate-making characteristics. Here, the (meth)acryloyl equivalent means the weight average molecular weight of the (meth)acryloyl group per mole in the block copolymer before the salt formation, and is represented by the following formula (1).

Numerical formula (1) (meth)acrylic acid equivalent (g/mol)=W'(g)/M'(mol)

(In the formula (1), W'represents the mass (g) of the block copolymer before the salt is formed, and M'represents the (meth)propylene contained in the block copolymer W'(g) before the salt is formed The number of moles of the base (mol).)

The above-mentioned (meth)acrylic acid equivalent weight can also be measured by, for example, the iodine value test method described in JIS K 0070: 1992 to measure the (meth)acrylic acid content per 1 g of the block copolymer before salt formation. Calculated based on the number.

In addition, in the synthesis of the block copolymer used in the present invention, by appropriately adjusting the feeding amount of each constituent unit, the constituent units of the block copolymer can be made to have the desired content ratio, and the Copolymer with desired performance. Among them, the above-mentioned hydroxyl group-containing monomer and the above-mentioned isocyanate group-containing (meth)acrylate are used to introduce the structural unit represented by the above general formula (B1) and the structural unit represented by the above general formula (B2) In the case of at least one of them, in the synthesis of the block copolymer, in terms of improving the brightness of the colored layer and the crack resistance of the ITO film, it is preferable that the feeding amount of the hydroxyl-containing monomer is relative to The total amount of monomers is 5% by mass or more, more preferably 10% by mass or more. Furthermore, in terms of solvent re-solubility, the feeding amount of the hydroxyl-containing monomer is preferably 50% by mass or less, and more preferably 40% by mass or less with respect to the total amount of monomers. In addition, in terms of improving the brightness of the colored layer and the crack resistance and adhesion of the ITO film, the feeding amount of the isocyanate group-containing (meth)acrylate is relative to the hydroxyl group-containing single The feeding amount of the body is preferably 10% by mass or more, more preferably 15% by mass or more, and in terms of solvent resolubility, development adhesion, brightness, and crack resistance of the ITO film, it is preferably It is 120% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

(Other building blocks)

The B block may further contain other structural units that improve the solvophilicity. As the above-mentioned other structural unit constituting the B block, a monomer having an unsaturated double bond capable of copolymerizing with the monomer deriving the structural unit represented by the above-mentioned general formula (I) can be mentioned, and among them, the following general formula is preferred (II) The constituent units indicated.

(In the 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 )-O] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ represents a univalent group; 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, A monovalent group represented by _{-CH 2} CHO or -CH ₂ COOR ^{9 , R 9} is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms; the above-mentioned hydrocarbon group may also have a substituent; x represents an integer of 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.)

In the general formula (II), A'is a direct bond or a divalent linking group. The so-called direct bond means that A'does not have atoms, that is, C (carbon atom) and R ⁵ in the general formula (II) are bonded without other atoms. As a divalent linking group, the same thing as A in general formula (I) can be mentioned. As A'of the general formula (II), in terms of solubility to organic solvents, it is preferably a direct bond or a divalent linking group containing a -CONH- group or a -COO- group.

基、異

基、雙環戊基、二環戊烯基、金剛烷基、 低級烷基取代金剛烷基等。上述碳原子數2~18之烯基可為直鏈狀、支鏈狀、環狀之任一者。作為此種烯基，例如可列舉：乙烯基、烯丙基、丙烯基等。烯基之雙鍵之位置並無限定，就所獲得之聚合物之反應性之方面而言，較佳為於烯基之末端具有雙鍵。作為烷基或烯基等脂肪族烴之取代基，可列舉硝基、鹵素原子等。 In the general formula (II), R ⁵ represents a hydrocarbon group, -[CH(R ⁶ )-CH(R ⁷ )-O] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ . The hydrocarbon group in 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 above-mentioned alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and 2 -Ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl,

Base, different

Group, dicyclopentyl, dicyclopentenyl, adamantyl, lower alkyl substituted adamantyl, etc. The above-mentioned alkenyl group having 2 to 18 carbon atoms may be linear, branched, and cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group, etc. are mentioned, for example. The position of the double bond of the alkenyl group is not limited. In terms of the reactivity of the obtained polymer, it is preferable to have a double bond at the end of the alkenyl group. Examples of the substituent of aliphatic hydrocarbons such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

As an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aryl group is preferably 6-24, and more preferably 6-12. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aralkyl group is preferably 7-20, and more preferably 7-14. As the substituent of the aromatic ring such as an aryl group or an aralkyl group, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom, etc. can be mentioned. Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In the above R ⁵ , x is an integer from 1 to 18, preferably an integer from 1 to 4, more preferably an integer from 1 to 2, and y is an integer from 1 to 5, preferably an integer from 1 to 4, and more Preferably it is 2 or 3. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.

The hydrocarbon group in the above R ⁸ is the same as that shown in the ^{above R 5.} R ⁹ may be a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be any of linear, branched, or cyclic. ^{In addition, 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 following solvents. Specifically, for example, a diol that is generally used as a solvent for the colored resin composition for color filters is used for the above-mentioned solvent. In the case of solvents such as ether acetate-based, ether-based, and ester-based solvents, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, etc. are preferred.

Furthermore, the above R ⁵ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an acidic group, an epoxy group, an isocyanate group, etc. within a range that does not hinder the dispersibility of the block copolymer, etc., and also, After the above-mentioned block copolymer is synthesized, it can be reacted with the compound having the above-mentioned substituent to add the above-mentioned substituent.

(Constituted units derived from monomers containing acidic groups)

In terms of improving the solvent affinity of the B block and improving the dispersibility and dispersion stability of the color material dispersion liquid, it is preferable that the B block further contains a structural unit derived from an acidic group-containing monomer. As the above-mentioned acidic group-containing monomer, for example, a monomer containing an unsaturated double bond and an acidic group which can be copolymerized with the monomer that derives the structural unit represented by the general formula (I) is mentioned. As said acidic group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a boronic acid group, etc. are mentioned, for example, Among them, a carboxyl group is preferable in terms of developability. Examples of carboxyl group-containing monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, and crotonic acid. , Cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, ω- Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, monomers containing acid anhydride groups, such as maleic anhydride, itaconic anhydride, and citraconic acid anhydride, may also be used as the carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.

In the case of containing the structural unit derived from the acidic group-containing monomer, the content ratio of the structural unit derived from the acidic group-containing monomer in the block copolymer before salt formation is not particularly limited. The total mass of the total constituent units of the stage copolymer is preferably 0.05 to 4.5% by mass, more preferably 0.07 to 3.7% by mass. By setting the content ratio of the structural unit derived from the acidic group-containing monomer to be above the above lower limit, the effect of suppressing development residues is excellent, and by being below the above upper limit, it is possible to prevent deterioration of development adhesion or resolving Deterioration of solubility. In addition, the structural unit derived from the acidic group-containing monomer may be composed of one type, or may include two or more types of structural units.

The number of structural units constituting the B block is not particularly limited. In terms of the solvent-philic part and the color-philic material part effectively functioning to improve the dispersibility of the color material, it is preferably 10 to 300, and more preferably It is 10 to 100 pieces, and more preferably 10 to 70 pieces.

In the B block in the block copolymer, the content ratio of the structural unit represented by the above general formula (II) is relative to the total structural unit of the B block in terms of improving the solubility of the solvent and the dispersibility of the color material. The total mass is preferably 30-95% by mass, more preferably 40-90% by mass. In addition, the content ratio of the above-mentioned structural unit is calculated from the feed mass when synthesizing the B block.

In addition, in the block copolymer before salt formation, the content ratio of the structural unit represented by the above general formula (II) is relative to the total of the total structural units of the block copolymer in terms of improving the dispersibility of the color material The mass is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content ratio of the above-mentioned structural unit is calculated from the feed mass when the block copolymer before the formation of the salt is synthesized.

The B block is preferably a constitutional unit appropriately selected so as to function as a solvophilic site. The constitutional unit represented by the above general formula (II) may be composed of one type or two or more types of constitutional units. . Two or more structural units contained in the B block may be randomly arranged in the block.

In the present invention, it is preferable that the B block of the block copolymer before the salt formation includes a structural unit derived from the above-mentioned hydroxyl group-containing monomer in terms of improving the adhesiveness of development. In the case of containing the structural unit derived from the above-mentioned hydroxyl-containing monomer, it is considered that it is likely to interact with glass or metal that is generally used as a substrate, and therefore the development adhesion is improved. When the B block contains the structural unit derived from the above-mentioned hydroxyl group-containing monomer, the development speed is further improved.

In the case of containing structural units derived from hydroxyl-containing monomers, the ratio of the content of structural units derived from hydroxyl-containing monomers to the total structural units of the block copolymer in the block copolymer before salt formation The total mass of the bismuth is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. If it is more than the said lower limit, it can become a thing with better development adhesiveness. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is less than the above upper limit, it can be preferable in terms of increasing the introduction ratio of other useful monomers. In addition, the content ratio of the above-mentioned structural unit is calculated from the feed mass when the block copolymer before the formation of the salt is synthesized.

Furthermore, in the present invention, it is preferable to include a structural unit derived from an aromatic group-containing monomer in the B block in terms of improving solvent resolubility. In the case of containing the structural unit derived from the aromatic group-containing monomer, it is considered that the compatibility with the solvent or other components is easily improved, and therefore the solvent resolubility is improved. As the structural unit derived from the aromatic group-containing monomer, a monomer containing an unsaturated double bond and an aromatic group that can be copolymerized with the monomer that derives the structural unit represented by the general formula (I) can be used. Examples of such monomers include acrylic esters such as benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and phenoxyethyl (meth)acrylate, Styrenes such as styrene, vinyl ethers such as phenyl vinyl ether. In terms of improving the development adhesion, among them, it is preferable to use the value of the glass transition temperature (Tgi) of the homopolymer of each monomer to be 0°C or higher and the aromatic group-containing monomer is more preferable to use Becomes an aromatic group-containing monomer above 10°C. In terms of easy improvement of resolubility, among them, it is preferably selected from the group consisting of benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and benzene (meth)acrylate One or more of the group consisting of oxyethyl ester, more preferably selected from the group consisting of benzyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate One or more of them.

In the case of containing structural units derived from aromatic group-containing monomers, in terms of improving solvent re-solubility, in the block copolymer before salt formation, it is derived from aromatic group-containing monomers. The content ratio of the constituent units relative to the total mass of the total constituent units of the block copolymer is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass the above. If it is more than the above-mentioned lower limit, it can become the one with better solvent resolubility. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is less than the above upper limit, it can be preferable in terms of increasing the introduction ratio of other useful monomers.

Furthermore, among them, in terms of improving development adhesion and solvent re-solubility, it is preferable that the B block contains (i) a constituent unit derived from a hydroxyl-containing monomer and a monomer derived from an aromatic group-containing monomer. The structural unit and (ii) at least one of structural units derived from a monomer containing a hydroxyl group and an aromatic group.

When (i) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer are included, relative to 1 part by mass of a structural unit derived from an aromatic group-containing monomer It is preferable to contain 0.15 parts by mass or more of structural units derived from a hydroxyl-containing monomer, and more preferably to contain 0.5 parts by mass or more. The reason is that if it is equal to or more than the above lower limit value, it can be excellent in development adhesiveness. Also, similarly, it is preferable to contain the structural unit derived from the hydroxyl-containing monomer in 15 parts by mass or less with respect to 1 part by mass of the structural unit of the aromatic group-containing monomer, and more preferably 7 parts by mass or less Contains structural units derived from hydroxyl-containing monomers. The reason is that if it is not more than the above upper limit value, it can be excellent in solvent resolubility. Among them, the value of the glass transition temperature (Tgi) relative to the homopolymer is 1 part by mass of the structural unit derived from the aromatic group-containing monomer at 10°C or higher, and the glass transition containing the homopolymer in the above range is particularly preferred. The value of temperature (Tgi) becomes a structural unit derived from a hydroxyl-containing monomer above 10°C. The reason is that by containing at least the above lower limit value, the development adhesiveness can be made more excellent, and by containing at the above upper limit value or less, the solvent resolubility can be made more excellent.

In addition, examples of (ii) monomers containing a hydroxyl group and an aromatic group in the structural unit derived from a monomer containing a hydroxyl group and an aromatic group include: (meth)acrylic acid 2-hydroxy-3-phenoxy group Propyl ester, 2-propenyloxyethyl-2-hydroxyethyl-phthalic acid and the like. The value of the glass transition temperature (Tgi) of the homopolymer is 10°C or more, and the effect obtained by the structural unit derived from the hydroxyl-containing monomer and the structural unit derived from the aromatic group-containing monomer can be obtained In terms of both the effects obtained, it is preferable to use 2-hydroxy-3-phenoxypropyl (meth)acrylate. That is, the reason is that it is preferable in terms of improvement in development adhesion, development speed, and solvent resolubility. In the case of containing (ii) a structural unit derived from a monomer containing a hydroxyl group and an aromatic group, a single structural unit can improve development adhesion, development speed, and solvent resolubility, so other functions can also be improved Advantages of the introduction ratio of sexual monomers.

Also, in terms of improving the development adhesion, it is preferable to make the value (Tgi) of the glass transition temperature (Tgi) of the homopolymer of the monomers of 10°C or more in the total of the monomers in the B block 75% by mass or more, More preferably, it is 85% by mass or more.

In the above-mentioned block copolymer, the ratio m/n of the unit number m of the structural unit of the A block to the unit number n of the structural unit of the B block is preferably in the range of 0.05 to 1.5. In terms of material dispersibility and dispersion stability, it is more preferably in the range of 0.1 to 1.0.

