TW201841960A - 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 color resin composition for color filter, color filter, display device   

The present invention relates to a color material dispersion for a color filter, a dispersant, a photosensitive colored resin composition for a color filter, a color filter, and a display device.

In recent years, with the development of personal computers, especially the development of portable personal computers, the demand for liquid crystal displays has increased. The popularity of mobile displays (mobile phones, smart phones, and tablet personal computers (PCs)) has also increased, and the market for liquid crystal displays is expanding. In addition, recently, organic light emitting display devices such as organic electroluminescence (EL) displays with high visibility due to self-emission have also attracted attention as next-generation image display devices. In the performance of these image display devices, further improvement in image quality such as improvement in contrast or color reproducibility or reduction in power consumption are strongly desired.

A color filter is used in these liquid crystal display devices or organic light emitting display devices. For example, the color image of a liquid crystal display device is formed by directly coloring the light passing through the color filter into the colors of the pixels constituting the color filter, and combining 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 where an organic light-emitting element emitting white light or an inorganic light-emitting element emitting white light is used. Further, in the organic light emitting display device, a color filter is used for color adjustment and the like. Under such circumstances, expectations for higher brightness, higher contrast, and improved color reproducibility are also expected for color filters.

Here, in general, the color filter includes: a transparent substrate; a colored layer formed on the transparent substrate and including a colored pattern of three primary colors of red, green, and blue; and a light-shielding portion to divide each colored pattern The method is formed on a transparent substrate.

As a method for forming pixels in a color filter, a pigment dispersion method having an average characteristic is most widely used in terms of spectral characteristics, durability, pattern shape, and accuracy. In a color filter having pixels formed using a pigment dispersion method, in order to achieve high brightness or high contrast, the miniaturization of pigments has been studied. It is considered that by miniaturizing the pigment, scattering of light transmitted through the color filter due to pigment particles can be reduced, and high brightness or high contrast can be achieved. However, since the finely-divided pigment particles easily aggregate, there is a problem that the dispersibility or dispersion stability is reduced.

As a method for improving the dispersibility of a finely-divided pigment, it is known that a dispersant is effective. For example, in Patent Document 1, in order to satisfy the initial dispersibility and dispersion stability over time of a micronized pigment dispersant, and further satisfy the requirements of high contrast, high brightness, and high developability of a liquid crystal display element, it is disclosed There is a coloring composition for a color filter, 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 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 which can form a colored layer having excellent chromaticity characteristics and heat resistance, and which has good dispersibility and storage stability, a coloring composition for a color filter is disclosed. As a pigment dispersant, the copolymer includes a specific repeating unit having an amine group and a repeating unit having a crosslinkable functional group, and the amine value is 80 to 250 mgKOH / g.

In addition, in Patent Documents 3 and 4, it is described that a specific colored resin composition is used in order to obtain a photosensitive colored resin composition that is excellent in color material dispersion stability, suppresses development residues, and has excellent development adhesion and solvent resolubility. Dispersant. As a specific dispersant, Patent Document 3 describes a block copolymer including a structure having a sulfonylamino group and a nitrogen site corresponding to a terminal end of the amine group, or a structure in which the nitrogen site forms a salt with a specific compound. A specific constituent unit further has a specific amine value and a specific glass transition temperature; Patent Document 4 describes a block copolymer containing: A block containing a nitrogen site having a terminal equivalent to an amine group Or a specific structural unit of a structure in which the nitrogen site forms a salt with a specific compound; and a B block containing a structural unit derived from a 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 years, color filters have been further improved in brightness and various tolerances. In general, a color filter is formed on a colored layer as an indium tin oxide (ITO) film that becomes a transparent electrode. However, in the conventional color filter, there are also problems in that cracks are easily generated in an ITO film formed adjacent to the colored layer, and display defects occur due to current flow due to cracks generated in the ITO film. The present invention has been made in view of the above circumstances, and an object thereof is to provide a color material dispersion liquid capable of forming a colored layer with high brightness and suppressing cracking of an ITO film formed adjacent to the colored layer. Another object of the present invention is to provide a dispersant for use in the color material dispersion liquid that can form a colored layer with high brightness and can suppress cracking of an ITO film formed adjacent to the colored layer. Another object of the present invention is to provide a photosensitive colored resin composition for a color filter that can form a colored layer with high brightness and can suppress cracking of an ITO film formed adjacent to the colored layer. Another object of the present invention is to provide a color filter formed using the photosensitive colored resin composition for a color filter. Another object of the present invention is to provide a display device having excellent display characteristics by using the color filter.

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

[Chemical 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 which may contain a hetero atom, and R ² and R ³ may Bond to each other to form a ring structure.)

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

[Chemical 3]

(In the general formula (B2), A ² represents a divalent linking group, A ³ and A ⁴ each independently represent a di-, tri-, or tetra-valent linking group, and R ¹³ represents that it may contain at least one selected from an oxygen atom and a nitrogen atom. A divalent hydrocarbon group, R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group which 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 means 0, ¹ , 2 or 3, n ² means 0 or 1, n ³ means 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 means 1, 2 or 3, m ² means 0, 1 or 2, and m ¹ + m ² is 1, 2 or 3.)

The dispersant of the present invention is a block copolymer containing an A block and a B block. The A block contains a structural unit represented by the general formula (I). The B block contains a member selected from the 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 includes at least a substrate and a coloring layer provided on the substrate, and at least one of the colored 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 includes the color filter of the present invention.

According to the present invention, it is possible to provide a color material dispersion liquid capable of forming a high-brightness colored layer and suppressing cracking of an ITO film formed adjacent to the colored layer. Furthermore, according to the present invention, it is possible to provide a dispersant for use in the color material dispersion liquid that can form a colored layer with high brightness and can suppress cracking of an ITO film formed adjacent to the colored 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 colored layer with high brightness and can suppress cracking of an ITO film formed adjacent to the colored layer. The present invention also provides a color filter formed using the photosensitive coloring 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 Department

3‧‧‧ colored layer

10‧‧‧ color filter

20‧‧‧ Opposite substrate

30‧‧‧LCD layer

40‧‧‧LCD display 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 a color filter of the present invention.

FIG. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention.

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

Hereinafter, the color material dispersion for a color filter, a dispersant, a photosensitive colored resin composition for a color filter, a color filter, and a display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and further includes radiation. The radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams having a wavelength of 5 μm or less. In the present invention, the (meth) acrylfluorenyl group means each of an acrylfluorenyl group and a methacrylmethyl group, and the (meth) acryl group means each of an acrylic group and a methacryl group, and the (meth) Acrylate means each of acrylate and methacrylate. In this specification, unless otherwise specified, the chromaticity coordinates x and y refer to the XYZ color system of JIS Z8701: 1999 for color measurement using a C light source.

1.Color material dispersion for color filters

The color material dispersion liquid for a color filter of the present invention 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 includes the following The structural unit represented by the formula (I), and the B block includes at least one selected from a structural unit represented by the following general formula (B1) and a 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 which may contain a hetero atom, and R ² and R ³ may Bond to each other to form a ring structure.)

[Chemical 5]