In addition, the amine value of the block copolymer before salt formation is not particularly limited. In terms of color material dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more , And more preferably 60 mgKOH/g or more. Moreover, as an upper limit, 140 mgKOH/g or less is preferable, 130 mgKOH/g or less is more preferable, and 120 mgKOH/g or less is still more preferable. If it is more than the above lower limit, the dispersion stability is more excellent. Moreover, if it is less than the said upper limit, the compatibility with other components will be excellent, and the solvent re-solubility will become favorable. Furthermore, in the present invention, the so-called amine value of the block copolymer before salt formation is expressed as the amount of hydrochloric acid required for 1 g of the solid content of the block copolymer before salt formation, expressed in equivalents The mass (mg) of potassium hydroxide is a value measured by the method described in JIS K 7237:1995.

The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, but it is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 3,000 in terms of good color material dispersibility and dispersion stability. ~12000. Here, the weight average molecular weight (Mw) is calculated as a standard polystyrene conversion value by gel permeation chromatography (GPC). In addition, in the present invention, the weight average molecular weight Mw of the block copolymer is determined as a standard polystyrene conversion value by GPC (gel permeation chromatography). The measurement system uses HLC-8120GPC manufactured by Tosoh Co., Ltd., the dissolution solvent is N-methylpyrrolidone added with 0.01 mol/L lithium bromide, and the polystyrene standard for the calibration curve is set to Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are made by Polymer Laboratories, Easi PS-2 series) and Mw1090000 (made by Tosoh Co., Ltd.), set the measuring column to TSK-GEL ALPHA- M×2 (manufactured by Tosoh Co., Ltd.). Furthermore, the macromonomers, salt-type block copolymers, and graft copolymers used as raw materials for the block copolymers are also carried out under the above-mentioned conditions.

In the present invention, the arrangement of each block of the block copolymer is not particularly limited. For example, it may be an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like. Among them, in terms of excellent dispersibility, AB block copolymers or ABA block copolymers are preferred.

The manufacturing method of the said block copolymer is not specifically limited. The block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method. The reason is that it is possible to produce copolymers with uniform molecular weights that are not prone to chain transfer or deactivation, and to improve dispersibility and the like. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization methods and radical transfer polymerization methods, living cationic polymerization methods, and the like. Copolymers can be produced by sequentially polymerizing monomers using these methods. For example, a block copolymer can be produced by first producing the A block and polymerizing the constituent units constituting the B block with the A block. In addition, in the above-mentioned production method, the order of polymerization of the A block and the B block may be reversed. In addition, the A block and the B block may be produced separately, and then the A block and the B block may be coupled.

{At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons}

In the present invention, the block copolymer is preferably at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) in terms of improving the dispersibility of the color material, and is selected from organic acids At least one of the group consisting of the compound and the halogenated hydrocarbon forms a salt-type block copolymer of a salt. As the above-mentioned organic acid compound, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferred, and as the above-mentioned halogenated hydrocarbon, among them, the following general formula (2) is preferred. ) Represented by the compound. That is, as at least one selected from the group consisting of the above-mentioned organic acid compounds and halogenated hydrocarbons, preferably one or more compounds selected from the group consisting of the following general formulas (1) to (3) can be used .

(In the general formula (1), R ^a represents a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms, a vinyl group, a substituted phenyl group or a benzyl group, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or an alkylene group with a carbon number of 1 to 4 (former yl) Bingxi Xi group; in formula 2) (, R ^b, R ^{b 'and} R ^{b "each} independently represent a hydrogen atom, an acidic group or an ester thereof, may have a substituent group of carbon number 1 to 20 of a linear Chain, branched or cyclic alkyl group, optionally substituted vinyl group, optionally substituted phenyl or benzyl group, or -OR ^f , R ^f represents optionally substituted carbon number 1-20 straight chain , Branched or cyclic alkyl group, optionally substituted vinyl group, optionally substituted phenyl or benzyl group, or (meth)acryloyl group with an alkylene having 1 to 4 carbon atoms, X represents a chlorine atom, a bromine atom or an iodine atom; in the general formula (3), R ^c and ^Rd each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms , Vinyl, phenyl or benzyl which may have substituents, or -OR ^e , R ^e represents linear, branched or cyclic alkyl with 1 to 20 carbons, vinyl, benzene which may have substituents (Meth)acryloyl group or benzyl group, or a (meth)acryloyl group with an alkylene having 1 to 4 ^{carbon atoms; wherein at least one of R c} and R ^d contains a carbon atom.)

(Selected from one or more compounds from the group consisting of the above general formulas (1) to (3))

In the general formula (1) to (3), as ^{R a, R b, R b} ', R b ", R c, R d, R e , and the carbon atoms in R ^f is a straight chain of 1 to 20, The branched or cyclic alkyl group may be either linear or branched, and may also include a cyclic structure. Specifically, examples include methyl, ethyl, n-propyl, and isopropyl , N-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, twelve Alkyl, cyclopentyl, cyclohexyl, tetradecyl, octadecyl, etc. Preferably, straight, branched or cyclic alkyl groups with 1 to 15 carbon atoms can be cited, and more preferably, the number of carbon atoms can be cited 1 to 8 of a linear, branched or cyclic alkyl group of. Furthermore, in R ^a, R ^c, R ^d and R ^e, the group as a substituent of a phenyl or benzyl substituent of the group, include e.g. Alkyl groups, acyl groups, acyloxy groups, etc. having 1 to 5 carbon atoms.

酸基(-B(OH)₂)、二取代硼酸基(>BOH)等，亦可為如羧酸酯基(-COO-)等般氫原子解離之陰離子，進而亦可為與鈉離子或鉀離子等鹼金屬離子形成鹽之酸性 鹽。又，作為酸性基之酯基，可列舉羧酸酯(-COOR)、磺酸酯(-SO₃R)、磷酸酯(-P(=O)(OR)₂)、(>P(=O)(OR))、

酸酯(-B(OR)₂)、二取代硼酸酯(>BOR)等。其中，作為酸性基之酯基，就分散性及分散穩定性之方面而言，較佳為羧酸酯(-COOR)。再者，R為烴基，並無特別限定，就分散性及分散穩定性之方面而言，其中較佳為碳原子數1~5之烷基，更佳為甲基或乙基。 In R ^b , R ^b' , R ^b" and R ^f , as the substituent of the optionally substituted phenyl or benzyl group, for example, an acidic group or an ester group thereof, and an alkane having 1 to 5 carbon atoms can be mentioned. Group, acyl group, acyloxy group, etc. In addition, in R ^b , R ^b' , R ^b" and R ^f , it is used as a linear, branched or cyclic alkane with 1 to 20 carbon atoms that may have a substituent The substituent of the group or the vinyl group includes an acidic group or its ester group, a phenyl group, an acyl group, and an acyloxy group. In R ^b , R ^b' , R ^b" and R ^f , the so-called acidic group refers to a group that releases protons in water to show acidity. Specific examples of acidic groups include carboxyl (-COOH), sulfo ( -SO ₃ H), phosphonic acid group (-P(=O)(OH) ₂ ), phosphonic acid subunit (>P(=O)(OH)),

Acid groups (-B(OH) ₂ ), di-substituted boronic acid groups (>BOH), etc., can also be anions that dissociate hydrogen atoms such as carboxylate groups (-COO-), and can also be anions with sodium ions or Alkali metal ions such as potassium ion form acid salt of salt. In addition, as the ester group of the acidic group, carboxylate (-COOR), sulfonate (-SO ₃ R), phosphate (-P(=O)(OR) ₂ ), (>P(=O) )(OR)),

Ester (-B(OR) ₂ ), disubstituted borate (>BOR), etc. Among them, the ester group as an acidic group is preferably a carboxylic acid ester (-COOR) in terms of dispersibility and dispersion stability. Furthermore, R is a hydrocarbon group and is not particularly limited. In terms of dispersibility and dispersion stability, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.

酸基、二取代硼酸基、該等之陰離子以及該等之鹼金屬鹽、及該等之酯中之1種以上之官能基，其中更佳為具有選自羧基、羧酸酯基、羧酸鹽基及羧酸酯中之官能基。於上述通式(2)之化合物具有酸性基及其酯基(以下稱為酸性基等)之情況下，推斷該化合物所具有之酸性基等側及鹵素原子側烴均可與末端之氮部位形成鹽，但相較末端之氮部位與酸性基等形成鹽之情況，末端之氮部位與鹵素原子側烴穩定地形成鹽。而且，推斷藉由使色材吸附至穩定地存在之鹽形成部位，分散性及分散穩定性提高。 In terms of dispersibility, dispersion stability, alkali developability and suppression of development residues, the compound of the above general formula (2) preferably has a carboxyl group,

One or more functional groups among acid groups, disubstituted boronic acid groups, these anions, alkali metal salts, and these esters, and more preferably have one selected from the group consisting of carboxyl, carboxylate, and carboxylic acid The functional group in the base and carboxylate. In the case where the compound of the above general formula (2) has an acidic group and its ester group (hereinafter referred to as acidic group, etc.), it is inferred that the acidic group and other side and halogen atom side hydrocarbons that the compound has can interact with the terminal nitrogen site A salt is formed, but compared to the case where the terminal nitrogen site forms a salt with an acidic group, the terminal nitrogen site and the halogen atom side hydrocarbon stably form a salt. Furthermore, it is inferred that the dispersibility and dispersion stability are improved by adsorbing the color material to the stably existing salt formation site.

When the compound of the aforementioned general formula (2) has the aforementioned acidic group and the like, it may have two or more of the aforementioned acidic group and the like. In the case of having two or more of the above-mentioned acidic groups, etc., the above-mentioned acidic groups and the like having several may be the same or different. The number of the acidic groups and the like possessed by the compound of the general formula (2) is preferably 1 to 3, more preferably 1 to 2, and even more preferably one.

In the above general formula (1) wherein R ^a having an aromatic ring, in the general formula (2) R ^b, R ^{b 'and} R ^{b "is} at least one having an aromatic ring, and in the above general formula (3) When ^{at least one of R c} and R ^d has an aromatic ring, the affinity with the skeleton of the following color material is improved, the color material dispersibility and dispersion stability become excellent, and a coloring composition with excellent contrast can be obtained , It is better in terms of the above.

In terms of improving the dispersibility of color materials, the molecular weight of one or more compounds selected from the group consisting of the above general formulas (1) to (3) is preferably 1000 or less, and among them, 50 to 800 are preferred. More preferably, it is 50-400, still more preferably 80-350, and most preferably 100-330.

Examples of the compound represented by the general formula (1) include: benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, mono-n-propylsulfuric acid, etc. . Furthermore, hydrates such as p-toluenesulfonic acid hydrate can also be used. Examples of the compound represented by the general formula (2) include: methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, and n-butyl chloride. Base, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, iodide Benzyl, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-iodophenylbenzoic acid , Chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3-(bromomethyl)phenylboronic acid, etc. Examples of the compound represented by the general formula (3) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenyl phosphinic acid, and phenyl phosphonic acid. , Dimethyl acryloxy ethyl acid phosphate, etc. In terms of particularly excellent dispersion stability, it is preferably selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethylacryloxy ethyl acid phosphate, dibutyl phosphoric acid, and benzyl chloride. , Benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid-hydrate. Among them, it is preferable to use one selected from phenylphosphinic acid, phenylphosphonic acid, and benzyl chloride. One or more of the group consisting of benzyl bromide, benzyl bromide, and p-toluenesulfonic acid monohydrate. In addition, in terms of improving the effect of suppressing development residue by the combination with the above-mentioned specific block copolymer, it is also preferable to use a compound represented by the general formula (2) having an acidic group and its ester group, Among them, it is also preferably used selected from α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid and 4-iodophenyl One or more of the group consisting of benzoic acid.

In the salt-type block copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is due to the fact that it is formed with the terminal nitrogen site of the structural unit represented by the general formula (I) Salt, therefore, it is preferable that the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0.01 moiety with respect to the terminal nitrogen site of the structural unit represented by the general formula (I). Ear or more, more preferably 0.1 mol or more, still more preferably 0.2 mol or more, and particularly preferably 0.3 mol or more. If it is more than the above lower limit, the effect of improving the dispersibility of the color material due to the salt formation is easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. If it is equal to or less than the above upper limit, it will be excellent in development adhesiveness or solvent resolubility. In addition, at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When combining two or more types, it is preferable that the total content is in the said range.

As a method for preparing the salt-type block copolymer, it can be exemplified by adding at least one selected from the group consisting of the above-mentioned organic acid compounds and halogenated hydrocarbons in a solvent in which the block copolymer before salt formation is dissolved or dispersed. And stirring, and then heating method as necessary. Furthermore, the terminal nitrogen portion of the structural unit represented by the general formula (I) of the block copolymer forms a salt with at least one selected from the group consisting of the above-mentioned organic acid compound and halogenated hydrocarbon, and The ratio can be confirmed by a known method such as Nuclear Magnetic Resonance (NMR).

Compared with the block copolymer before salt formation, the amine value of the obtained salt-type block copolymer becomes smaller corresponding to the amount of salt formed. However, since the salt formation site is the same as the nitrogen site corresponding to the end of the amine group, or in order to become a strengthened color material adsorption site, the salt formation improves the color material dispersibility or the color material dispersion stability. tendency. In addition, the salt formation site is the same as the amine group, if too much, it will adversely affect the solvent resolubility. Therefore, in the present invention, the amine value of the block copolymer before salt formation can be used as an index for improving the dispersion stability of the color material and the solvent resolubility. The amine value of the obtained salt-type block copolymer is preferably 0 to 130 mgKOH/g, and more preferably 0 to 120 mgKOH/g. If it is less than the above upper limit, the compatibility with other components is excellent, and the solvent re-solubility becomes good.