(In the general formula (B1), A ¹ represents a divalent linking group, R ¹¹ represents an aliphatic hydrocarbon group or a carbon atom of two, three or four valences of oxygen atoms, 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 di-, tri-, or tetra-valent linking group, and R ¹³ represents that it may contain at least one selected from an oxygen atom and a nitrogen atom. A divalent hydrocarbon group, R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group which 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 means 0, ¹ , 2 or 3, n ² means 0 or 1, n ³ means 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 means 1, 2 or 3, m ² means 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 specific A block and the specific B block as a dispersant, the photosensitive coloring resin for a color filter prepared by using the color material dispersion The composition can form a colored layer with high brightness, and can suppress cracking of the ITO film formed adjacent to the colored layer. Although the role of exerting such an effect is not clear, it is estimated as follows. It is considered that the specific block copolymer described above 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 structure selected from the group consisting of the general formula (B1). In at least one of the unit and the structural unit represented by the above-mentioned general formula (B2), (meth) acrylic acid is easily crosslinked with other crosslinkable groups when forming a colored layer. When it is a conventional dispersant, the crosslinking density near the color material is insufficient, and swelling is easily caused by the solvent. Therefore, after forming an ITO film adjacent to the colored layer, it is considered that the solvent such as NMP (N-methyl-2-pyrrolidone) contained in the coating liquid applied to the ITO film in the next step is considered. As a result, the colored layer under the ITO film swells, so it is easy for the ITO film, which is an inorganic substance, to crack. In contrast, the dispersant used in the present invention is considered to have at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) that the B block has. The (meth) acryl fluorene group is crosslinked with other crosslinkable groups, and it is particularly easy to crosslink between the molecules of the dispersant adsorbed to the color material, and it can increase the crosslink density near the color material in the coloring layer. , To reduce the cross-linked density of the sparse part, thereby improving the film strength. Therefore, in the present invention, the coloring layer can also ensure the crosslink density near the color material, which can reduce the portion where the crosslink density becomes sparse, thereby suppressing the swelling caused by the solvent. Therefore, it is concluded that the color layer has excellent solvent resistance. Since the ITO film formed adjacent to the colored layer does not crack (crack), it is easy to form a color filter. In addition, since the color material in the coloring layer is in a state of being coated with a hardened film having a high cross-linking density, the thermal movement during the baking of the color material molecules is reduced, and the deterioration of the color material is suppressed, so the decrease in the brightness of the color layer is suppressed. Therefore, it is inferred that a colored layer with high brightness can be formed. In addition, it is considered that the (meth) acrylfluorenyl group having at least one selected from the constitutional unit represented by the general formula (B1) and the constitutional unit represented by the general formula (B2) in the side chain is more oxocyclic than Other crosslinkable groups such as butyl are excellent in photopolymerization when combined with a radical polymerization initiator. Therefore, when a colored layer is formed, the reaction can be sufficiently reacted by exposure to increase the crosslink density. After baking, When the crosslinking density is higher, the effect of suppressing the decrease in brightness can be obtained, and the brightness of the colored layer formed is further improved. In addition, it is considered that (meth) acrylic acid is more excellent in storage stability under acidic or basic conditions than other crosslinkable groups such as oxetanyl group, so it coexists with the acidic group of the resin or the basic group of the dispersant The stability is excellent, so the viscosity stability is further improved. Moreover, in the manufacturing process of a color filter, a colored material sublimes or precipitates, and adheres to a colored layer, and it may become a cause of a foreign material defect. If the color material is sublimated from the coloring layer of the color filter, there are problems such that not only the color tone of the coloring layer changes, but also the color tone of the other coloring layer changes due to adhesion to other coloring layers, etc., resulting in a decrease in brightness, or Contamination inside the heating device. In contrast, in the present invention, by using the specific block copolymer described above as a dispersant, the color material in coloring is in a state of being coated with a hardened film having a high crosslinking density, thereby suppressing the sublimation and precipitation of the color material.

If the color material dispersion liquid of the present invention contains at least a color material, a dispersant, and a solvent, it 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 in order 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 includes a structural unit represented by the general formula (I), and the B block includes a member selected from the general formula At least one of a structural unit represented by (B1) and a structural unit represented by the general formula (B2). The block copolymer may form a salt from at least a part of the nitrogen site at the terminal of the structural unit represented by the general formula (I) and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon (hereinafter (Sometimes referred to as salt-type block copolymers). First, the self-block copolymer will be described.

{A block}

(Constitutional unit represented by general formula (I))

The constituent unit represented by the general formula (I) contained in the A block has basicity and functions as an adsorption site for a color material. In the general formula (I), A is a divalent linking group. Examples of the divalent linking group include 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 alkylene) and combinations thereof. Among these, in terms of dispersibility, A in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group.

Examples of the hydrocarbon group in the hydrocarbon group which may contain a hetero atom among R ² and R ³ include an alkyl group, an aralkyl group, and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a third butyl group, a 2-ethylhexyl group, a cyclopentyl group, and a cyclohexyl group. It is preferably 1 to 18, more preferably methyl or ethyl. Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl. The number of carbon atoms of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14. Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, and xylyl. The number of carbon atoms of the aryl group is preferably 6 to 24, and more preferably 6 to 12. In addition, the above-mentioned preferable number of carbon atoms does not include the number of carbon atoms of a substituent. The heteroatom-containing hydrocarbon group has a structure in which a carbon atom in the hydrocarbon group is substituted with a heteroatom. Examples of the hetero atom that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. 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, or a bromine atom.

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 through a nitrogen atom. The ring structure formed by R ² and R ³ may contain a hetero atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, Porphyrin ring and so on.

In the present invention, it is preferred that R ² and R ³ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ^{3 are} bonded to form a pyrrolidine ring or a piperidine ring. , Porphyrin ring.

As a monomer which derives the structural unit represented by the said General formula (I), a dimethylaminoethyl (meth) acrylate, a dimethylaminopropyl (meth) acrylate, and a (meth) acrylic acid dimer are mentioned. Ethylaminoethyl, diethylaminopropyl (meth) acrylate, etc. (meth) acrylates containing alkyl substituted amino groups, etc., dimethylaminoethyl (meth) acrylamide, dimethylamine (Meth) acrylamide and the like containing alkyl substituted amino groups such as propylpropyl (meth) acrylamide. Among these, in terms of improving dispersibility and dispersion stability, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl ( Methacrylamide. 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 General formula (I), it is preferable that the structural unit represented by General formula (I) contains three or more. Among these, in terms of improving the 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 constitutional unit other than the constitutional unit represented by the general formula (I) as long as it can achieve the purpose of the present invention, as long as it is a constitutional unit that can be copolymerized with the constitutional unit represented by the general formula (I). May contain. For example, as the constitutional unit other than the constitutional unit represented by the general formula (I) as the A block, the "other constitutional units" listed in the following B block can be used. Specifically, for example, The structural unit and the like represented by the general formula (II) are described. In the A block in the block copolymer before the salt formation, the content ratio of the constituent units represented by the general formula (I) is preferably 50 to 100% by mass relative to the total mass of the total constituent units of the A block. , More preferably 80 to 100% by mass, and 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 on the color material, and the better the dispersibility and dispersion stability of the block copolymer. In addition, the content ratio of the said structural unit is calculated from the feed mass at the time of synthesizing the A block which has the structural unit represented by General formula (I).

In addition, in terms of dispersibility and dispersion stability, in the block copolymer before the salt formation, the content ratio of the constituent unit represented by the general formula (I) is preferably relative to the block copolymer. The total mass of the total constituent units is 5 to 60% by mass, and more preferably 10 to 50% by mass. The content ratio of each constituent unit in the block copolymer is calculated from the feed mass at the time of the block copolymer before the formation of the synthetic salt. The constituent unit represented by the general formula (I) is only required to have an affinity with the color material, and may be composed of one kind or may include two or more kinds of constituent units.

{B block}

The B block does not contain a structural unit represented by the general formula (I), and 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). A block, and a block containing another constituent unit may be contained within the range which does not impair the effect of this invention. As the B block, in terms of dispersibility and dispersion stability, it is preferably used from a monomer having an unsaturated double bond that can be copolymerized with a monomer derived from the constituent unit represented by the general formula (I). A block constituted by appropriately selecting a solvent according to a solvent in a solubilizing manner. As a standard, the B block is preferably introduced so that the solubility of the copolymer at 23 ° C becomes 20 (g / 100 g solvent) or more with respect to the solvent used in combination.

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

The B block contains at least one selected from the structural units represented by the general formula (B1) and the structural units represented by the general formula (B2). As the divalent linking group of A ¹ in the above general formula (B1) and A ² , A ³ and A ⁴ in the general formula (B2), and the trivalent or tetravalent linking group in A ³ and A ⁴ , for example, Represents an aliphatic hydrocarbon group, an aromatic group, a -CONH- group, a -COO- group, and a combination thereof. The carbon chain may contain O (oxygen atom), S (sulfur atom), and N (nitrogen atom). It may have a substituent. The tetravalent linking group may be a carbon atom. The aliphatic hydrocarbon group in A ¹ , A ² , A ^3, and A ⁴ may be any of saturated, unsaturated, straight, branched, or cyclic chains, and may have a substituent, or O, S, N and other heteroatoms. For example, the carbon chain may contain an ether group, a thioether group, a carbonyl group, an oxycarbonyl group, an amido group, and the like. Examples of the substituent include a halogen atom, an alkoxy group, and a phenoxy group. Examples of the aromatic group in A ¹ , A ² , A ³ and A ⁴ include a monocyclic or polycyclic aromatic group, which may have a substituent or a heterocyclic ring containing O, S, and N. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring, and among them, a group containing a benzene ring is preferred. Examples of the substituent include the same as those described above. Examples of the combination of the aliphatic hydrocarbon group and the aromatic group in A ¹ , A ² , A ^3, and A ⁴ include a structure in which the aliphatic hydrocarbon group and the aromatic group are directly bonded, or the aliphatic hydrocarbon group and the aromatic group. The group is connected by a hetero atom-containing linking group such as the ether group described above. 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 which 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 in the general formula (B2), an alkylene group having 1 to 10 carbon atoms is preferred. A ^{1 in} the general formula (B1) and the alkylene groups in A ² , A ^3, and A ⁴ in the general formula (B2) may be any of linear, branched, and cyclic, preferably It is linear. 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 in the general formula (B2), among them, the remaining atomic group after removing 3 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 10 carbon atoms is more preferable, and more preferably The remaining atomic group after removing 3 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 5 carbon atoms. These aliphatic saturated hydrocarbon groups may have a substituent, 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 in the general formula (B2), the remaining atomic group or carbon atom after removing 4 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 10 carbon atoms is preferred, More preferably, it is the remaining atomic group or carbon atom after removing 4 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 5 carbon atoms. These aliphatic saturated hydrocarbon groups may have a substituent, and may contain heteroatoms such as O, S, and N in the carbon chain.

The divalent hydrocarbon group which may contain at least one selected from the group consisting of an oxygen atom and a nitrogen atom in R ¹³ of the general formula (B2) may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. A straight chain, branched chain or cyclic alkylene group and an alkenyl group, an arylene group, and a combination of these from at least one of an oxygen atom and a nitrogen atom may also contain a -CONH- group in the carbon chain, -COO- group, ether group, etc.

Examples of the divalent aliphatic hydrocarbon group that may contain an oxygen atom in R ¹¹ of the general formula (B1) and R ¹⁴ , R ¹⁶ , R ^18, and R ¹⁹ of the general formula (B2) include linear and branched chains. Or a cyclic alkylene group and an alkylene group, and an ether group or the like may be contained in the carbon chain. Among these, an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom is preferred. When there are several R ¹⁴ , R ¹⁶ , R ^18, or R ¹⁹ in the general formula (B2), the multiple R ¹⁴ , multiple R ¹⁶ , multiple R ^18, and multiple R ¹⁹ may be respectively The same or different. The trivalent or tetravalent aliphatic hydrocarbon group which may contain an oxygen atom in R ¹¹ of the general formula (B1) includes, for example, a linear, branched, or cyclic aliphatic saturated hydrocarbon or an aliphatic compound. Saturated hydrocarbons, which have 3 or 4 hydrogen atoms remaining, are aliphatic hydrocarbon groups or carbon atoms, and may contain ether groups in the carbon chain. Among them, it is preferably an aliphatic saturated hydrocarbon group or a carbon atom remaining after removing 3 or 4 hydrogen atoms from a linear, branched or cyclic aliphatic saturated hydrocarbon having 1 to 10 carbon atoms which may contain an oxygen atom. .

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

In the said general formula (B2), it is preferable from the point which the hydroxyl value of a dispersing agent becomes suitable suitably, the solvent re-solubility, the image development adhesiveness, and the brightness and the crack resistance of an ITO film. N ¹ + n ² > n ³ , and more preferably m ¹ > m ² .

The number of (meth) acrylfluorenyl groups having at least one selected from the constitutional unit represented by the general formula (B1) and the constitutional unit represented by the general formula (B2) in the side chain is not particularly limited. In terms of improving the crack resistance of the ITO film, two or more are preferable, and on the other hand, in terms of dispersion stability, six or less are preferable, and three or less are more preferable. 1 or 2.

At least one selected from the structural units represented by the general formula (B1) and the structural units represented by the general formula (B2) can be, for example, by using a unit having a structural unit represented by the general formula (I). Monomers with unsaturated double bonds and hydroxyl groups (hereinafter referred to as "hydroxyl-containing monomers"), which are introduced into the structural unit having a hydroxyl group, so that a compound having an isocyanate group and a (meth) acryl group ( An isocyanate group (hereinafter referred to as "isocyanate-containing (meth) acrylate") is introduced by reacting with a hydroxyl group in the aforementioned structural unit. Moreover, the structural unit represented by the said general formula (B2) can also introduce the structural unit which has a hydroxyl group by using a hydroxyl-containing monomer, for example, and can make one isocyanate group of a diisocyanate compound react with the hydroxyl group in the said 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) acrylfluorenyl group. Here, the hydroxyl group means an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon. The hydroxyl group has high reactivity with isocyanate group, and the reaction temperature can be reduced to about 70 to 90 ° C without using 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 constituent unit represented by the above-mentioned general formula (B2) can suppress yellowing caused by heating or catalyst during the reaction, and therefore can also suppress yellowing of the colored layer and improve the brightness of the colored layer. . In addition, since the hydroxyl value can be easily adjusted in the above-mentioned introduction method, the solvent resolubility can be improved by making the hydroxyl value an appropriate value.

The above-mentioned hydroxyl group-containing monomer is not particularly limited as long as it has an unsaturated double bond capable of copolymerizing with a monomer derived from the constituent unit represented by the general formula (I) and a monomer having at least one hydroxyl group. Examples: 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate, cyclohexanedimethanol Mono (meth) acrylates such as hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, 2-hydroxy-3- (meth) acrylate Hydroxyaryloxyalkyl (meth) acrylates such as phenoxypropyl, hydroxyalkoxyalkyl (meth) acrylates, glycerol mono (meth) acrylates, polyethylene glycol mono (methyl) (Meth) acrylate monomers having a hydroxyl group such as ε-caprolactone 1 mol adduct of acrylate, 2-hydroxyethyl (meth) acrylate; N- (2-hydroxyethyl) (formaldehyde) N- (hydroxyalkyl) (methyl) such as acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide (Meth) acrylamide-based monomers such as acrylamide Vinyl ether monomers having hydroxyl groups such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxybutyl vinyl ether, and other hydroxyalkyl vinyl ethers Body; 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, 2- (or 3- or 4-) hydroxybutyl allyl ether, etc. Among allyl ether-based monomers such as a hydroxyl group, a (meth) acrylate-based monomer having a hydroxyl group is preferred, and having a primary hydroxyl group is preferable to having a secondary hydroxyl group in terms of improving developability. In addition, the so-called primary hydroxyl group means a hydroxyl group in which a carbon atom bonded to a hydroxyl group is a primary carbon atom, and the so-called secondary hydroxyl group means a hydroxyl group in which a carbon atom bonded to a hydroxyl group is a secondary carbon atom. In terms of improving the development adhesion, it is preferable to use a hydroxyl-containing monomer having a glass transition temperature value (Tgi) of a homopolymer of each monomer to be 0 ° C or higher, and more preferably used as Hydroxyl-containing monomers above 10 ° C. The (meth) acrylate-based monomer having a hydroxyl group is more preferably selected from hydroxyalkyl (meth) acrylate, hydroxyaryl alkyl (meth) acrylate, and hydroxyalkoxy (meth) acrylate At least one of an alkyl ester and a hydroxyaryloxyalkyl (meth) acrylate, and more preferably selected from the group consisting of a hydroxyalkyl (meth) acrylate and a hydroxyaryloxy (meth) acrylate At least one of them is particularly preferably selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate One or more of the group.

Examples of the isocyanate-containing (meth) acrylate used when introducing the structural unit represented by the general formula (B1) include, for example, (meth) acrylic acid 2-isocyanatoethyl ester and (formaldehyde) (Propyl) 3-isocyanatopropyl acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethyl (meth) acrylate Ethyl ester, 4-isocyanatocyclohexyl (meth) acrylate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, 1,1- (bispropene isocyanate) Oxymethyl) ethyl ester and derivatives thereof. Examples of the derivative include compounds having an isocyanate group blocked by a blocking agent and at least one (meth) acrylfluorenyl group, and examples thereof include 2-[(3,5-dimethylpyridine) (Oxazolyl) carbonylamino] ethyl, 2- (0- [1'-methylpropyleneamino] carboxyamino) ethyl methacrylate, and the like. Examples of such 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 manufactured by Showa Denko Corporation), and the like.