Furthermore, in the salt-type block copolymer, the amine value of the salt-type block copolymer formed by salt formation from the compound represented by the above general formula (2) can be set by the method described in JIS K 7237:1995 The measured value. The reason is that the compound of the above general formula (2) forms a salt with the halogen atom-side hydrocarbon at the terminal nitrogen portion of the structural unit represented by the general formula (I), and therefore, even by this measurement method, it will not affect The state of salt formation brings about changes, and the amine value can be measured. On the other hand, in the salt-type block copolymer, the amine value of the salt-type block copolymer formed by the compound represented by the above-mentioned general formula (1) or (3) can be determined by the amine value of the salt-type block copolymer before the formation of the salt. The amine value of the stage copolymer is calculated and determined as described below. The reason is that the compound represented by the above-mentioned general formula (1) or (3) forms a salt with an acidic group at the end of the structural unit represented by the general formula (I). Therefore, if the compound represented by the above-mentioned JIS K 7237 : The method described in 1995 to measure the amine value of this salt-type block copolymer will change the state of salt formation, and the accurate value cannot be measured. First, by the above method, the amine value of the block copolymer before salt formation is obtained. Next, the 13C-NMR spectrum of the salt-type block copolymer was measured using a nuclear magnetic resonance device. In the obtained spectrum data, the nitrogen portion of the terminal of the structural unit represented by the above general formula (I) was not salted. The ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom formed and the peak of the carbon atom adjacent to the nitrogen atom undergoing salt formation is determined. The salt type block copolymer is selected from the above general formula (1) or (3). The reaction rate of one or more compounds in the group to the terminal nitrogen site of the structural unit represented by the general formula (I) (the rate of the terminal nitrogen site that undergoes salt formation). Regarding the salt formation of one or more compounds selected from the group consisting of the above-mentioned general formula (1) or (3), the nitrogen site at the end of the structural unit represented by the general formula (I) is based on the amine value Set to 0, subtract from the amine value of the block copolymer before salt formation by (the amine value of the block copolymer before salt formation measured by the method described in JIS K 7237: 1995) × (from 13C- The value of the amine consumed due to salt formation calculated by the ratio of nitrogen sites at the end of salt formation (%)/100) calculated by NMR spectroscopy is used to obtain this value. The amine value of the salt-type block copolymer={Amine value of the block copolymer before salt formation measured by the method described in JIS K 7237:1995}-{Measured by the method described in JIS K 7237:1995 The amine value of the block copolymer before the salt formation}×{The ratio of the nitrogen site at the end of the salt formation calculated from the 13C-NMR spectrum (%)/100}

The acid value of the dispersant used in the present invention is not particularly limited, but it is preferably 18 mgKOH/g or less, more preferably 12 mgKOH/g or less in terms of developing adhesion and solvent resolubility. On the other hand, the acid value of the dispersant used in the present invention is preferably 0 mgKOH/g in terms of further improving solvent resolubility and development adhesiveness, substrate adhesiveness and dispersion stability. The smaller the acid value, the less likely it is to be corroded by the alkaline developer, so it is considered that the development adhesiveness becomes better. On the other hand, in terms of the effect of suppressing development residues, it is preferably 1 mgKOH/g or more, and more preferably 2 mgKOH/g or more. In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 12 mgKOH in terms of developing adhesion and solvent re-solubility. /g or less. In addition, in terms of further improving solvent resolubility and development adhesion, and in terms of substrate adhesion and dispersion stability, the acid value of the block copolymer before salt formation is preferably 0 mgKOH/g. On the other hand, in terms of the effect of suppressing development residues, it is preferably 1 mgKOH/g or more, and more preferably 2 mgKOH/g or more.

As mentioned above, the acid value of the block copolymer before salt formation means the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1g of the solid component of the block copolymer, by Measured by the method described in JIS K 0070: 1992. In addition, regarding the salt-type block copolymer, the acid value of the salt-type block copolymer formed by salt formation from the compound represented by the above general formula (2) is also measured by the method described in JIS K 0070: 1992 Got the value. The reason is that the compound of the above general formula (2) forms a salt with the halogen atom-side hydrocarbon at the terminal nitrogen portion of the structural unit represented by the general formula (I), and therefore, even by this measurement method, it will not affect The state of salt formation brings about changes and can be measured. On the other hand, when the salt-type block copolymer is a salt-type block copolymer in which salt is formed by the compound represented by the above general formula (1) or (3), the acidic group used for salt formation is removed And calculate the acid value. The reason is that the acidic group used for salt formation cannot function as an acidic group that increases the acid value of the dispersant. Therefore, in this case, the acid value of the salt-type block copolymer formed by salt formation with the compound represented by the above general formula (1) or (3) is calculated from the value obtained by the following formula. The reason is that if the acid value of the salt type block copolymer formed by the compound represented by the general formula (1) or (3) is measured by the method described in JIS K 0070: 1992, the salt The state of formation brings about changes, and the exact value cannot be measured.

The acid value of the salt-type block copolymer = (total acid value of the compound represented by the above general formula (1) or (3) used for salt formation-acid value consumed for salt formation) + block copolymerization before salt formation The acid value of the body

Here, the total acid value of the compound represented by the above general formula (1) or (3) used for salt formation can be measured by the method described in the above JIS K 0070:1992. On the other hand, the acid value consumed for salt formation was calculated from the salt formation ratio obtained by NMR. Specifically, the acid value consumed for salt formation, for example, is measured by the 13C-NMR spectrum of the salt-type block copolymer using a nuclear magnetic resonance device, and the obtained spectrum data is based on the nitrogen in the terminal nitrogen site that has not undergone salt formation. The ratio of the integral value of the carbon atom peak adjacent to the atom to the carbon atom peak adjacent to the nitrogen atom undergoing salt formation is calculated as the ratio of the number of nitrogen sites at the end of the salt formation to the total number of nitrogen sites at the end. By {the amine value of the block copolymer before the salt formation measured by the method described in JIS K 7237:1995}×{calculated from 13C-NMR spectrum the ratio of the nitrogen site at the end of the salt formation (%)/100 }, calculate the consumed amine value, which is the same value as the acid value consumed for salt formation. However, when the compound represented by the general formula (1) is 1 mol or less to form a salt with respect to the nitrogen site at the terminal of the structural unit represented by the general formula (I), it may have one When the compound represented by the above general formula (3) of the acidic group is 1 mol or less for salt formation, or the compound represented by the above general formula (3) having 2 acidic groups is 0.5 mol or less for the salt formation In the case of formation, as long as the total amount of acidic groups forms a salt with the terminal nitrogen site of the structural unit represented by the general formula (I), the acidic block copolymer in the salt-type block copolymer after salt formation The base does not affect the acid value, so it can have the same acid value as the block copolymer before the salt is formed. On the other hand, when the compound represented by the above-mentioned general formula (3) having two acidic groups is added in a molar number exceeding the above-mentioned number of moles, there are acidic groups that have not undergone salt formation in the dispersant after the salt is formed. Therefore, as shown in the above formula, the acid value of the amount of acidic groups that have not undergone salt formation is added to the acid value of the block copolymer before salt formation to calculate the acid value of the dispersant.

Furthermore, in the present invention, the hydroxyl value of the dispersant is preferably 120 mgKOH/g or less, more preferably 80 mgKOH/g or less, and still more preferably 60 mgKOH/g or less. If the hydroxyl value of the dispersant is too high, the re-solubility of the solvent may decrease. On the other hand, in terms of dispersibility and dispersion stability, the hydroxyl value of the dispersant is preferably 2 mgKOH/g or more, more preferably 5 mgKOH/g or more. Furthermore, in the present invention, the hydroxyl value refers to the mass (mg) of KOH required to neutralize the acetic acid bound to the acetyl compound obtained from 1g of the solid content, and refers to titration by potentiometric titration in accordance with JIS K 0070: 1992 The value obtained by the law.

In the color material dispersion of the present invention, as a dispersant, at least one of the above-mentioned block copolymer and salt type block copolymer is used, and the content depends on the type of color material used, and further according to the following color filter The concentration of the solid content in the photosensitive colored resin composition is appropriately selected. The content of the dispersant relative to 100 parts by mass of the total solid content in the color material dispersion is preferably 3 to 45 parts by mass, more preferably 5 to 35 parts by mass. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of the photosensitive colored resin composition for color filters will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a coating film or colored layer with a high color material concentration, the content of the dispersant is preferably 3-25 parts by mass, more preferably 3-25 parts by mass, relative to 100 parts by mass of the total solid content in the color material dispersion. It is formulated at a ratio of 5-20 parts by mass. Furthermore, in the present invention, the solid content refers to owners other than the above-mentioned solvent, and also includes monomers dissolved in the solvent, etc.

<color material>

In the present invention, the color material is not particularly limited as long as it can achieve the desired color development when forming the coloring layer of the color filter. Various organic pigments, inorganic pigments, dispersible dyes, and dyes can be used. A salt-forming compound etc. are used individually or in mixture of 2 or more types. Among them, organic pigments are preferably used due to higher color rendering properties and higher heat resistance. Examples of organic pigments include compounds classified as pigments in the color index (C.I.; issued by The Society of Dyers and Colourists), and specifically, those with a color index (C.I.) number as described below can be cited.

CI Pigment Yellow 1, 3, 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, 155 , 156, 166, 168, 175, 185, and CI Pigment Yellow 150 derivative pigments; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 272; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; CI Pigment Green 7, 36, 58, 59; CI Pigment Brown 23, 25; CI Pigment Black 1, 7.

In addition, specific examples of the above-mentioned inorganic pigments include: titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow plum, zinc yellow, iron plum (iron oxide red (III)), cadmium red, ultramarine, Iron blue, chrome oxide green, cobalt green, umber, titanium black, synthetic iron black, carbon black, etc.

For example, when the color material dispersion of the present invention is used as the following photosensitive colored resin composition for color filters to form the pattern of the light-shielding layer on the substrate of the color filter, the light-shielding property is higher when blended in the ink The black pigment. As black pigments with high light-shielding properties, for example, inorganic pigments such as carbon black or triiron tetroxide, or organic pigments such as cyanine black can be used.

Examples of the above-mentioned dispersible dyes include dyes that can be dispersible by imparting various substituents to the dye or using it in combination with a solvent with low solubility. The salt-forming compound of the dye refers to a compound in which the dye forms a salt with an opposite ion. For example, a salt-forming compound of a basic dye and an acid, and a salt-forming compound of an acid dye and a base are included. The salting method is to dissolve the soluble dye in the solvent, and the lake pigment that is insoluble in the solvent. In the present invention, the dispersibility or dispersion stability of the color material can be improved by using a color material containing at least one selected from a dye and a salt-forming compound of the dye in combination with the above-mentioned dispersant of the present invention.

染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。再者，作為標準，只要相對於10g之溶劑(或混合溶劑)，染料之溶解量為10mg以下，則判定為該染料能夠於該溶劑(或混合溶劑)中分散。 As the above-mentioned dye, it can be suitably selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes,

Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc. Furthermore, as a standard, as long as the dissolved amount of the dye is 10 mg or less with respect to 10 g of the solvent (or mixed solvent), it is determined that the dye can be dispersed in the solvent (or mixed solvent).

Among them, the color material contains diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salts of these dyes. In the case of at least one of the group consisting of the compound, the effect of suppressing the sublimation or precipitation of the color material caused by the use of the above-mentioned dispersing agent is high, and a high-brightness colored layer can be formed. In addition, as the color material, it is preferable to contain at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone dyes.

As the diketopyrrolopyrrole pigment, for example, CI Pigment Red 254, 255, 264, 272, and the diketopyrrolopyrrole pigment represented by the following general formula (i) can be cited. Among them, it is preferably selected from CI Pigment Red 254 , 272, and in the following general formula (i), R ²¹ and R ²² are each at least one of 4-bromophenyl diketopyrrolopyrrole pigments.

(In the general formula (i), R ²¹ and R ²² are each independently 4-chlorophenyl or 4-bromophenyl)

As a quinophthalone pigment, C.I. Pigment Yellow 138 etc. are mentioned, for example. Examples of copper phthalocyanine pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, CI Pigment Green 7, 36, etc. It is CI Pigment Blue 15:6. As a zinc phthalocyanine pigment, C.I. Pigment Green 58, 59 etc. are mentioned, for example. Examples of the quinophthalone dye include: C.I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. Solvent Yellow 114, 157, etc. Among them, C.I. Disperse Yellow 54 is preferred.

As the average primary particle size of the color material used in the present invention, when it is used as the coloring layer of a color filter, it is not particularly limited as long as it can achieve the desired color development. The type of color material varies, preferably in the range of 10-100nm, more preferably 15-60nm. By setting the average primary particle size of the color material within the above range, a display device equipped with a color filter manufactured using the color material dispersion liquid of the present invention can be a high-contrast and high-quality display device.

In addition, the average dispersed particle diameter of the color material in the color material dispersion liquid also differs according to the type of color material used, and is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. The average dispersed particle diameter of the color material in the color material dispersion is the dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. For the measurement of particle size using a laser light scattering particle size distribution meter, the color material dispersion liquid can be appropriately diluted (for example, 1000 times, etc.) with the solvent used in the color material dispersion liquid to a concentration that can be measured by the laser light scattering particle size distribution meter , Use a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.) to measure by dynamic light scattering at 23°C. The average distribution particle size here is the volume average particle size.

The color material used in the present invention can be produced by a known method such as a recrystallization method and a solvent salt milling method. In addition, a commercially available color material can also be used by subjecting it to finer processing.

In the color material dispersion of the present invention, the content of the color material is not particularly limited. Regarding the content of the color material, in terms of dispersibility and dispersion stability, it is preferably 5 to 80 parts by mass, more preferably 8 to 100 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. Blended at a ratio of 70 parts by mass. Especially in the case of forming a coating film or a colored layer with a high color material concentration, relative to 100 parts by mass of the total solid content in the color material dispersion, it is preferably 30 to 80 parts by mass, more preferably 40 to 40 parts by mass. Blended at a ratio of 75 parts by mass.

<Solvent>

The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the color material dispersion liquid and can dissolve or disperse the same. A solvent can be used individually or in combination of 2 or more types. Specific examples of solvents include, for example, alcoholic solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxy Carbitol solvents such as ethyl alcohol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate , Ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate and other ester solvents; acetone, methyl ethyl Ketone solvents such as ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.; methoxy ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1- Glycol ether acetate solvents such as butyl acetate, 3-methoxy butyl acetate, and ethoxy ethyl acetate; methoxy ethoxy ethyl acetate, ethoxy ethoxy ethyl acetate, butyl Carbitol acetate solvents such as base carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, Glycol ether series such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether Solvents; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; Cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; aromatics such as toluene and xylene Organic solvents such as hydrocarbons. Among these solvents, in terms of solubility of other components, it is preferable to use glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol acetic acid in terms of solubility or coating suitability of other components. Ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxy butyl acetate More than species.

The color material dispersion of the present invention is preferably such that the above solvent is usually in the range of 55 to 95% by mass relative to the total amount of the color material dispersion containing the solvent, and preferably in the range of 65 to 90% by mass, and more It is preferably in the range of 70 to 88% by mass. If the solvent is too small, the viscosity will increase and the dispersibility will tend to decrease. In addition, if the solvent is too much, the concentration of the colored material decreases and it is difficult to achieve the target chromaticity coordinates.

<Other ingredients>

In the color material dispersion of the present invention, as long as the effect of the present invention is not impaired, a dispersion auxiliary resin and other components may be further formulated as needed. Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the following photosensitive colored resin composition for color filters. There are cases where the color material particles are not easily contacted by the steric hindrance of the alkali-soluble resin, and the dispersion stabilization or its dispersion stabilization effect has the effect of reducing the dispersant. In addition, as other components, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, defoaming agents, anti-shrinking agents, antioxidants, anti-cohesion agents, ultraviolet absorbers, etc. can be cited.

The color material dispersion of the present invention is used as a preliminary preparation for preparing the following photosensitive colored resin composition for color filters. In other words, the so-called color material dispersion refers to (the mass of the color material in the composition)/(the color material in the composition other than the color material in the composition) prepared in advance before the preparation of the photosensitive colored resin composition for the color filter below. The quality of solid content) is relatively high color material dispersion liquid. Specifically, the ratio of (mass of color material components in the composition)/(mass of solid components other than the color material components in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid with the following components, a photosensitive colored resin composition for color filters with excellent dispersibility can be prepared.

<Method for manufacturing color material dispersion>

In the present invention, if the method for producing the color material dispersion liquid is such that a color material dispersion liquid obtained by dispersing the color material in a solvent by the dispersant of the block copolymer or salt type block copolymer can be obtained The method is not particularly limited. Among them, in terms of excellent dispersibility and dispersion stability of the color material, it is preferably set to either of the following two production methods.

That is, the first production method of the color material dispersion of the present invention has the following steps: preparing a dispersant for the block copolymer or salt type block copolymer; and making the color material in the presence of the dispersant in a solvent dispersion.

In addition, the second method of producing the color material dispersion of the present invention when used as a dispersant for the salt-type block copolymer has the following steps: at the same time, the solvent, the block copolymer, the organic acid compound, etc., and the color material By mixing, at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) forms a salt with an organic acid compound, etc., while dispersing the color material.

In the case of using a salt-type block copolymer, according to the first manufacturing method described above, after the salt-type block copolymer is prepared, the salt-type block copolymer is used as a dispersant to disperse the color material, so that the color material can be dispersed accurately. It is preferable in this respect to confirm the reaction end point or reaction rate of the block copolymer and the organic acid compound before salt formation. In addition, according to the second manufacturing method described above, the color material is dispersed while preparing the dispersant for the salt-type block copolymer. Therefore, the salt-type block copolymer does not self-agglomerate, and the color material dispersion can be prepared efficiently. Can improve dispersion.

In the above-mentioned first manufacturing method and the above-mentioned second manufacturing method, the color material can be dispersed using a conventionally known dispersing machine. Specific examples of the dispersing machine include roller mills such as two-roll and three-roll mills, ball mills such as ball mills, vibrating ball mills, paint conditioners, continuous disc bead mills, continuous annular bead mills, and other bead mills. As a preferable dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03~3.0mm, more preferably 0.05~2.0mm.

Specifically, it can be exemplified by pre-dispersing with 2.0 mm zirconia beads with a relatively large bead diameter, and then performing formal dispersion with 0.1 mm zirconia beads with a relatively small bead diameter. Furthermore, after dispersion, it is preferable to filter with a filter of 0.5 to 2 μm.

II. Photosensitive colored resin composition for color filters

The photosensitive colored resin composition for a color filter of the present invention is characterized by containing the color material dispersion liquid of the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. The photosensitive colored resin composition for color filters of the present invention can form a high-brightness colored layer by using the color material dispersion liquid of the present invention, and can suppress cracks in the ITO film formed adjacent to the colored layer.

The photosensitive colored resin composition for a color filter of the present invention contains at least a color material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and can be further used within a range that does not impair the effects of the present invention. Contains other ingredients. Hereinafter, the components contained in the photosensitive colored resin composition for color filters of the present invention will be described. The dispersant, color material, and solvent are the same as those described in the color material dispersion liquid of the present invention. , So the description here is omitted.

<Alkali-soluble resin>

The alkali-soluble resin in the present invention has an acidic group, functions as a binder resin, and can be appropriately selected and used from those that are soluble in the alkaline developer used for pattern formation. In the present invention, the so-called alkali-soluble resin may have an acid value of 40 mgKOH/g or more as a standard. Preferred alkali-soluble resins in the present invention are resins having acidic groups and usually having carboxyl groups. Specifically, acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups, Epoxy (meth)acrylate resin with carboxyl group, etc. Among these, particularly preferable ones are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. The reason is that the film strength of the formed cured film is improved by containing the photopolymerizable functional group. In addition, acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination of two or more types.

Acrylic resins such as acrylic copolymers containing structural units having a carboxyl group and styrene-acrylic copolymers having a carboxyl group are, for example, carboxyl-containing ethylenically unsaturated monomers that can be copolymerized by a known method. A (co)polymer obtained by (co)polymerizing other polymerized monomers. Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, and itaconic acid. Acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, ω- Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as the carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.

烷、三環[5.2.1.0(2,6)]癸烷(二環戊烷)、金剛烷等脂肪族烴環；苯、萘、蒽、菲、茀等芳香族環；聯苯、聯三苯、二苯基甲烷、三苯基甲烷、茋等鏈狀多環或下述化學式(ii)所示之Cardo構造等。 In terms of excellent adhesion of the colored layer, the alkali-soluble resin preferably further has a hydrocarbon ring. It was found that the coloring layer obtained has solvent resistance due to the hydrocarbon ring as a bulky group in the alkali-soluble resin, and especially the swelling of the coloring layer can be suppressed. Although the effect is not clear, it is inferred that the coloring layer contains a large hydrocarbon ring and inhibits the movement of molecules in the coloring layer. As a result, the strength of the coating film becomes higher and the swelling caused by the solvent is suppressed. Examples of such a hydrocarbon ring include a cycloaliphatic hydrocarbon ring that may have a substituent, an aromatic ring that may have a substituent, and combinations of these. The hydrocarbon ring may also have a carbonyl group, a carboxyl group, an oxycarbonyl group, and an amide group. Substituents such as groups. Among them, in the case of containing an aliphatic ring, the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved. Specific examples of the hydrocarbon ring include: cyclopropane, cyclobutane, cyclopentane, cyclohexane,

Alkanes, tricyclic [5.2.1.0(2,6)] decane (dicyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, sulphur and other aromatic rings; biphenyl, dicyclopentane Chain polycyclic rings such as benzene, diphenylmethane, triphenylmethane, stilbene, or the Cardo structure shown in the following chemical formula (ii), etc.

In addition, the alkali-soluble resin also preferably has a maleimide structure represented by the following general formula (iii).

(In the general formula (iii), R ^M is a substituted hydrocarbon ring.)

When the alkali-soluble resin has the maleimide structure represented by the above general formula (iii), since the hydrocarbon ring has a nitrogen atom, it has excellent compatibility with the dispersant of the present invention and suppresses development residue The effect is improved. ^{As specific examples of the hydrocarbon ring which may be substituted in R M} of the above general formula (iii), the same as the specific examples of the above hydrocarbon ring can be cited.

In the case of containing an aliphatic ring as a hydrocarbon ring, the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved, which is preferable in this respect. In addition, when the Cardo structure represented by the above chemical formula (ii) is included, the hardenability of the colored layer is improved, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable in this respect.

酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯等，就於加熱處理中亦維持顯影後之著色層之剖面形狀之效果較大之方面而言，較佳為(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯，尤佳為苯乙烯。又，就顯影殘渣之抑制效果之方面而言，作為上述具有烴環之乙烯系不飽和單體，較佳為具有上述順丁烯二醯亞胺構造之單體，較佳為苯乙烯，尤佳為苯乙烯。 In the alkali-soluble resin used in the present invention, the use of an acrylic copolymer containing the structural unit having the above-mentioned hydrocarbon ring different from the structural unit having a carboxyl group makes it easy to adjust the amount of each structural unit and increase the amount of the structural unit having the above-mentioned hydrocarbon ring. It is easy to improve the function of the constituent unit, which is preferable in this respect. The acrylic copolymer containing a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other monomer capable of copolymerization". As the above-mentioned ethylenically unsaturated monomer having a hydrocarbon ring, for example, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, (meth) Acrylic Iso

Ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., are more effective in maintaining the cross-sectional shape of the colored layer after development during heat treatment. Preferred are cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, Styrene is particularly preferably styrene. Also, in terms of the effect of suppressing development residues, as the above-mentioned ethylenically unsaturated monomer having a hydrocarbon ring, a monomer having the above-mentioned maleimide structure is preferred, and styrene is preferred, and particularly It is preferably styrene.

In addition, the alkali-soluble resin used in the present invention preferably has an ethylene-based double bond in the side chain. In the case of having an ethylene-based double bond, the alkali-soluble resin and the dispersant of the present invention can form a cross-linked bond during the curing step of the resin composition when the color filter is manufactured, and the alkali-soluble resin is mutually Or the alkali-soluble resin and the photopolymerizable compound may form a crosslinked bond. Therefore, if an alkali-soluble resin having an ethylene-based double bond in the side chain is used in combination with the dispersant of the present invention, the film strength of the cured film will be further improved by a synergistic effect, and the brightness of the colored layer and ITO can be further improved The cracking property of the film further improves the development resistance, and the heat shrinkage of the cured film is suppressed to make it excellent in adhesion to the substrate. The method of introducing the ethylene-based double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a compound having an epoxy group and a vinyl double bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of an alkali-soluble resin, and the vinyl group is introduced into the side chain. Double bond method; or introduce the structural unit with hydroxyl group into the copolymer in advance, make it add to the compound with isocyanate group and ethylene double bond in the molecule, and introduce ethylene double bond to the side chain The method and so on.

The alkali-soluble resin used in the present invention may further contain other structural units such as methyl (meth)acrylate, ethyl (meth)acrylate, etc., structural units having an ester group. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the photosensitive colored resin composition for color filters, but also functions as a component that improves solubility in solvents and further improves solvent resolubility.

The alkali-soluble resin used in the present invention preferably includes acrylic resins such as acrylic copolymers and styrene-acrylic copolymers containing structural units having a carboxyl group and structural units having a hydrocarbon ring, and more preferably includes a structure having a carboxyl group Acrylic resins such as units, structural units having a hydrocarbon ring, and structural units having a vinyl double bond, and acrylic resins such as styrene-acrylic copolymers.

The alkali-soluble resin can be made into an alkali-soluble resin with desired performance by appropriately adjusting the feeding amount of each constituent unit.

In terms of obtaining a good pattern, the feeding amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, and more preferably 10% by mass or more with respect to the total amount of monomers. On the other hand, in terms of suppressing film roughness on the pattern surface after development, etc., the feeding amount of the carboxyl-containing ethylenic unsaturated monomer is preferably 50% by mass or less relative to the total amount of monomers, and more preferably It is 40% by mass or less. If the ratio of the carboxyl group-containing ethylenically unsaturated monomer is more than the above lower limit, the obtained coating film will have sufficient solubility in alkaline developer, and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is When the value is below the above upper limit, it tends to be difficult to cause the formed pattern to fall off from the substrate or the film on the surface of the pattern is rough during development using an alkaline developer.

In addition, in acrylic resins such as acrylic copolymers and styrene-acrylic copolymers containing structural units having ethylenic double bonds, which are more preferably used as alkali-soluble resins, they have both epoxy groups and vinyl double bonds. The compound of the bond is preferably 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass relative to the feeding amount of the carboxyl-containing ethylenically unsaturated monomer.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. If it is less than 1,000, the adhesive function after curing may be significantly reduced, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer. Furthermore, the above-mentioned weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, and it is preferably an epoxy (meth)acrylic acid obtained by reacting a reactant of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride Ester compound. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, respectively, and may use 2 or more types together.

Regarding the alkali-soluble resin, it is preferable to select one having an acid value of 50 mgKOH/g or more in terms of the developability (solubility) of the alkaline aqueous solution used in the developer. Regarding the alkali-soluble resin, it is preferable that the acid value is 70 mgKOH/g or more and 300 mgKOH/g in terms of the developability (solubility) to the alkaline aqueous solution used in the developer and the adhesion to the substrate. Hereinafter, among them, it is preferably 70 mgKOH/g or more and 280 mgKOH/g or less. Furthermore, the acid value of the alkali-soluble resin can be measured in accordance with JIS K 0070:1992.