Examples of the isocyanate-containing (meth) acrylate used when introducing the structural unit represented by the general formula (B2) include, for example, the molar ratio of the hydroxyl group-containing (meth) acrylate to the diisocyanate compound. Reaction product of about 1: 1. Examples of the hydroxyl-containing (meth) acrylate in the reaction product include the hydroxyl-containing (meth) acrylate-based corpuscle which can be used as the hydroxyl-containing monomer and a 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) acrylfluorenyl groups, and is not particularly limited, and preferably has 1 to 4 hydroxyl groups and 2 to 5 (Meth) acrylfluorenyl groups. Specific examples of the hydroxyl-containing polyfunctional (meth) acrylate include trimethylolpropane di (meth) acrylate, pentaerythritol bis or tri (meth) acrylate, dipentaerythritol bis, Three, four or five (meth) acrylates and so on. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- or 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and isocyanate 3,5,5- Trimethyl-3-isocyanatomethylcyclohexyl, m- or p-xylylene diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, ionamine Acid diisocyanate, pyridyl isocyanate and the like.

The isocyanate-containing (meth) acrylate is 1 equivalent to the hydroxyl group of the hydroxyl-containing monomer, and the isocyanate group is preferably at least 0.1 equivalents and at most 0.9 equivalents, and more preferably at least 0.15 equivalents. Moreover, it is easy to make a hydroxyl value into an appropriate value when it is used in the form of 0.8 equivalent or less, It is preferable from the point of the development adhesiveness and solvent resolubility, and the adhesiveness of a colored resin composition.

The isocyanate-containing (meth) acrylate is preferably 1 equivalent to the hydroxyl group of the hydroxyl-containing monomer, and the (meth) acrylfluorenyl group is preferably at least 0.1 equivalent and at most 3.0 equivalent. 0.15 equivalents or more and 2.5 equivalents or less are preferable in terms of brightness and crack resistance of the ITO film.

In addition, the constitutional unit represented by the general formula (B2) is a reaction of an isocyanate group of a diisocyanate compound with a hydroxyl group of a constitutional unit derived from the above-mentioned hydroxyl-containing monomer, and further a hydroxyl group-containing (methyl ) In the case where the acrylate is introduced by the reaction of another isocyanate group of a diisocyanate compound, the hydroxyl group-containing (meth) acrylate may be used in combination with the hydroxyl group-containing (meth) acrylate and The reaction product of the diisocyanate compound having a molar ratio of about 1: 1 is the same as that described in the reaction product. In this case, with respect to 1 equivalent of the hydroxyl group derived from the constituent unit derived from the above-mentioned hydroxyl-containing monomer, one isocyanate group of the diisocyanate compound is preferably 0.1 equivalent or more and 0.9 equivalent or less, and more preferably 0.15 equivalent or more. In addition, the use of a diisocyanate compound in a manner of 0.8 equivalent or less is easy to make the hydroxyl value appropriate, and it is preferable in terms of development adhesiveness and solvent resolubility, and adhesiveness of the colored resin composition. Moreover, it is preferable that the hydroxyl group of the hydroxyl group-containing (meth) acrylic acid ester is 1 equivalent to another isocyanate group with respect to the diisocyanate compound, and is preferably 0.1 equivalent or more and 0.9 equivalent or less, and more preferably 0.15 equivalent or more and A hydroxyl group-containing (meth) acrylate is used for 0.8 equivalents or less.

In the above block copolymer, the content ratio of at least one selected from the constitutional unit represented by the general formula (B1) and the constitutional unit represented by the general formula (B2) is not particularly limited. The total mass of the total constituent unit is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more. On the other hand, it is preferably 35% by mass or less, and more preferably 30% by mass. Below, it may be 20% by mass or less. When the content ratio of at least one selected from the constitutional unit represented by the general formula (B1) and the constitutional unit represented by the general formula (B2) is equal to or more than the above-mentioned lower limit value, the brightness of the colored layer and suppression of adjacent coloration are suppressed. 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-mentioned upper limit value. In addition, at least one selected from the structural units represented by the general formula (B1) and the structural units represented by the general formula (B2) may be composed of one type or may include two or more types of structural units.

In the block copolymer before salt formation, the (meth) acrylfluorenyl equivalent contained in the side chain is preferably in the range of 100 to 6000, and more preferably in the range of 250 to 4500. If the (meth) acryl fluorene equivalent is above the lower limit, the brightness of the colored layer and the crack resistance of the ITO film will be further improved. If it is below the upper limit, the alkali developability and color material dispersion will be improved. And plate making characteristics. Here, the (meth) acrylfluorenyl equivalent refers to the weight average molecular weight per mol of the (meth) acrylfluorenyl group in the block copolymer before the salt formation, and is expressed by the following formula (1).

Formula (1) (meth) acrylfluorenyl equivalent (g / mol) = W '(g) / M' (mol)

(In formula (1), W 'represents the mass (g) of the block copolymer before salt formation, and M' represents the (meth) propylene contained in the block copolymer W '(g) before salt formation. Molar number of fluorenyl (mol).)

The (meth) acrylfluorene equivalent can also be used to measure the (meth) acrylic acid per 1 g of the block copolymer before the salt formation by a test method based on the iodine value described in JIS K 0070: 1992, for example. The number of bases is calculated.

In addition, in the synthesis of the block copolymer used in the present invention, by appropriately adjusting the feed amount of each constituent unit, the constituent unit of the block copolymer can be made into a desired content ratio, so as to have a desired content ratio. A copolymer of desired properties. Wherein, the above-mentioned hydroxyl-containing monomer and the isocyanate-containing (meth) acrylate are used to introduce a structural unit selected from the general formula (B1) and the structural unit represented by the general formula (B2). In the case of at least one of these, 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 feed amount of the hydroxyl-containing monomer is relative to The total amount of monomers is 5 mass% or more, and more preferably 10 mass% or more. In terms of solvent resolubility, the amount of the hydroxyl group-containing monomer to be fed is preferably 50% by mass or less, more preferably 40% by mass or less with respect to the total amount of the monomers. In addition, in terms of improving the brightness of the colored layer and the crack resistance and adhesion of the ITO film, the feed amount of the isocyanate-containing (meth) acrylate is higher than that of the hydroxyl-containing monomer. The feed amount of the body is preferably 10% by mass or more, and more preferably 15% by mass or more. In terms of solvent resolubility, development adhesion, brightness, and crack resistance of the ITO film, it is preferably 120% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

(Other components)

The B block may further contain other constituent units which enhance the solubility in a solvent. Examples of the other constituent units constituting the B block include monomers having an unsaturated double bond that can be copolymerized with a monomer derived from the constituent unit represented by the general formula (I). Among them, the following general formula is preferred. (II) The constituent unit shown.

(In general formula (II), A 'is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, and-[CH (R ⁶ ) -CH (R ⁷ ) -O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ is a monovalent 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, -CH ₂ CHO or -CH ₂ COOR ⁹ is a monovalent group, R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; the above-mentioned hydrocarbon group may also have a substituent; x represents an integer of 1 to 18, y is an integer from 1 to 5, and z is 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 ′ has no atom, that is, C (carbon atom) in the general formula (II) and R ⁵ are bonded through no other atom. Examples of the divalent linking group include the same ones as A in the general formula (I). As A 'of the general formula (II), in terms of solubility in an organic solvent, a direct bond or a divalent linking group containing a -CONH- group or a -COO- group is preferred.

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 alkyl group having 1 to 18 carbon atoms may be any of linear, branched, and cyclic groups, and examples thereof 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 and the like. The alkenyl group having 2 to 18 carbon atoms may be any of linear, branched, and cyclic. Examples of such alkenyl include vinyl, allyl, and propenyl. 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 terminal of the alkenyl group. Examples of the substituent of an aliphatic hydrocarbon such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

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

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

The hydrocarbon group in R ⁸ is the same as that shown in 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. R ⁵ in the structural unit represented by the general formula (II) may be the same as or different from each other.

Among these, R ^{5 is} preferably selected so as to be excellent in compatibility with the following solvents. Specifically, for example, a diol generally used as a solvent for a colored resin composition for a color filter is used in the above-mentioned solvent. In the case of solvents such as ether acetates, ethers, and esters, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, and benzyl are preferred.

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

(Constituting unit derived from acidic group-containing monomer)

From the standpoint of improving the philophilicity of the B block and improving the dispersibility and dispersion stability of the color material dispersion liquid, the B block is preferably further composed of a constituent unit derived from an acidic group-containing monomer. Examples of the acidic group-containing monomer include monomers containing an unsaturated double bond and an acidic group that can be copolymerized with the monomer derived from the structural unit represented by the general formula (I). Examples of the acidic group include a carboxyl group, a phosphate group, a sulfo group, and a boric acid group. Among these, a carboxyl group is preferred in terms of developability. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, and butenoic acid. , Cinnamic acid, acrylic acid dimer, etc. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride or phthalic anhydride, cyclohexanedicarboxylic anhydride, or ω- Carboxy-polycaprolactone mono (meth) acrylate and the like. In addition, an anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as the carboxyl precursor. Among these, (meth) acrylic acid is particularly preferable in terms of copolymerization or cost, solubility, glass transition temperature, and the like.