In terms of the effect of improving the film strength of the cured film and improving the development resistance, and the excellent adhesion to the substrate, the equivalent of the ethylenic unsaturated bond when the side chain of the alkali-soluble resin has an ethylenic unsaturated group It is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. If the ethylene-based unsaturated bond equivalent is 100 or more, the development resistance or adhesion is excellent. In addition, if it is 2000 or less, the ratio of other structural units such as the structural unit having a carboxyl group or the structural unit having a hydrocarbon ring can be relatively increased, and therefore the developability and heat resistance are excellent. In addition, in terms of the excellent synergistic effect when combined with the above-mentioned dispersing agent, further improving the brightness of the colored layer and the ITO crack resistance, the above-mentioned dispersing agent is preferably the one in the block copolymer before salt formation. The (meth)acrylic acid group equivalent contained in the side chain is in the above-mentioned preferable range, and the ethylene-based unsaturated bond equivalent of the alkali-soluble resin is in the above-mentioned preferable range. Here, the ethylene-based unsaturated bond equivalent is the weight average molecular weight per mole of the ethylene-based unsaturated bond in the alkali-soluble resin, and is represented by the following formula (2).

Formula (2) Ethylene unsaturated bond equivalent (g/mol)=W(g)/M(mol)

(In the formula (2), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylene double bond contained in the alkali-soluble resin W(g))

The above-mentioned ethylene-based unsaturated bond equivalent can also be calculated by measuring the number of ethylene-based double bonds per 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992, for example.

The alkali-soluble resin used in the photosensitive colored resin composition for color filters may be used singly or in combination of two or more. There is no particular limitation on the content thereof. Compared to photosensitive color filters for color filters, the alkali-soluble resin may be used alone or in combination. The total amount of solid content of the colored resin composition, the alkali-soluble resin is preferably 5% by mass to 60% by mass, and more preferably in the range of 10% by mass to 40% by mass. If the content of the alkali-soluble resin is more than the above lower limit, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is less than the above upper limit, film roughness or pattern defects can be suppressed during development.

<Multifunctional monomer>

The polyfunctional monomer used in the photosensitive colored resin composition for color filters is not particularly limited as long as it can be polymerized by the following photoinitiator. Generally, an ethylene-based monomer having two or more monomers is used. The compound with an unsaturated double bond is particularly preferably a multifunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups. As such a polyfunctional (meth)acrylate, what is necessary is just to select it suitably from a well-known well-known thing, and use. As a specific example, for example, those described in JP 2013-029832 A, etc. can be cited.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the photosensitive colored resin composition for color filters of the present invention is required to have excellent photocuring properties (high sensitivity), it is preferable that the multifunctional monomer has three (trifunctional) or more polymerizable monomers. Double bonds are preferably poly(meth)acrylates of trivalent or higher polyols or their dicarboxylic acid modifiers. Specifically, trimethylolpropane tri(meth)acrylic acid is preferred Esters, pentaerythritol tri(meth)acrylate, succinic acid modification product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate ) Acrylate, succinic acid modification of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. The content of the above-mentioned polyfunctional monomer used in the photosensitive colored resin composition for color filters is not particularly limited, and the polyfunctional monofunctional monomer is relative to the total solid content of the photosensitive colored resin composition for color filters. The body is preferably 5-60% by mass, and more preferably within the range of 10-40% by mass. If the content of the multifunctional monomer is less than the above lower limit, the photocuring cannot be carried out sufficiently, and the exposed part may be eluted during development, and if the content of the multifunctional monomer is more than the above upper limit, there will be The alkali developability may decrease.

<Photoinitiator>

二唑化合物、α-胺基酮、聯咪唑類、N,N-二甲胺基二苯甲酮、鹵甲基-S-三

系化合物、9-氧硫

等。作為光起始劑之具體例，可列舉：二苯甲酮、4,4'-雙二乙胺基二苯甲酮、4-甲氧基-4'-二甲胺基二苯甲酮等芳香族酮類、安息香甲醚等安息香醚類、乙基安息香等安息香、2-(鄰氯苯基)-4,5-苯基咪唑二聚物等雙咪唑類、2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-

二唑等鹵甲基

二唑化合物、2-(4-丁氧基-萘-1-基)-4,6-雙-三氯甲基-S-三

等鹵甲基-S-三

系化合物、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-

啉基丙酮、1,2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁酮-1,1-羥基-環己基-苯基酮、二苯基乙二酮、苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯硫醚、聯苯醯二甲基縮酮、二甲胺基苯甲酸酯、對二甲胺基苯甲酸異戊酯、2-正丁氧基乙基-4-二甲胺基苯甲酸酯、2-氯-9-氧硫

、2,4-二乙基-9-氧硫

、2,4-二甲基-9-氧硫

、異丙基-9-氧硫

、4-苯甲醯基-甲基二苯硫醚、1-羥基-環己基-苯基酮、2-苄基-2-(二甲胺基)-1-[4-(4-

啉基)苯基]-1-丁酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮、α-二甲氧基-α-苯基苯乙酮、苯基 雙(2,4,6-三甲基苯甲醯基)氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-(4-

啉基)-1-丙酮等。其中，較佳為使用2-甲基-1-[4-(甲硫基)苯基]-2-

啉基丙烷-1-酮、2-苄基-2-(二甲胺基)-1-(4-

啉基苯基)-1-丁酮、4,4'-雙(二乙胺基)二苯甲酮、二乙基-9-氧硫

。進而，就感度調整、抑制滲水、提高耐顯影性之方面而言，較佳為將如2-甲基-1-[4-(甲硫基)苯基]-2-

啉基丙烷-1-酮之α-胺基苯乙酮系起始劑與如二乙基-9-氧硫

之9-氧硫

系起始劑組合。使用α-胺基苯乙酮系起始劑與9-氧硫

系起始劑之情況下之該等之合計含量相對於著色樹脂組成物之固形物成分總量，較佳為5質量%~15質量%。若起始劑量為15質量%以下，則製造製程中之昇華物減少，因此較佳。若起始劑量為5質量%以上，則滲水等耐顯影性提高。 The photoinitiator used in the colored resin composition for the color filter of the present invention is not particularly limited, and it can be used alone or in combination of two or more of various known initiators. Examples of photoinitiators include aromatic ketones, benzoin ethers, and halomethyl

Diazole compounds, α-amino ketones, biimidazoles, N,N-dimethylamino benzophenone, halomethyl-S-tri

Series compounds, 9-oxysulfur

Wait. Specific examples of the photoinitiator include benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Aromatic ketones, benzoin ethers such as methyl benzoin, benzoin such as ethyl benzoin, bisimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-trichloromethyl- 5-(p-methoxystyryl)-1,3,4-

Halomethyl

Diazole compound, 2-(4-butoxy-naphthalene-1-yl)-4,6-bis-trichloromethyl-S-tri

Isohalomethyl-S-tri

Series compound, 2,2-Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-

Alkylacetone, 1,2-benzyl-2-dimethylamino-1-(4-

(Hydroxyphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, diphenyl ethylenedione, benzyl benzoic acid, benzyl benzoic acid, methyl benzyl benzoate, 4-benzyl- 4'-Methyl diphenyl sulfide, biphenyl dimethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4- Dimethylaminobenzoate, 2-chloro-9-oxysulfur

, 2,4-Diethyl-9-oxysulfur

, 2,4-Dimethyl-9-oxysulfur

, Isopropyl-9-oxysulfur

, 4-Benzyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-

Linyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

(Hydroxy)phenyl)-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzyl) phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4-

(Alpinyl)-1-acetone and the like. Among them, it is preferable to use 2-methyl-1-[4-(methylthio)phenyl]-2-

Linylpropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-

(Hydroxyphenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, diethyl-9-oxysulfur

. Furthermore, in terms of sensitivity adjustment, suppression of water seepage, and improvement of development resistance, it is preferable to use 2-methyl-1-[4-(methylthio)phenyl]-2-

Alpha-aminoacetophenone initiators of hydroxypropane-1-one and diethyl-9-oxysulfur

Of 9-oxysulfur

Department of initiator combination. Using α-aminoacetophenone-based initiator and 9-oxysulfur

In the case of the initiator, the total content of these is preferably 5% by mass to 15% by mass relative to the total solid content of the colored resin composition. If the starting dose is 15% by mass or less, the sublimation in the manufacturing process is reduced, which is preferable. If the starting dose is 5% by mass or more, the development resistance such as water penetration improves.

In the present invention, the photoinitiator preferably contains an oxime ester-based photoinitiator in terms of improving sensitivity. In addition, by using the oxime ester-based photoinitiator, the unevenness of the line width in the plane can be easily suppressed when the thin line pattern is formed. Furthermore, by using an oxime ester-based photoinitiator, there is a tendency that the residual film rate is increased and the effect of suppressing water seepage generation is improved. Furthermore, the so-called water seepage means that if a component that improves alkali developability is used, it will produce traces such as water seepage after being rinsed with pure water after alkali development. This kind of water seepage disappears after post-baking, so there is no problem as a product, but it will be detected as an uneven abnormality in the appearance inspection of the patterned surface after development, causing a problem that normal products and abnormal products cannot be distinguished. Therefore, if the inspection sensitivity of the inspection device is lowered during the appearance inspection, it will result in a decrease in the yield of the final color filter product, which becomes a problem. As the oxime ester-based photoinitiator, in terms of reducing pollution of the colored resin composition for color filters or device pollution caused by decomposition products, those having an aromatic ring are preferred, and those having an aromatic ring are more preferred. Those having a condensed ring containing an aromatic ring further preferably have a condensed ring containing a benzene ring and a heterocyclic ring. As the oxime ester-based photoinitiator, it can be selected from 1,2-octanedione-1-[4-(phenylthio)-, 2-(O-benzyloxime)], ethyl ketone, 1-[ 9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-, 1-(O-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, Among the oxime ester-based photoinitiators described in JP 2001-233842, JP 2010-527339, JP 2010-527338, JP 2013-041153, etc., are appropriately selected. As commercially available products, Irgacure OXE-01, Adeka Arkls NCI-930 with a diphenyl sulfide skeleton, TR-PBG-345, TR-PBG-304 with a carbazole skeleton, and TR- with a pyridine skeleton can also be used. PBG-365, TR-PBG-3057 with a diphenyl sulfide skeleton (the above are manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), etc. Particularly in terms of brightness, it is preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a sulphur skeleton. Moreover, in terms of high sensitivity, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton. In addition, the combined use of two or more oxime ester-based photoinitiators is preferable in that it is easy to improve the brightness, the residual film rate, and the effect of suppressing the occurrence of water seepage is high. In particular, in terms of high brightness and high heat resistance, it is preferable to use two kinds of oxime ester photoinitiators having a diphenyl sulfide skeleton in combination or to use an oxime ester photoinitiator having a diphenyl sulfide skeleton in combination. Starter and oxime ester-based photoinitiator with citron skeleton. In addition, in terms of excellent sensitivity and brightness, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having a pyridine skeleton or an oxime ester photoinitiator having a diphenyl sulfide in combination. Light initiator.

啉基丙烷-1-酮(例如Irgacure907， BASF公司製造)、2-苄基-2-(二甲胺基)-1-(4-

啉基苯基)-1-丁酮(例如Irgacure369，BASF公司製造)、4,4'-雙(二乙胺基)二苯甲酮(例如HiCure ABP，川口藥品製造)等。又，對肟酯系光起始劑組合9-氧硫

系起始劑就感度調整、抑制滲水、提高耐顯影性之方面而言較佳，將2種以上之肟酯系光起始劑與9-氧硫

系起始劑組合就提高亮度、殘膜率、容易進行感度調整、抑制滲水產生之效果較高及提高耐顯影性之方面而言較佳。 Moreover, in terms of suppressing water seepage and improving sensitivity, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester-based photoinitiator. The reason is that a photoinitiator with a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, so free radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. As a commercially available product of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-

Alkylpropan-1-one (for example, Irgacure907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-

(Alolinylphenyl)-1-butanone (for example, Irgacure369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)benzophenone (for example, HiCure ABP, manufactured by Kawaguchi Pharmaceutical), and the like. In addition, 9-oxysulfur is combined with oxime ester-based photoinitiator

The initiator is preferable in terms of sensitivity adjustment, suppression of water seepage, and improvement of development resistance. Two or more oxime ester-based photoinitiators and 9-oxysulfur

The combination of initiators is preferable in terms of improving brightness, residual film rate, easy adjustment of sensitivity, high effect of suppressing water seepage, and improvement of development resistance.

The content of the photoinitiator used in the colored resin composition for color filters of the present invention is generally 0.01 to 100 parts by mass, preferably 5 parts by mass, relative to 100 parts by mass of the above-mentioned multifunctional monomer ~60 parts by mass. If the content is more than the above lower limit, the photohardening is sufficiently performed and the exposed part is prevented from eluting during development. On the other hand, if the content is less than the above upper limit, the yellowing of the obtained colored layer can be suppressed from becoming weak. The resulting brightness decreases. In addition, as the photoinitiator used in the colored resin composition for color filters of the present invention, the total content of two or more oxime ester-based photoinitiators is relative to the solid state of the colored resin composition for color filters It is preferable that the total amount of the material components is within the range of 0.1% by mass to 12.0% by mass, and more preferably 1.0% by mass to 8.0% by mass, in terms of sufficiently exhibiting the effect of the combined use of the photoinitiators.

Regarding the binder components used in the colored resin composition for color filters of the present invention, the total content of these relative to the total solid content of the colored resin composition for color filters is preferably 35% by mass~ 97% by mass, more preferably blended at a ratio of 40% to 96% by mass. If it is more than the above lower limit, a colored layer having excellent hardness and adhesion to the substrate can be obtained. In addition, if it is less than the above upper limit value, the developability is excellent, and the generation of fine wrinkles due to thermal shrinkage is also suppressed.

<Antioxidant>

The photosensitive colored resin composition for a color filter of the present invention further contains an antioxidant in terms of improving heat resistance, suppressing color fading of the color material, and improving brightness. What is necessary is just to select an antioxidant suitably from a well-known thing. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. In terms of heat resistance, it is preferable to use Hindered phenolic antioxidants. It can also be a latent antioxidant as described in International Publication No. 2014/021023.

Examples of hindered phenol-based antioxidants include: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation), 1, 3,5-Tris(3,5-Di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3 ,5-Di-tert-butylbenzyl) mesitylene (trade name: IRGANOX1330, 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: IRGANOX1081, manufactured by BASF), 3,5-di-tert-butyl Diethyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF) and the like. Among them, in terms of heat resistance and light resistance, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, BASF Corporation manufacture).

If the photosensitive colored resin composition for a color filter of the present invention contains the above-mentioned oxime ester-based photoinitiator and antioxidant in combination, the synergistic effect will increase the brightness and increase the residual film rate. It is preferable in terms of the linearity is further improved when the thin line pattern is formed, or the ability to form the thin line pattern like the design of the mask line width is improved.

As the compounding amount of the antioxidant, relative to 100 parts by mass of the total solid content in the colored resin composition, the antioxidant is preferably 0.1 parts by mass to 10.0 parts by mass, more preferably 0.5 parts by mass to 5.0 parts by mass. If it is more than the said lower limit, it will be excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

When an antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, as the blending amount of the antioxidant, relative to 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator, the antioxidant is preferably 1 mass Parts to 250 parts by mass, more preferably 3 parts by mass to 80 parts by mass, and still more preferably 5 parts by mass to 45 parts by mass. If it is in the above range, the effect of the above combination is excellent.

<Optional ingredients>

In the photosensitive colored resin composition for color filters of the present invention, in addition to the above-mentioned antioxidant, various additives may be contained as needed. Examples of additives include polymerization terminator, chain transfer agent, leveling agent, plasticizer, surfactant, defoamer, silane coupling agent, ultraviolet absorber, adhesion promoter, and the like. As a specific example of a surfactant and a plasticizer, what is described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned, for example.

Moreover, as the silane coupling agent, for example, 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 Silicones), etc. Among them, in terms of the adhesiveness of the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having a methacryl group and an acrylic group are preferable.

As the content of the silane coupling agent, relative to 100 parts by mass of the total solid content in the photosensitive colored resin composition, the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass. Parts by mass or less. If it is more than the said lower limit and less than the said upper limit, the board|substrate adhesiveness will be excellent.

<The blending ratio of the components in the photosensitive colored resin composition for color filters>

The total content of the color materials is preferably 3 to 65% by mass, more preferably 4 to 60% by mass relative to the total solid content of the photosensitive colored resin composition for color filters. If it is more than the above lower limit, the colored layer has sufficient color density when the photosensitive colored resin composition for color filters is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). Moreover, if it is less than the said upper limit, the coloring layer which is excellent in storage stability and has sufficient hardness or has adhesiveness with a board|substrate can be obtained. Especially in the case of forming a coloring layer with a high color material concentration, the content of the color material relative to the total solid content of the photosensitive coloring resin composition for color filters is preferably 15-65% by mass, and more It is better to mix at a ratio of 25-60% by mass. In addition, the content of the dispersant is not particularly limited as long as it can uniformly disperse the color material. For example, it can be 1-40 mass relative to the total solid content of the photosensitive colored resin composition for color filters. The ratio of% is used. Furthermore, it is preferable to mix|blend at the ratio of 2-30 mass% with respect to the total amount of the solid content of the photosensitive colored resin composition for color filters, and it is especially preferable to mix it at the ratio of 3-25 mass %. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of the photosensitive colored resin composition for color filters will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a coloring layer with a high color material concentration, the content of the dispersant relative to the total solid content of the photosensitive color resin composition for color filters is preferably 2-25% by mass, more It is better to mix with a ratio of 3-20% by mass. Furthermore, in the case of a salt-type block copolymer, the mass of the dispersant is the total mass of the block copolymer and the organic acid compound, etc. before the salt is formed. In addition, the content of the solvent may be appropriately set within a range in which the colored layer can be formed accurately. The total amount of the photosensitive colored resin composition for color filters containing the solvent is generally preferably in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass. By making the content of the above-mentioned solvent within the above-mentioned range, it is possible to have excellent coatability.

<Manufacturing Method of Photosensitive Colored Resin Composition for Color Filter>

The method for producing the photosensitive colored resin composition for color filters of the present invention is not particularly limited. For example, it can be achieved by adding alkali-soluble resin, polyfunctional monomer, photoinitiator, and the above-mentioned color material dispersion of the present invention. It can be obtained by mixing other ingredients as needed and using a well-known mixing method.

III. Color filter

The color filter of the present invention is provided with at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a cured product of the photosensitive coloring resin composition for a color filter of the present invention.

The color filter of 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 coloring layer 3.

<Colored layer>

At least one of the colored layers used in the color filter of the present invention is the colored layer of the cured product of the photosensitive colored resin composition for the color filter of the present invention. The colored layer is usually formed in the opening of the light-shielding portion on the following substrate, and usually contains a colored pattern of more than three colors. In addition, the arrangement of the colored layer is not particularly limited, and it can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type. In addition, the width and area of the colored layer can be set arbitrarily. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the photosensitive colored resin composition for color filters, and the like, and it is usually preferably in the range of 1 to 5 μm.

This colored layer can be formed by the following method, for example. First, use spray coating, dip coating, bar coating, roll coating, spin coating, die nozzle coating and other coating methods to color the above-mentioned photosensitive color filter of the present invention. The resin composition is applied on the following substrate to form a wet coating film. Among them, the spin coating method and the die nozzle coating method can be preferably used. Then, after the wet coating film is dried using a hot plate, an oven, etc., it is exposed through a mask of a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, etc. are subjected to a photopolymerization reaction to form a cured coating film. As a light source used for exposure, ultraviolet rays, electron beams, etc., such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, can be mentioned, for example. The amount of exposure is appropriately adjusted according to the light source used or the thickness of the coating film. In addition, in order to promote the polymerization reaction after exposure, heat treatment may also be performed. The heating conditions are appropriately selected according to the blending ratio of the components in the photosensitive colored resin composition for color filters used, the thickness of the coating film, and the like.

Next, by performing a development process with a developer, the unexposed part is dissolved and removed, and a coating film is formed in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. It is also possible to add an appropriate amount of surfactants and the like to the alkaline solution. In addition, general methods can be used for the development method. After the development process, the developer is usually washed, and the cured coating film of the photosensitive colored resin composition for color filters is dried to form a colored layer. In addition, after the development treatment, heat treatment may be performed in order to sufficiently harden the coating film. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

<Shading part>

The light-shielding part in the color filter of the present invention is formed in a pattern on the following substrate, which can be the same as the light-shielding part in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and examples include shapes such as a stripe shape and a matrix shape. The light-shielding part may also be a metal thin film such as chromium obtained by a sputtering method, a vacuum vapor 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, and organic pigments in a resin adhesive. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, and a photosensitive resist. Methods of thermal transfer, etc.

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

<Substrate>

As the substrate, it is used for the following transparent substrates, silicon substrates, and those having aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the transparent substrates or silicon substrates. Other color filter layers, resin layers, transistors such as TFTs, circuits, etc. can also be formed on these substrates. The transparent substrate of the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for general color filters can be used. Specifically, examples include: non-flexible transparent rigid materials such as quartz glass, alkali-free glass, synthetic quartz plates, or transparent resin films, optical resin plates, flexible glass, and other flexible transparent and flexible materials Sex material. The thickness of the transparent substrate is not particularly limited, and according to the use of the color filter of the present invention, for example, about 100 μm to 1 mm can be used. Furthermore, the color filter of the present invention may also be formed with, for example, an overcoat layer or a transparent electrode layer, and further an alignment film or columnar spacers, etc., besides the above-mentioned substrate, light-shielding portion, and coloring layer.

IV. Display device

The display device of the present invention is characterized by having the above-mentioned color filter of the present invention. In the present invention, the structure of the display device is not particularly limited, and it can be appropriately selected from conventionally known display devices. For example, a liquid crystal display device or an organic light-emitting display device can be cited.

[Liquid crystal display device]

Examples of the liquid crystal display device of the present invention include a liquid crystal display device having the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. The 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 liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a liquid crystal layer formed between the color filter 10 and the counter substrate 20 30. In addition, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2 and may be a configuration generally known as a liquid crystal display device using a color filter.

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. As such a driving method, for example, a twisted nematic (TN, Twisted Nematic) method, a lateral electric field effect display technology (IPS, In-plane Switching) method, an optically compensated birefringence (OCB, Optically Compensated Birefringence) method, and more Domain vertical alignment (MVA, Multi-Domain Vertical Alignment) method, etc. In the present invention, any of these methods can be preferably used. In addition, as the counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method of forming the liquid crystal layer, a method generally used as a method of producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method or a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, by slowly cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.

[Organic Light Emitting Display Device]

As the organic light-emitting display device of the present invention, for example, an organic light-emitting display device having the above-mentioned color filter and organic light-emitting body of the present invention can be cited. 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 an example of the organic light emitting display device of the present invention. As shown 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. It is also possible to have an organic protective layer 50 or an inorganic oxide film 60 between the color filter 10 and the organic light-emitting body 80.

As a layering method of the organic light-emitting body 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; or a method of attaching an organic light-emitting body 80 formed on another substrate to an inorganic oxide film 60, etc. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light-emitting body 80, and other configurations can be appropriately used known ones. The organic light-emitting display device 100 fabricated in this way can be applied to, for example, an organic EL display in a passive driving mode, and can also be applied to an organic EL display in an active driving mode. Furthermore, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a configuration generally known as an organic light-emitting display device using color filters.

[Example]

Hereinafter, the present invention will be explained in detail with examples. The present invention is not limited by these descriptions. The acid value of the block copolymer before salt formation, and the acid value of the salt-type block copolymer formed by the compound represented by the general formula (2) described above are described in accordance with JIS K 0070:1992 Method by method. The amine value of the block copolymer before salt formation, and the amine value of the salt-type block copolymer formed by the compound represented by the above general formula (2) as the salt is based on JIS K 7237: 1995 Method by method. The hydroxyl value of the block copolymer before and after salt formation is obtained by a method based on the method described in JIS K 0070:1992. The weight-average molecular weight (Mw) of the block copolymer before salt formation is determined by GPC (gel permeation chromatography) as a standard polystyrene conversion value in accordance with the above-mentioned measuring method of the present invention.

(Example 1: Synthesis of salt type block copolymer A-1)

250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed four-neck separable flask equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and nitrogen substitution was carried out sufficiently. 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 part by mass of methyl isobutyrate were injected using a syringe. Using the addition funnel, the monomers for the B block were added dropwise over a period of 60 minutes with 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 12.1 parts by mass of 2-ethylhexyl methacrylate (EHMA), and A 12.9 parts by mass of n-butyl acrylate (BMA), 9.0 parts by mass of benzyl methacrylate (BzMA), 16.6 parts by mass of methyl methacrylate (MMA), and 17.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA) . After 30 minutes, 25.3 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane and filtered, purified by vacuum drying, and diluted with PGMEA to prepare a 30% by mass solution of solid content. 32.5 parts by mass of water was added, the temperature was raised to 100°C, and the reaction was carried out for 7 hours to deprotect the structural unit derived from EEMA to prepare the structural unit derived from methacrylic acid (MAA). The obtained block copolymer A-1" PGMEA solution was reprecipitated in hexane and filtered, and purified by vacuum drying. The purified block copolymer A-1" was re-dissolved in 400 parts by mass of PGMEA , Add isocyanate A (2-isocyanatoethyl methacrylate, trade name: Karenz MOI, manufactured by Showa Denko) 5.3 parts by mass, dibutyltin (trade name: Neostann U-100, manufactured by Nitto Kasei Co., Ltd.) 0.008 Parts by mass, heated to 80°C and reacted for 2 hours to obtain an A block containing the structural unit represented by the general formula (I), and the constituent unit represented by the general formula (B1) and derived from a carboxyl group-containing monomer The B block copolymer A-1' solution (solid content 20% by mass) of the constituent unit.

50 parts by mass of the obtained block copolymer A-1' solution was added to a 100 mL round-bottom flask, and 1.27 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) as the compound represented by the above general formula (3) was added (PPA is 0.5 mol with respect to 1 mol of DMMA unit of block copolymer A-1'), stirred at a reaction temperature of 30°C for 20 hours, thereby obtaining a salt-type block copolymer with a solid content of 20% by mass A-1 solution. The acid value of the salt-type block copolymer A-1 after the salt formation is the same as the block copolymer A-1′ before the salt formation, and the amine value after the salt formation is specifically calculated as follows. Add 1g of a solution of 9 parts by mass of salt-type block copolymer A-1 (solid after reprecipitation) and 191 parts by mass of deuterated chloroform-D for NMR in the NMR sample tube, and use a nuclear magnetic resonance device ( Made by JEOL, FT NMR, JNM-AL400), 13C-NMR spectrum was measured under the conditions of room temperature and cumulative times of 10,000 times. The obtained spectrum data is calculated based on the ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom that does not undergo salt formation at the terminal nitrogen site (amine group) and the peak of the carbon atom adjacent to the nitrogen atom undergoing salt formation The ratio of the number of amine groups for salt formation to the total number of amine groups was confirmed to be the same as the theoretical salt formation ratio (all phenylphosphonic acids form a salt with the nitrogen site at the end of the DMMA of the block copolymer A-1').