In the case where the constituent unit derived from the acid-group-containing monomer is contained, the content ratio of the constituent unit derived from the acid-group-containing monomer in the block copolymer before the salt formation is not particularly limited, and it is relative to the embedded copolymer. The total mass of the total constituent units of the segment copolymer is preferably 0.05 to 4.5% by mass, and more preferably 0.07 to 3.7% by mass. By setting the content ratio of the constituent unit derived from the monomer containing an acidic group to be above the lower limit value, the effect of suppressing the development residue is excellent. By being less than the above upper limit value, it is possible to prevent the deterioration of the development adhesion and the solvent re- Degradation of solubility. In addition, the constituent unit derived from the acidic group-containing monomer may be composed of one kind, or may include two or more kinds of constituent units.

The number of the constituent units constituting the B block is not particularly limited. In terms of effectively functioning the solvent-soluble portion and the color-friendly material portion and improving the dispersibility of the color material, it is preferably 10 to 300, more preferably The number is 10 to 100, and more preferably 10 to 70.

In the B block in the block copolymer, the content ratio of the constituent unit represented by the general formula (II) is higher than the total constituent unit of the B block in terms of improving the solvent-solvent property or the dispersibility of the color material. The total mass is preferably 30 to 95% by mass, and more preferably 40 to 90% by mass. In addition, the content ratio of the said structural unit is calculated from the feed mass at the time of synthesizing a B block.

In addition, in the block copolymer before the salt formation, the content ratio of the constituent units represented by the general formula (II) described above is in terms of improving the dispersibility of the color material with respect to the total of the total constituent units of the block copolymer. The mass is preferably 40 to 95% by mass, and more preferably 50 to 90% by mass. In addition, the content ratio of the said structural unit is calculated from the feed mass at the time of a block copolymer before a synthetic salt is formed.

The B block is preferably selected as a constitutional unit so as to function as a lipophilic site. The constitutional unit represented by the general formula (II) may be composed of one species or may include two or more constitutional units. . Two or more kinds of constituent units included in the B block may be randomly arranged in the block.

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

In the case of containing a structural unit derived from a hydroxyl-containing monomer, the content ratio of the structural unit derived from a hydroxyl-containing monomer in the block copolymer before salt formation is relative to the total constituent unit of the block copolymer The total mass is preferably 1 mass% or more, more preferably 2 mass% or more, still more preferably 3 mass% or more, and even more preferably 4 mass% or more. If it is more than the said lower limit value, it can become the one with favorable 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 even more preferably 40% by mass or less. If it is below the above-mentioned upper limit, it may be preferable in terms of increasing the introduction ratio of other useful monomers. In addition, the content ratio of the said structural unit is calculated from the feed mass at the time of a block copolymer before a synthetic salt is formed.

Further, in the present invention, in terms of improving the solvent resolubility, it is preferable to include a structural unit derived from an aromatic group-containing monomer in the B block. In the case of including a structural unit derived from an aromatic group-containing monomer, it is considered that it is easy to improve the compatibility with a solvent or other components, and therefore the solvent resolubility is improved. As the constituent 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 derived from the constituent 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, Styrene such as styrene, vinyl ether such as phenyl vinyl ether. In terms of improving development adhesion, among them, it is preferable to use an aromatic group-containing monomer having a glass transition temperature value (Tgi) of a homopolymer of each monomer of 0 ° C or higher, and more preferably used. It becomes an aromatic group-containing monomer at 10 ° C or higher. Among them, it is preferable to select from the group consisting of benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and benzene (meth) acrylate, from the viewpoint of easily improving re-solubility. One or more of the group consisting of oxyethyl esters, and further preferably selected from the group consisting of benzyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate More than one.

In the case of containing a constituent unit derived from an aromatic group-containing monomer, in terms of improving solvent resolubility, in a block copolymer before salt formation, The content ratio of the structural unit is preferably 1 mass% or more, more preferably 2 mass% or more, still more preferably 3 mass% or more, and even more preferably 4 mass% with respect to the total mass of the total constituent units of the block copolymer. the above. If it is more than the said lower limit, it will become a solvent with good re-solubility. 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 even more preferably 40% by mass or less. If it is below the above-mentioned upper limit, it may be preferable in terms of increasing the introduction ratio of other useful monomers.

Among these, in terms of improving the development adhesion and the solvent resolubility, the B block preferably contains (i) a structural unit derived from a hydroxyl-containing monomer and an aromatic group-containing monomer. A structural unit and (ii) at least one of a structural unit derived from a hydroxyl group and an aromatic group containing monomer.

In the case where (i) a constituent unit derived from a hydroxyl group-containing monomer and a constituent unit derived from an aromatic group-containing monomer are included, 1 part by mass relative to a constituent unit derived from an aromatic group-containing monomer Preferably, it contains 0.15 mass parts or more of the structural unit derived from the hydroxyl group-containing monomer, and more preferably contains 0.5 mass parts or more. The reason is that if it is at least the above-mentioned lower limit value, it can be excellent in development adhesiveness. In the same manner, it is preferable that the amount of the constituent unit derived from a hydroxyl group-containing monomer is 15 parts by mass or less with respect to 1 part by mass of the constituent unit of the aromatic group-containing monomer, and it is more preferably 7 parts by mass or less. Contains constituent units derived from a hydroxyl-containing monomer. The reason is that if it is equal to or less than the above-mentioned upper limit value, it can be excellent in solvent resolubility. Among them, the value of the glass transition temperature (Tgi) with respect to the homopolymer is 1 part by mass or more of the constituent unit derived from the aromatic group-containing monomer, and the glass transition containing the homopolymer in the above range is particularly preferred. The value of temperature (Tgi) is a structural unit derived from a hydroxyl-containing monomer at 10 ° C or higher. The reason for this is that by including the above-mentioned lower limit value, the development adhesiveness can be more excellent, and by containing it below the above-mentioned upper limit value, the solvent resolubility can be made more excellent.

Examples of the (ii) hydroxyl- and aromatic-group-containing monomer in the structural unit derived from the hydroxyl- and aromatic-group-containing monomer include, for example, (meth) acrylic acid 2-hydroxy-3-phenoxy Propyl ester, 2-propenyloxyethyl-2-hydroxyethyl-phthalic acid, and the like. The homopolymer has a glass transition temperature value (Tgi) of 10 ° C or higher, and the effect obtained from the structural unit derived from a hydroxyl group-containing monomer and the structural unit derived from an 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 improving development adhesion, development speed, and solvent resolubility. In the case where (ii) a constitutional unit derived from a monomer containing a hydroxyl group and an aromatic group, the development adhesion, the development speed, and the solvent resolubility can be improved by one constitutional unit, so other functions can be improved. Advantages of introduction ratio of sex monomer.

In terms of improving the development adhesion, it is preferable that the monomers whose total glass transition temperature value (Tgi) is 10 ° C. or higher are 75 mass% or more in the B block. It is more preferably 85% by mass or more.

In the above-mentioned block copolymer, the ratio m / n of the number m of the constituent units of the A block to the number n of the constituent units 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 within a range of 0.1 to 1.0.

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

The weight average molecular weight Mw of the above block copolymer is not particularly limited. In terms of making the color material dispersibility and dispersion stability good, it is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 3000 ~ 12000. Here, the weight average molecular weight (Mw) is calculated as a standard polystyrene conversion value by gel permeation chromatography (GPC). In addition, in this invention, the weight average molecular weight Mw of a block copolymer is calculated | required by GPC (gel permeation chromatography) as a standard polystyrene conversion value. For the measurement, HLC-8120GPC manufactured by Tosoh Co., Ltd. was used. The dissolution solvent was set to N-methylpyrrolidone with 0.01 mol / L of lithium bromide, and the polystyrene standards for calibration curves were set to Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are manufactured by Polymer Laboratories, Easi PS-2 series) and Mw1090000 (manufactured by Tosoh Co., Ltd.), and the measurement column is set to TSK-GEL ALPHA- M × 2 (manufactured by Tosoh Co., Ltd.). The macromonomer, the salt-type block copolymer, and the graft copolymer, which are the raw materials of the block copolymer, are also carried out under the conditions described above.

In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.

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 for this is that a copolymer having a uniform molecular weight, which is less prone to chain transfer or inactivation, can be produced, and dispersibility can be improved. Examples of the living polymerization method include living anionic polymerization methods such as a living radical polymerization method and a radical transfer polymerization method, and living cationic polymerization methods. A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, a block copolymer can be produced by first manufacturing the A block and polymerizing the constituent units constituting the B block with the A block. In the above-mentioned production method, the order of polymerization of the A block and the B block may be reversed. Alternatively, the A block and the B block may be produced separately, and thereafter 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, as the block copolymer, in terms of improving the dispersibility of the color material, at least a part of the nitrogen site at the terminal of the structural unit represented by the general formula (I) is preferably selected from the group consisting of organic acids. At least one of the group consisting of a compound and a halogenated hydrocarbon forms a salt-type block copolymer. Among the above-mentioned organic acid compounds, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferred, and among the above-mentioned halogenated hydrocarbons, the following general formula (2) is preferred ). That is, as at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon, one or more compounds selected from the group consisting of the following general formulae (1) to (3) are preferably used. .

(In the general formula (1), R ^a represents ^a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl or benzyl group which may have a substituent, or an alkylene group having 1 to 4 carbon atoms Group) propenyl group; in the general formula (2), R ^b , R ^{b ′} and R ^{b ″} each independently represent a hydrogen atom, an acid group or an ester group thereof, and a carbon number of 1 to 20 which may have a substituent. A chain, branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl or benzyl group which may have a substituent, or -OR ^f , where R ^f represents a straight chain having 1 to 20 carbon atoms which may have a substituent , A branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl or benzyl group which may have a substituent, or a (meth) acrylfluorenyl group with an alkylene group separated by 1 to 4, X represents a chlorine atom, a bromine atom, or an iodine atom; in the general formula (3), R ^c and R ^d each independently represent a hydrogen atom, a hydroxyl group, and a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; vinyl, may have a substituent of phenyl or benzyl group, or -OR ^e, R ^e represents C 1 - 20 linear, branched or cyclic alkyl groups, vinyl groups, phenyl or benzyl groups which may have substituents, or (meth) acrylfluorenyl groups with an alkylene group separated by 1 to 4 carbon atoms; of which , At least one of R ^c and R ^d includes a carbon atom.)

(One or more compounds selected from the group consisting of the above general formulae (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 a straight chain or a branched chain, and may include a cyclic structure. Specific examples include methyl, ethyl, n-propyl, and isopropyl. , N-butyl, isobutyl, second butyl, third butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, twelve Alkyl, cyclopentyl, cyclohexyl, tetradecyl, octadecyl, etc. Preferred examples include straight, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, and more preferred examples include carbon number 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, fluorenyl, fluorenyl and the like having 1 to 5 carbon atoms.

In R ^b , R ^{b ′} , R ^{b ″,} and R ^f , examples of the substituent which may have a phenyl group or a benzyl group include an acid group or an ester group thereof, and an alkane having 1 to 5 carbon atoms. Group, fluorenyl group, fluorenyloxy group, etc. In R ^b , R ^{b ′} , R ^{b ″,} and R ^f , a linear, branched, or cyclic alkane having 1 to 20 carbon atoms which may have a substituent Examples of the substituents for a group or a vinyl group include an acid group or an ester group thereof, a phenyl group, a fluorenyl group, and a fluorenyl group. In R ^b , R ^{b ′} , R ^{b ″,} and R ^f , an acidic group refers to a group that releases protons in water to show acidity. Specific examples of the acidic group include a carboxyl group (-COOH) and a sulfo group ( -SO ₃ H), phosphonic acid group (-P (= O) (OH) ₂ ), phosphonic acid subunit (> P (= O) (OH)), An acid group (-B (OH) ₂ ), a di-substituted boronic acid group (> BOH), etc., may also be anions that dissociate hydrogen atoms such as carboxylic acid ester groups (-COO-), etc. Alkali metal ions such as potassium ions form acidic salts of salts. Examples of the acidic ester group include a carboxylic acid ester (-COOR), a sulfonic acid ester (-SO ₃ R), a phosphoric acid ester (-P (= O) (OR) ₂ ), and (> P (= O ) (OR)), Acid ester (-B (OR) ₂ ), disubstituted borate (> BOR), and the like. Among them, the ester group as the acidic group is preferably a carboxylic acid ester (-COOR) in terms of dispersibility and dispersion stability. In addition, R is a hydrocarbon group, which is not particularly limited. Among them, in terms of dispersibility and dispersion stability, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

In terms of dispersibility, dispersion stability, alkali developability, and suppression of development residues, the compound of the general formula (2) preferably has a group selected from carboxyl groups, One or more functional groups among acid groups, disubstituted boric acid groups, anions of these, alkali metal salts of these, and esters of these, more preferably having a functional group selected from the group consisting of carboxyl, carboxylic acid ester, and carboxylic acid Functional groups in salt and carboxylic acid esters. In the case where the compound of the general formula (2) has an acidic group and an ester group (hereinafter referred to as an acidic group, etc.), it is inferred that both the acidic group side and the halogen atom side hydrocarbons possessed by the compound may have a nitrogen site at the terminal. Although a salt is formed, compared with the case where a terminal nitrogen site forms an acid group, etc., the terminal nitrogen site forms a salt with a halogen atom side hydrocarbon stably. In addition, it is presumed that the dispersibility and dispersion stability are improved by adsorbing the color material to a salt-forming site stably existing.

When the compound of the said general formula (2) has the said acidic group, etc., it may have 2 or more of the said acidic group. When there are two or more of the above-mentioned acidic groups and the like, the above-mentioned acidic groups and the like having a plurality of them may be the same or different. The number of the above-mentioned acidic groups and the like of the compound of the general formula (2) is preferably 1-3, more preferably 1-2, and even more preferably one.

R ^a has an aromatic ring in the general formula (1), at least one of R ^b , R ^{b ′} and R ^{b ”} in the general formula (2) has an aromatic ring, and in the 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 colored composition having excellent contrast can be obtained. In terms of the above, it is better.

In terms of improving the dispersibility of the color material, the molecular weight of one or more compounds selected from the group consisting of the general formulae (1) to (3) is preferably 1,000 or less, and preferably 50 to 800. It is more preferably 50 to 400, still more preferably 80 to 350, and most preferably 100 to 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, and mono-n-propylsulfuric acid. . 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, cetyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, iodination 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, α-bromophenylacetic acid methyl ester, 3- (bromomethyl) phenylboronic acid, and the like. 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, phenylphosphinic acid, and phenylphosphonic acid. , Dimethyl propylene ethoxy ethyl acid phosphate and the like. In terms of particularly excellent dispersion stability, it is preferably selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethylacryloxyethyl ethyl acid phosphate, dibutyl phosphoric acid, and benzyl chloride. , Benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid-hydrate, one or more of which are preferably selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, and benzyl chloride One or more of the group consisting of a methyl group, a benzyl bromide group, and a p-toluenesulfonic acid-hydrate. In addition, in terms of improving the inhibitory effect of the development residue by combination with the specific block copolymer described above, it is also preferable to use a compound represented by the general formula (2) having an acidic group and an ester group thereof, Among these, it is also preferable to use a member selected from the group consisting of 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 an organic acid compound and a halogenated hydrocarbon is formed due to the formation of a nitrogen site at the terminal of the structural unit represented by the general formula (I). Salt, it is preferable that the total of at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon is 0.01 Mo with respect to the terminal nitrogen site of the structural unit represented by the general formula (I) It is more preferably 0.1 mol or more, more preferably 0.2 mol or more, and even more preferably 0.3 mol or more. If it is more than the said lower limit value, the effect which improves the dispersibility of a color material by salt formation will become easy to be acquired. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.7 mol or less, and even more preferably 0.6 mol or less. If it is below the said upper limit, it can be excellent in the development adhesiveness or solvent resolubility. In addition, at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon may be used alone or in combination of two or more. When two or more types are combined, the total content is preferably within the above range.

As a method for preparing the salt-type block copolymer, a solvent in which the block copolymer before the salt formation is dissolved or dispersed is added, and at least one selected from the group consisting of the organic acid compound and a halogenated hydrocarbon is added. A method of stirring and then heating if necessary. Furthermore, the terminal nitrogen site 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 organic acid compound and a halogenated hydrocarbon, and The ratio can be confirmed by a known method such as nuclear magnetic resonance (NMR, Nuclear Magnetic Resonance).