(Examples 2~14: Synthesis of salt block copolymers A-2~A-14)

In Example 1, the A block material was changed to the content shown in Table 1, and the B block material was changed to the type and content shown in Table 1. Otherwise, the same as the salt type of Example 1 In the same way as block copolymer A-1, solutions of salt type block copolymers A-2 to A-14 were obtained. Furthermore, 1-ethoxyethyl methacrylate (EEMA) uses the same molar amount as the MAA in Table 1. In addition, in Table 1, the amount of the organic acid compound or halogenated hydrocarbon used as the salt-forming compound is 1 mol of the above compound relative to the nitrogen site (DMMA) of the structural unit represented by the general formula (I) The number of moles said. In addition, in Example 2, the purified block copolymer A-1" was dissolved again in 400 parts by mass of PGMEA, and isocyanate B (methacrylic acid 2-(0-[1'-methylpropylene amine Carboxylamino) ethyl ester, Karenz MOI-BM, manufactured by Showa Denko) 12.0 parts by mass, 0.01 parts by mass of dibutyltin dilaurate, heated at 130°C for 2 hours, thereby obtaining a compound having the general formula (I) The A block of the structural unit represented by the formula (B1) and the block copolymer A-2' solution of the B block of the structural unit derived from the carboxyl group-containing monomer and the structural unit represented by the general formula (B1) (solid content 20 Mass%).

(Comparative Examples 1~2: Comparison of the synthesis of salt block copolymers AC-1~AC-2)

In Example 1, the A block material was changed to the content shown in Table 1, and the B block material was changed to the type and content shown in Table 1. Otherwise, the same as the salt type of Example 1 In the same way as the block copolymer A-1 solution, the comparative salt type block copolymer AC-1~AC-2 solution was obtained. Furthermore, in Comparative Example 1, the purified comparative block copolymer AC-1" was not reacted with an isocyanate compound, and a comparative salt type block copolymer AC-1 solution was obtained. In Comparative Example 2, acrylic acid (3-Ethyloxetane-3-yl) methyl ester is added together with B block monomers such as EEMA to obtain a comparative block copolymer AC-2" without copolymerizing the purified comparative block The composite AC-2" reacted with the isocyanate compound to obtain a comparative salt type block copolymer AC-2 solution.

The salt type block copolymers A-1 to A-14 obtained in Examples 1 to 14 and the comparative salt type block copolymers AC-1 to AC-2 obtained in Comparative Examples 1 to 2 The acid value, amine value, hydroxyl value, and weight average molecular weight (Mw) before salt formation before and after salt formation are shown in Table 1. Furthermore, the amine value of the salt-type block copolymer after salt formation is calculated by subtracting the amine value of the DMMA unit from the amine value before salt formation.

(Example 15: Synthesis of block copolymer A-15)

In Example 1, a block copolymer A-15 solution was obtained in the same manner as in Example 1, except that salt formation was not performed.

(Example 16: Synthesis of block copolymer A-16)

In Example 3, a block copolymer A-16 solution was obtained in the same manner as in Example 3 except that salt formation was not performed.

(Example 17: Synthesis of block copolymer A-17)

In Example 5, a block copolymer A-17 solution was obtained in the same manner as in Example 5 except that salt formation was not performed.

(Example 18: Synthesis of salt type block copolymer A-18)

After depressurizing and drying a 500ml four-neck separable flask, it was replaced with Ar (argon). While performing Ar flow, add 100 parts by mass of dehydrated THF, 2.0 parts by mass of methyl trimethylsilyl dimethyl ketene acetal, and 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB) 0.15 ml, 0.2 parts by mass of mesitylene. Using a dropping funnel, 12.1 parts by mass of 2-ethylhexyl methacrylate (EHMA), 12.9 parts by mass of n-butyl methacrylate (BMA), and benzyl methacrylate (BzMA) were added dropwise over 45 minutes. 9.0 parts by mass, 17.7 parts by mass of methyl methacrylate (MMA), and 17.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA). As the reaction progresses, heat is generated, so the temperature was kept below 40°C by cooling in an ice bath. After 1 hour, 25.3 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain block copolymer A-18". The block copolymer A-18" was dissolved in 400 parts by mass of PGMEA, and isocyanate A (2-isocyanatoethyl methacrylate, trade name : Karenz MOI, manufactured by Showa Denko Corporation) 5.3 parts by mass, dibutyltin (trade name: Neostann U-100, manufactured by Nitto Kasei Co., Ltd.) 0.008 parts by mass, heated to 80° C., reacted for 2 hours to obtain a compound having the general formula ( I) the A block of the structural unit represented by the general formula (B1) and the block copolymer A-18' solution (solid form) containing the structural unit represented by the general formula (B1) and the B block of the structural unit derived from the carboxyl group-containing monomer Material composition 20% by mass). In Example 1, the block copolymer A-18' solution was used instead of the block copolymer A-1' solution. Except for this, in the same manner as in Example 1, a salt type with a solid content of 20% by mass was obtained. Block copolymer A-18 solution.

The acid value, amine value, hydroxyl value and weight average molecular weight (Mw) of block copolymers A-15 to A-17 and salt type block copolymers A-18 obtained in Examples 15 to 18 are shown in Table 1.

Here, the abbreviations in the table are as follows.

DMMA: Dimethylaminoethyl methacrylate

MAA: Methacrylic acid

EHMA: 2-ethylhexyl methacrylate

BMA: n-butyl methacrylate

BzMA: Benzyl methacrylate

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

HPhPA: 2-hydroxy-3-phenoxypropyl acrylate (trade name: M-600A, manufactured by Kyoeisha Chemical Co., Ltd.)

4HBA: 4-hydroxybutyl acrylate

Isocyanate A: 2-isocyanatoethyl methacrylate (trade name: Karenz MOI, manufactured by Showa Denko)

Isocyanate B: 2-(0-[1'-methylpropyleneamino]carboxyamino)ethyl methacrylate (trade name: Karenz MOI-BM, manufactured by Showa Denko)

Isocyanate C: 1,1-(bisacryloxymethyl)ethyl isocyanate (trade name: Karenz BEI, manufactured by Showa Denko)

Isocyanate D: 2-methacryloxy ethoxy ethyl isocyanate (trade name: Karenz MOI-EG, manufactured by Showa Denko)

Isocyanate E: 2-isocyanatoethyl acrylate (trade name: Karenz AOI-VM, manufactured by Showa Denko)

(Synthesis example 1: Synthesis of alkali-soluble resin A solution)

Add 300 parts by mass of PGMEA to the polymerization tank. After the temperature is raised to 100°C in a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, and methacrylic acid are continuously added dropwise over 1.5 hours. (MAA) 36 parts by mass, 6 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan). Thereafter, the reaction was continued at 100°C, and 2 hours after the completion of the dropwise addition of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization. Next, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy-containing compound was added. After the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added, and the temperature was carried out at 110°C for 15%. The hourly addition reaction gave an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass). Furthermore, the above-mentioned method for measuring the weight average molecular weight is to measure the weight average molecular weight by Shodex GPC System-21H using polystyrene as the standard substance and THF as the eluent. In addition, the acid value measurement method is based on JIS K 0070:1992.

(Example 21)

(1) Manufacturing of color material dispersion G1

14.8 parts by mass of the salt block copolymer A-1 solution (solid content 20% by mass) of Example 1 as a dispersant, 10.4 parts by mass of CI Pigment Green 58 (PG58) as a color material, and CI Pigment Yellow 138 (PY138) 2.6 parts by mass, 14.6 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, 57.6 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are placed in a mayonnaise bottle as a pre-crush , Shake for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.), then take out the 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 similarly, as a formal crushing, Dispersion was performed in a paint shaker for 4 hours to obtain a color material dispersion G1.

(2) Manufacturing of photosensitive colored resin composition G1 for color filters

(日本化藥公司製造，「DETX-S」)0.12質量份、作為抗氧化劑之受阻酚系抗氧化劑(IRGANOX1010，BASF公司製造)0.11質量份、3-甲基丙烯醯氧基丙基三甲氧基矽烷(商品名：KBM503，信越化學工業股份有限公司製造)0.4質量份、Megafac F-559(DIC製造)0.04質量份及作為溶劑之PGMEA 41.4質量份，其後混合至變得均勻為止，獲得彩色濾光片用感光性著色樹脂組成物G1。 Add 43.8 parts by mass of the color material dispersion G1 obtained in (1) above, 6.3 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, and a multifunctional monomer (trade name Aronix M-403, Toagosei Co., Ltd. Made by the company) 5.9 parts by mass, 0.92 parts by mass of the oxime ester initiator as a photoinitiator (manufactured by ADEKA, "Adeka arkls NCI-930"), and 0.92 parts by mass of the oxime ester initiator (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) , "TR-PBG-3057") 0.69 parts by mass, diethyl-9-oxysulfur

(Manufactured by Nippon Kayaku Co., Ltd., "DETX-S") 0.12 parts by mass, hindered phenol antioxidant (IRGANOX 1010, manufactured by BASF Corporation) as an antioxidant, 0.11 parts by mass, 3-methacryloxypropyl trimethoxy Silane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.4 parts by mass, Megafac F-559 (manufactured by DIC) 0.04 parts by mass, and 41.4 parts by mass of PGMEA as a solvent, and then mixed until it becomes uniform to obtain a color Photosensitive colored resin composition G1 for filters.

(3) Formation of colored layer

Use a spin coater to apply the colored resin composition G1 obtained in (2) above on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm and 100 mm × 100 mm, and then heat it. The board was dried at 80°C for 3 minutes, irradiated with 60mJ/cm ² of ultraviolet light using an ultra-high pressure mercury lamp, and then post-baked in a clean oven at 230°C for 30 minutes to adjust the cured film thickness to 2.5μm The film is thick and the colored layer G1 is formed.

(Examples 22 to 38, Comparative Examples 11 to 12)

(1) Manufacturing of color material dispersion G2~G18 and comparison color material dispersion GC1~GC2

In (1) of Example 21, instead of the salt-type block copolymer A-1 solution, as shown in Table 2, the solid content was the same as that of the salt-type block copolymer A-1. Use the salt type block copolymers A-2~A-14 solutions of Examples 2-14, the block copolymers A-15~A-17 of Examples 15-18, and the salt type block copolymers A-18 respectively. , The comparative salt-type block copolymer AC-1~AC-2 solutions of Comparative Examples 1 and 2, adjust the amount of PGMEA so that the total amount becomes 100 parts by mass. Except for this, the same as in Example 21 (1) In this way, color material dispersion liquids G2 to G18 and comparative color material dispersion liquids GC1 to GC2 are obtained.

(2) Manufacture of photosensitive colored resin compositions G2 to G18 for color filters, and photosensitive colored resin compositions GC1 to GC2 for comparative color filters

In (2) of Example 21, the color material dispersions G2 to G18 and the comparative color material dispersions GC1 to GC2 were used instead of the color material dispersion G1. Otherwise, the same as in Example 21 (2) In the same manner, photosensitive colored resin compositions G2 to G18 for color filters and photosensitive colored resin compositions GC1 to GC2 for comparative color filters were obtained.

(3) Formation of colored layer

In (3) of Example 21, the colored resin composition G2 to G18, GC1 to GC2 were used instead of the colored resin composition G1. Except for this, the colored resin composition was obtained in the same manner as in (3) of Example 21. Layers G2~G18, GC1~GC2.

(Example 41)

(1) Manufacturing of color material dispersion R1

In (1) of Example 21, 13 parts by mass of diketopyrrolopyrrole pigment (Irgaphor RED S 3621CF, manufactured by BASF) represented by the following chemical formula (R1) was used instead of 10.4 parts by mass of CI Pigment Green 58 (PG58) Except for 2.6 parts by mass of CI Pigment Yellow 138 (PY138), the color material dispersion liquid R1 was obtained in the same manner as in (1) of Example 21.

(2) Manufacturing of photosensitive colored resin composition R1 for color filters

In (2) of Example 21, the color material dispersion liquid R1 obtained above was used instead of the color material dispersion liquid G1. Except for this, the photosensitive material for color filter was obtained in the same manner as in Example 21 (2). Colored resin composition R1.

(3) Formation of colored layer

In Example 21 (3), except that the colored resin composition R1 was used instead of the colored resin composition G1, a colored layer R1 was obtained in the same manner as in Example 21 (3).

(Example 42)

(1) Manufacturing of color material dispersion B1

In Example 21 (1), CI Pigment Blue 15:6 (PB15:6) 13 parts by mass was used instead of CI Pigment Green 58 (PG58) 10.4 parts by mass and CI Pigment Yellow 138 (PY138) 2.6 parts by mass, except for this Otherwise, the color material dispersion liquid B1 was obtained in the same manner as in (1) of Example 21.

(2) Manufacturing of photosensitive colored resin composition B1 for color filters

In (2) of Example 21, the color material dispersion liquid B1 obtained above was used instead of the color material dispersion liquid G1. Except for this, the photosensitive material for color filter was obtained in the same manner as in Example 21 (2). Colored resin composition B1.

(3) Formation of colored layer

In Example 21 (3), except that the colored resin composition B1 was used instead of the colored resin composition G1, a colored layer B1 was obtained in the same manner as in Example 21 (3).

(Example 43)

(1) Manufacturing of color material dispersion Y1

In Example 21 (1), 13 parts by mass of CI Disperse Yellow 54 (trade name: KPPlast Yellow HR, manufactured by Kiwa Chemical Co., Ltd.) was used instead of 10.4 parts by mass of CI Pigment Green 58 (PG58) and CI Pigment Yellow 138 (PY138) 2.6 Except for the parts by mass, the color material dispersion liquid Y1 was obtained in the same manner as in Example 21 (1).

(2) Manufacturing of photosensitive colored resin composition Y1 for color filters

In (2) of Example 21, the color material dispersion Y1 obtained above was used instead of the color material dispersion G1. Except for this, the photosensitive material for color filter was obtained in the same manner as in Example 21 (2). Colored resin composition Y1.

(3) Formation of colored layer

In Example 21 (3), except that the colored resin composition Y1 was used instead of the colored resin composition G1, a colored layer Y1 was obtained in the same manner as in Example 21 (3).