The amine value of the obtained salt-type block copolymer is smaller than that of the block copolymer before salt formation, and the smaller the value corresponds to the amount of salt formation. However, since the salt-forming site is the same as the nitrogen site corresponding to the terminal end of the amine group, or in order to become an enhanced color material adsorption site, there is a possibility that the color material dispersibility or color material dispersion stability is improved by salt formation. tendency. In addition, like the amine group, if the salt formation site is too much, the solvent resolubility is adversely affected. Therefore, in the present invention, the amine value of the block copolymer before salt formation can be used as an index for improving the color material dispersion stability and 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 below the above upper limit value, the compatibility with other components will be excellent, and the solvent re-solubility will be good.

In addition, in the salt-type block copolymer, the amine value of the salt-type block copolymer in which a salt is formed by the compound represented by the general formula (2) can be set according to the method described in JIS K 7237: 1995. Measured value. The reason is that the compound of the general formula (2) is a salt of a terminal nitrogen site of a structural unit represented by the general formula (I) and a hydrocarbon on the side of the halogen atom. The state of salt formation 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 in which a salt is formed by using the compound represented by the general formula (1) or (3) can be obtained by inserting the salt-type block copolymer according to The amine value of the segment copolymer is calculated and calculated as described below. This is because the compound represented by the general formula (1) or (3) is a terminal nitrogen site of the structural unit represented by the general formula (I) and the acidic group forms a salt. Therefore, if the JIS K 7237 is used, : The method described in 1995 for measuring the amine value of such a salt-type block copolymer results in a change in the state of salt formation, and an accurate value cannot be measured. First, the amine value of the block copolymer before salt formation was determined by the above method. Next, the 13C-NMR spectrum of the salt-type block copolymer was measured using a nuclear magnetic resonance apparatus. According to the obtained spectrum data, no salt was formed in the nitrogen site of the terminal of the structural unit represented by the general formula (I). The ratio of the integral value of the peak of the carbon atom adjacent to the formed nitrogen atom to the peak of the carbon atom adjacent to the nitrogen atom formed by the salt is determined. The salt type block copolymer is selected from the group consisting of the general formula (1) or (3). The reaction rate of one or more compounds in the group with respect to the terminal nitrogen site of the structural unit represented by the general formula (I) (the ratio of the nitrogen site at the terminal where the salt is formed). The amine value of the terminal nitrogen site of the structural unit represented by the general formula (I) in which one or more compounds selected from the group consisting of the above-mentioned general formula (1) or (3) are salt-formed is represented by the amine value. Set to 0, subtract the amine value of the block copolymer before salt formation from (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 by the salt formation calculated from the ratio of the nitrogen site at the end of the salt formation (%) / 100 calculated from the NMR spectrum was calculated. Amine value of salt type block copolymer = {Amine value of block copolymer before salt formation measured by method described in JIS K 7237: 1995}-{Measured by method described in JIS K 7237: 1995 Amine value of the block copolymer before salt formation} × {Ratio of nitrogen sites at the salt formation end calculated from 13C-NMR spectrum (%) / 100}

The acid value of the dispersant used in the present invention is not particularly limited. Among them, in terms of development adhesion and solvent resolubility, it is preferably 18 mgKOH / g or less, and more preferably 12 mgKOH / g or less. 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 the solvent re-solubility and development adhesiveness, and the substrate adhesiveness and dispersion stability. The smaller the acid value, the less likely it is to be attacked by the alkaline developer, and therefore it is considered that the development adhesion is good. On the other hand, in terms of the inhibitory effect of the development residue, 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 the salt formation is preferably 18 mgKOH / g or less, and more preferably 12 mgKOH, in terms of development adhesion and solvent resolubility. / g or less. In addition, in terms of further improving the solvent resolubility and development adhesion, and the 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 inhibitory effect of the development residue, it is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more.

As described above, the acid value of the block copolymer before the salt formation indicates the mass (mg) of potassium hydroxide required to neutralize the acid component contained in 1 g of the solid content of the block copolymer, by Measured by the method described in JIS K 0070: 1992. In addition, as for the salt-type block copolymer, the acid value of the salt-type block copolymer obtained by salt formation using the compound represented by the general formula (2) is also measured by a method described in JIS K 0070: 1992. Get the value. The reason is that the compound of the general formula (2) is a salt of a terminal nitrogen site of a structural unit represented by the general formula (I) and a hydrocarbon on the side of the halogen atom. Changes in the state of salt formation can be measured. On the other hand, when the salt-type block copolymer is a salt-type block copolymer that is salt-formed with a compound represented by the general formula (1) or (3), the acidic group 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 in which a salt is formed from the compound represented by the general formula (1) or (3) is calculated from the value obtained by the following formula. The reason for this is that if the acid value of a salt-type block copolymer in which a salt is formed from a compound represented by the general formula (1) or (3) is measured using the method described in JIS K 0070: 1992, the salt is measured. The formed state changes, and accurate values cannot be measured.

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

Here, the total acid value of the compound represented by the above-mentioned general formula (1) or (3) for salt formation can be measured by the method described in the aforementioned JIS K 0070: 1992. On the other hand, the acid value consumed for salt formation is calculated from the salt formation ratio obtained by NMR. Specifically, the acid value consumed for salt formation is measured by, for example, a 13C-NMR spectrum of a salt-type block copolymer using a nuclear magnetic resonance apparatus. According to the obtained spectral data, nitrogen is not formed at the terminal nitrogen site. The ratio of the integral value of the peak of the carbon atom adjacent to the atom to the peak of the peak of the carbon atom adjacent to the nitrogen atom forming the salt was calculated, and 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 was calculated. By {the amine value of the block copolymer before the salt formation measured by the method described in JIS K 7237: 1995} × {the ratio of the nitrogen site at the end of the salt formation calculated from the 13C-NMR spectrum (%) / 100 } To calculate the consumed amine value, which is the same value as the acid value consumed by salt formation. However, when forming a salt with the compound represented by the general formula (1) at 1 mol or less with respect to the terminal nitrogen site of the structural unit represented by the general formula (I), one When a salt of the compound represented by the above-mentioned general formula (3) with an acidic group is 1 mol or less, or when the salt of the compound represented by the above-mentioned general formula (3) with two acidic groups is 0.5 mol or less 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 acidity in the salt-type block copolymer after the salt formation is The group does not affect the acid value, and therefore may have the same acid value as the block copolymer before the salt formation. 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, an acidic group that does not undergo salt formation also exists in the dispersant after the salt formation. Therefore, as shown in the above formula, the acid value of the amount of acidic groups not subjected to salt formation and the acid value of the block copolymer before salt formation are added to calculate the acid value of the dispersant.

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 even 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, and more preferably 5 mgKOH / g or more. In addition, in the present invention, the hydroxyl value indicates the mass (mg) of KOH required to neutralize acetic acid combined with the acetic acid compound obtained from 1 g of the solid content, which refers to titration by potential difference in accordance with JIS K 0070: 1992. Value obtained by law.

In the color material dispersion liquid of the present invention, as the dispersant, at least one of the above-mentioned block copolymers and salt-type block copolymers is used, and the content thereof depends on the type of the color material to be used, and further on the following color filters. It is appropriately selected depending on the concentration of the solid matter component in the photosensitive colored resin composition and the like. The content of the dispersant is preferably 3 to 45 parts by mass, and more preferably 5 to 35 parts by mass relative to 100 parts by mass of the total solids component in the color material dispersion. If it is at least the above lower limit value, the dispersibility and dispersion stability of the color material will be excellent, and the storage stability of the photosensitive colored resin composition for a color filter 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 a colored layer with a high color material concentration, the content of the dispersant is preferably 3 to 25 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion liquid. It is formulated at a ratio of 5 to 20 parts by mass. In addition, in this invention, a solid content means the owner other than the said solvent, and includes the monomer etc. which were melt | dissolved in a solvent.

<Color material>

In the present invention, the color material is not particularly limited as long as it can achieve a desired color development when forming a coloring layer of a color filter. Various organic pigments, inorganic pigments, dispersible dyes, and dyes can be used. Salt-forming compounds and the like are used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color rendering properties and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the color index (C.I .; issued by The Society of Dyers and Colourists), and specific examples include those with a color index (C.I.) number as described below.

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 derivatives of CI Pigment Yellow 150; 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, 1 78, 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.