[Evaluation method]

<Evaluation of Viscosity Stability of Color Material Dispersion>

For the color material dispersions obtained in the Examples and Comparative Examples, the viscosity immediately after preparation and after storage at 25°C for 30 days were measured, and the viscosity change rate was calculated from the viscosity before and after storage to evaluate the viscosity stability. Viscosity is measured by vibrating viscometer at 25.0±0.5℃. The results are shown in Tables 2 and 3.

(Viscosity stability evaluation standard)

AA: The change rate of viscosity before and after storage is less than 10%

A: The change rate of viscosity before and after storage is more than 10% and less than 15%

B: The change rate of the viscosity before and after storage is more than 15% and less than 25%

C: The change rate of viscosity before and after storage is more than 25% and less than 40%

D: The change rate of viscosity before and after storage is more than 40%

Among them, the viscosity of the color material dispersion is the value when the color material is 13% by mass relative to the total mass including the solvent of the color material dispersion. Even if the evaluation result is C, the color material dispersion can be used in practical applications. If the evaluation result is B, the color material dispersion is better, and if the evaluation result is A, the dispersion stability of the color material dispersion is excellent.

<ITO crack resistance evaluation>

Use a spin coater to apply the photosensitive colored resin composition for color filters obtained in the examples and comparative examples to the thickness of 0.7mm and 100mm×100mm so that the film thickness after baking becomes about 2.5μm. On the glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35"). After that, it was heated and dried on a hot plate at 80°C for 3 minutes. An ultra-high pressure mercury lamp was used to irradiate 40mJ/cm ² of ultraviolet rays without intervening a light shield, and post-baking was performed in a clean oven at 230°C for 30 minutes to obtain a cured film (colored film). A sputtering device (manufactured by ULVAC, CS-200) was used to form ITO with a thickness of 120 nm on the obtained cured film. After immersing the film in N-methylpyrrolidone at 25°C for 120 minutes, it was visually observed whether the substrate had cracks in the ITO film.

(Evaluation criteria for ITO crack resistance)

AA: no cracks

A: The number of cracks is less than 5

B: Cracks on the whole surface

C: The whole surface is cracked and the ITO is partially peeled off

If the above evaluation criterion is AA or A, it can be used in practical applications, and if the evaluation result is AA, the effect is more excellent.

<Evaluation of developing adhesion>

The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., NH TECHNO GLASS Co., Ltd.) with a thickness of 0.7 mm and a thickness of 100 mm×100 mm using a spin coater. NA35") was then dried using a hot plate at 80°C for 3 minutes, thereby forming a coloring layer with a thickness of 2.5 μm. An ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of ^{60mJ/cm 2 in a} mask with a mask opening width of 2~80μm between the colored layer. Using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, the glass plate on which the colored layer was formed was shower-developed for 60 seconds. Observe the developed substrate with an optical microscope to observe the presence or absence of the colored layer relative to the line width of the mask opening. The results are shown in Tables 2 and 3.

(Evaluation Criteria for Development Adhesion)

AA: The colored layer is observed in the part where the line width of the mask opening is less than 10μm

A: The colored layer is observed in the part where the line width of the mask opening is 10μm or more and less than 20μm

B: The colored layer is observed in the part where the line width of the mask opening is 20μm or more and less than 50μm

C: The colored layer is observed in the part where the width of the mask opening is 50μm or more and less than 80μm

D: No colored layer is observed in the part of the mask opening line width below 80μm

Even if the evaluation result is B, the photosensitive colored resin composition for color filters can be used in practical applications. If the evaluation result is A, the photosensitive colored resin composition for color filters is more suitable for high definition. If the evaluation result is AA, the photosensitive colored resin composition for color filters is more suitable for high definition.

<Evaluation of developing residue>

The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., NH TECHNO GLASS Co., Ltd.) with a thickness of 0.7 mm and a thickness of 100 mm×100 mm using a spin coater. NA35") was then dried using a hot plate at 60°C for 3 minutes, thereby forming a coloring layer with a thickness of 2.5 μm. The glass plate on which the colored layer was formed was shower-developed for 120 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer. After visually observing the unexposed part (50mm×50mm) of the glass substrate after the formation of the colored layer, wipe it thoroughly with an alcohol-containing lens cleaner (manufactured by Toray, trade name Toraysee MK Clean Cloth), and observe the lens visually The degree of coloring of the cleaner. The results are shown in Tables 2 and 3.

(Evaluation criteria for developing residue)

A: The developing residue is not confirmed visually, and the lens cleaner is not colored at all

B: The development residue was not confirmed visually, and the coloring of the lens cleaner was slightly confirmed

C: The developing residue is slightly confirmed visually, and the coloring of the lens cleaner is slightly confirmed

D: The developing residue is slightly confirmed visually, and the coloring of the lens cleaner is confirmed

E: Visually confirm the development residue and confirm the coloring of the lens cleaner

If the development residue evaluation standard is A, B, or C, it is evaluated that the generation of development residue is sufficiently suppressed, and it can be used in practical applications without any problems.

<Evaluation of Solvent Resolubility>

The front end of a glass substrate with a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for color filters obtained in the Examples and Comparative Examples, and coated on the 1 cm portion of the glass substrate. Put the lifted glass substrate into a constant temperature and humidity machine such that the glass surface becomes horizontal, and dry it under the conditions of a temperature of 23°C and a humidity of 80%RH for 30 minutes. Next, the glass substrate with the dried coating film attached was immersed in PGMEA for 15 seconds. At this time, the re-dissolution state of the dried coating film was visually judged and evaluated. The results are shown in Tables 2 and 3.

(Evaluation criteria for solvent resolubility)

AA: The dried coating film is completely dissolved

A: A flake with a dry coating film is produced in a solvent, and the flake will dissolve soon

B: In the solvent to produce dry film flakes, the solution is colored

C: Produce dry film flakes in the solvent, the solution is not colored

D: No dry film flakes are produced in the solvent, and the solution is not colored

If the development residue evaluation standard is AA, A, or B, it is evaluated that the solvent resolubility is good, and it can be used without any problems in practical applications.

<Evaluation of color material sublimation>

The photosensitive coloring compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate with a thickness of 0.7 mm using a spin coater, and heated and dried on a hot plate at 80°C for 3 minutes. Thereby, a coloring layer with a thickness of 2.5 μm is formed. An ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of ^{40 mJ/cm 2} on a mask with a stripe pattern of 80 μm lines and gaps drawn on the colored layer. Thereafter, the glass plate on which the colored layer was formed was spray-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then washed with ultrapure water for 60 seconds. A glass substrate was placed on the 0.7 mm upper surface of the obtained glass substrate with the colored pattern formed, and heated on a hot plate at 230°C for 30 minutes. By visually confirming the presence or absence of sublimation on the glass substrate on the upper surface, it was used as an evaluation of the sublimation property of the color material.

(Evaluation criteria for sublimation of color materials)

A: The glass substrate on the upper surface does not have the coloring and precipitation produced by the sublimation

B: Although the glass substrate on the upper surface is colored by sublimation, there is no precipitate

C: On the upper surface of the glass substrate, there is coloration caused by sublimation, and precipitates are also confirmed

<Evaluation of Adhesion to Substrate>

The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater . Thereafter, after heating and drying on a hot plate at 80°C for 3 minutes, an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays at ^{60 mJ/cm 2.} Thereafter, post-baking was performed in a clean oven at 230°C for 30 minutes to obtain a colored film with a thickness of 2.5 μm. After cutting out grid-like slits on the obtained colored film with a utility knife, a backing tape is attached to it, and it is quickly peeled off in the vertical direction. The state of the colored film was visually observed and evaluated based on the following evaluation criteria. The results are shown in Tables 2 and 3.

(Evaluation criteria for substrate adhesion)

AA: Peeling is not confirmed at all

A: Peeling is slightly confirmed along the grid-shaped slit

B: Peeling is also confirmed inside the part surrounded by the slit

If the evaluation result is AA or A, the adhesion to the substrate is excellent, and the evaluation is in the practical range.

<Optical performance evaluation>

The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., NH TECHNO GLASS Co., Ltd.) with a thickness of 0.7 mm and a thickness of 100 mm × 100 mm using a spin coater NA35") was then dried using a hot plate at 80°C for 3 minutes to form a colored layer. An ultra-high pressure mercury lamp was used to irradiate the colored layer with ultraviolet rays of ^{60 mJ/cm 2.} Secondly, the colored substrate was post-baked in a clean oven at 230°C for 30 minutes, and the chromaticity (x, y) and brightness (Y) of the obtained colored substrate were measured using the microscope OSP-SP200 manufactured by Olympus. ). The results are shown in Tables 2 and 3 together. Furthermore, the C light source is used as the light source.

[Summary of Results]

From the results in Tables 2 and 3, it can be seen that the coloring layer formed by using the photosensitive colored resin composition for color filters of Examples 21 to 38 and Examples 41 to 43 has higher brightness and the ITO film is resistant to cracking Excellent performance, further development adhesion and solvent resolubility, inhibit the sublimation and precipitation of the color material in the colored layer, and excellent substrate adhesion. The above-mentioned Examples 21 to 38 and Examples 41 to 43 are used for color filters The photosensitive colored resin composition uses the following block copolymer as a dispersant, the block copolymer containing the A block containing the structural unit represented by the above general formula (I), and containing selected from the above general formula (B1) B block of at least one of the structural unit represented by) and the structural unit represented by the general formula (B2). On the other hand, regarding the use of a salt-type block copolymer in which the B block does not contain at least one selected from the structural unit represented by the above general formula (B1) and the structural unit represented by the above general formula (B2) as a dispersant In Comparative Examples 11 and 12, the brightness is low, the crack resistance of the ITO film is poor, and the development adhesion and solvent resolubility are also poor. Sublimation or precipitation of the color material in the color layer is confirmed.

Claims (11)

A color material dispersion liquid for color filters, which contains a color material, a dispersant, and a solvent, and the dispersant contains a block copolymer of A block and B block, and the A block contains the following general The structural unit represented by the formula (I), the B block contains at least one selected from the structural unit represented by the following general formula (B1) and the structural unit represented by the following general formula (B2),

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ² and R ³ can be Mutual bonding to form a ring structure)

(In the general formula (B1), A ¹ represents a divalent linking group, R ¹¹ represents a two-, three- or four-valent aliphatic hydrocarbon group or a carbon atom that may contain an oxygen atom, and R ¹⁰ and R ¹² each independently represent a hydrogen atom or Methyl; n is 1, 2 or 3)

(In the general formula (B2), A ² represents a divalent linking group, A ³ and A ⁴ each independently represent a divalent, trivalent or tetravalent linking group, and R ¹³ represents that it may contain at least one selected from the group consisting of oxygen atoms and nitrogen atoms A divalent hydrocarbon group, R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group that may contain an oxygen atom, and R ¹⁰ , R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or a methyl group; n ¹ represents 0, 1, 2 or 3, n ² represents 0 or 1, n ³ represents 0, 1 or 2, n ¹ + n ² is 1, 2 or 3, n ¹ + n ² + n ³ is 1, 2 or 3; m ¹ represents 1, 2 or 3, m ² represents 0, 1 or 2, and m ¹ + m ² is 1, 2 or 3). The color material dispersion liquid for color filters of claim 1, wherein the acid value of the dispersant is 1 mgKOH/g or more and 18 mgKOH/g or less. The color material dispersion liquid for color filters according to claim 1 or 2, wherein the dispersant contains at least a part of the terminal nitrogen portion of the structural unit represented by the general formula (I), and is selected from organic At least one of the acid compound and the halogenated hydrocarbon forms a salt type block copolymer. The color material dispersion liquid for color filters of claim 1 or 2, wherein the hydroxy value of the dispersant is 120 mgKOH/g or less. According to claim 1 or 2, the color material dispersion liquid for color filters, wherein the color material contains a diketopyrrolopyrrole pigment, a quinophthalone pigment, a copper phthalocyanine pigment, a zinc phthalocyanine pigment, and a quinophthalone At least one of the group consisting of dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes. A dispersing agent containing a block copolymer of A block and B block, the A block contains the structural unit represented by the following general formula (I), and the B block contains selected from the following general formula ( At least one of the structural unit represented by B1) and the structural unit represented by the following general formula (B2),

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent linking group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ² and R ³ can be Mutual bonding to form a ring structure)

(In the general formula (B1), A ¹ represents a divalent linking group, R ¹¹ represents a two-, three-, or four-valent aliphatic hydrocarbon group or carbon atom that may contain an oxygen atom, and R ¹⁰ and R ¹² each independently represent a hydrogen atom or Methyl; n is 1, 2 or 3)

(In the general formula (B2), A ² represents a divalent linking group, A ³ and A ⁴ each independently represent a divalent, trivalent or tetravalent linking group, and R ¹³ represents that it may contain at least one selected from the group consisting of oxygen atoms and nitrogen atoms A divalent hydrocarbon group, R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group that may contain an oxygen atom, and R ¹⁰ , R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or a methyl group; n ¹ represents 0, 1, 2 or 3, n represents 0 or 1, n ³ represents 0, 1 or 2, n ¹ + n ² is 1, 2 or 3, n ¹ + n ² + n ³ is 1, 2 Or 3; m ¹ represents 1, 2 or 3, m ² represents 0, 1 or 2, and m ¹ + m ² is 1, 2 or 3). A photosensitive colored resin composition for a color filter, which contains the color material dispersion liquid for a color filter according to any one of claims 1 to 5, an alkali-soluble resin, a multifunctional monomer, and a photoinitiator. The photosensitive colored resin composition for color filters according to claim 7, wherein the photoinitiator contains an oxime ester. The photosensitive colored resin composition for color filters according to claim 7, wherein the photoinitiator contains at least two oxime esters and further contains an antioxidant. A color filter comprising at least a substrate and a coloring layer provided on the substrate, characterized in that: at least one of the coloring layers is used for the color filter of any one of claims 7 to 9 above Hardened product of photosensitive colored resin composition. A display device having the color filter of claim 10 above.

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