Specific examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, Huang Dan, zinc yellow, iron iron (iron oxide red (III)), cadmium red, ultramarine, Iron blue, chrome oxide green, cobalt green, brown earth, titanium black, synthetic iron black, carbon black, etc.

For example, in the case where a pattern of a light-shielding layer is formed on the substrate of a color filter by using the color material dispersion of the present invention as a photosensitive coloring resin composition for a color filter described below, the light-shielding property is adjusted in the ink. Black pigment. As the black pigment having a high light-shielding property, for example, an inorganic pigment such as carbon black or ferric oxide, or an organic pigment such as cyanine black can be used.

Examples of the dispersible dye include those capable of dispersing by adding various substituents to the dye or using a solvent with a low solubility in combination. As a salt-forming compound of a dye, it refers to a compound that forms a salt with a dye and a counter ion, for example, a salt-forming compound of a basic dye and an acid, a salt-forming compound of an acidic dye and a base, and the use of a known lake (forming The salinization) method dissolves a soluble dye in a solvent, and insoluble lake pigment in the solvent. In the present invention, 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 dispersant of the present invention, the dispersibility or dispersion stability of the color material can be improved.

The dye can be appropriately selected from dyes known in the art. Examples of such dyes include azo dyes, metal salt azo dyes, anthraquinone dyes, triphenylmethane dyes, Dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, phthalocyanine dyes, and the like. In addition, as a standard, if 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 a salt selected from pyrrolopyrrole dione 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 a compound, it is preferable from the viewpoint that the effect of suppressing the sublimation or precipitation of the color material caused by using the dispersant is high, and a coloring layer with high brightness can be formed. The color material preferably contains at least one selected from the group consisting of a pyrrolopyrrole dione pigment, a quinophthalone pigment, a copper phthalocyanine pigment, a zinc phthalocyanine pigment, and a quinophthalone dye.

Examples of the pyrrolopyrrole dione pigment include CI Pigment Red 254, 255, 264, and 272, and the pyrrolopyrrole dione pigment represented by the following general formula (i). Among them, CI Pigment Red 254 is preferred. , 272, and at least one of pyrrolopyrrole dione pigments in which R ²¹ and R ²² are 4-bromophenyl groups in the following general formula (i).

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

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

The average primary particle diameter of the color material used in the present invention is not particularly limited as long as it is a coloring layer of a color filter, as long as it can achieve the desired color development. The type of color material varies, but it is preferably in the range of 10 to 100 nm, and more preferably 15 to 60 nm. By setting the average primary particle diameter of the color material to be in the above range, a display device having a color filter manufactured using the color material dispersion of the present invention can be made to have high contrast and high quality.

The average dispersion particle size of the color material in the color material dispersion liquid also varies depending on the type of the 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. As a particle size measurement using a laser light scattering particle size distribution meter, the color material dispersion liquid can be appropriately diluted (for example, 1000 times, etc.) to a concentration that can be measured by a laser light scattering particle size distribution meter using a solvent used in the color material dispersion liquid. , Using 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 at 23 ° C. by a dynamic light scattering method. Here, the average distribution particle diameter is a volume average particle diameter.

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 may be subjected to a miniaturization treatment and used.

The content of the color material in the color material dispersion of the present invention 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, and more preferably 8 to 30 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. 70 mass parts ratio. Especially in the case of forming a coating film or a colored layer with a high color material concentration, it is preferably 30 to 80 parts by mass, and more preferably 40 to 30 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. 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 and can dissolve or disperse these. The solvent may be used alone or in combination of two or more. Specific examples of the solvent include alcohol-based solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol and ethoxyethoxy Carbitol solvents such as ethyl alcohol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate , Ester solvents such as ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate; acetone, methyl ethyl Ketone solvents such as ketones, methyl isobutyl ketones, cyclohexanone, and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1- Glycol ether acetate solvents such as butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl acetate Carbitol acetate solvents such as carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol two Glycol ether solvents such as methyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; N, N-dimethyl methyl ether Aprotic solvents such as amidine, N, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; benzene, Unsaturated hydrocarbon solvents such as toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, in terms of the 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 butylcarbitol acetic acid in terms of solubility of other components or coating suitability. 1 of the group consisting of esters (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate More than that.

The color material dispersion of the present invention is preferably such that the above solvent is generally in a range of 55 to 95% by mass with respect to the total amount of the color material dispersion containing the solvent, and more preferably in a range of 65 to 90% by mass. It is preferably within a range of 70 to 88% by mass. When the solvent is too small, the viscosity increases and the dispersibility tends to decrease. Moreover, when there are too many solvents, the density | concentration of a color material may fall and it may become difficult to reach the target chromaticity coordinate.

<Other ingredients>

In the color material dispersion liquid 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 blended as necessary. Examples of the dispersion assisting resin include alkali-soluble resins exemplified in the following photosensitive color resin composition for color filters. There are cases in which the color material particles are difficult to contact with each other due to the steric hindrance of the alkali-soluble resin, and the effect of reducing the dispersant is achieved by dispersion stabilization or the dispersion stabilization effect. Examples of the other components include a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-shrinking agent, an antioxidant, an anti-agglomerating agent, and an ultraviolet absorber.

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

<Manufacturing method of color material dispersion liquid>

In the present invention, if the method for producing a color material dispersion is to obtain a color material dispersion obtained by dispersing the color material in a solvent by using the dispersant of the block copolymer or the salt-type block copolymer described above, 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 any of the following two production methods.

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

Moreover, the second manufacturing method of the color material dispersion of the present invention in the case of using a dispersant as a salt-type block copolymer has the following steps: a solvent, the above-mentioned block copolymer, an organic acid compound, etc., and a color material The color material is dispersed while mixing at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) to form an organic acid compound or the like.

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

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

Specifically, it can be pre-dispersed with 2.0 mm zirconia beads with a relatively large bead diameter, and then formally dispersed with 0.1 mm zirconia beads with a relatively small bead diameter. After the dispersion, it is preferably filtered through 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 of the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. The photosensitive colored resin composition for a color filter of the present invention can form a colored layer with high brightness by using the color material dispersion of the present invention, and can suppress cracking of 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 within a range that does not impair the effect of the present invention. Contains other ingredients. Hereinafter, each component contained in the photosensitive colored resin composition for a color filter of the present invention will be described. The dispersant, the color material, and the solvent are the same as those described in the color material dispersion 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 among those soluble in an alkaline developing solution used in pattern formation. In the present invention, the 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 an acidic group and usually having a carboxyl group, and specifically, acrylic resins such as an acrylic copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group, Epoxy (meth) acrylate resin having a carboxyl group and the like. Among them, those having a carboxyl group in a side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain are particularly preferred. This is because the film strength of the cured film formed by containing a photopolymerizable functional group is improved. Moreover, these acrylic copolymers, acrylic resins, such as a styrene-acrylic copolymer, and an epoxy acrylate resin may be used in mixture of 2 or more types.

Acrylic resins such as an acrylic copolymer having a carboxyl group as a structural unit and a styrene-acrylic copolymer having a carboxyl group are, for example, a carboxyl group-containing ethylenically unsaturated monomer by a known method, and if necessary, copolymerization A (co) polymer obtained by (co) polymerizing other polymerized monomers. Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic Acid, butenoic acid, cinnamic acid, acrylic acid dimer, etc. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride or phthalic anhydride, cyclohexanedicarboxylic anhydride, or ω- Carboxy-polycaprolactone mono (meth) acrylate and the like. In addition, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as the carboxyl precursor. Among these, (meth) acrylic acid is particularly preferable in terms of copolymerization or cost, solubility, glass transition temperature, and the like.

In terms of excellent adhesion of the colored layer, the alkali-soluble resin preferably further has a hydrocarbon ring. It was found that, because an alkali-soluble resin has a hydrocarbon ring as a bulky base, the obtained colored layer has solvent resistance, and in particular, swelling of the colored layer can be suppressed. Although the effect is not clear, it is inferred that the molecules in the colored layer are inhibited from moving due to the large number of hydrocarbon rings contained in the colored layer. As a result, the strength of the coating film is increased and swelling caused by the solvent is suppressed. Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and combinations thereof. The hydrocarbon ring may also have a carbonyl group, a carboxyl group, an oxycarbonyl group, and amidine. And other substituents. Among them, when an aliphatic ring is contained, 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, and Alkane, tricyclic [5.2.1.0 (2,6)] decane (dicyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, fluorene and other aromatic rings; biphenyl, bitriene Chain polycyclics such as benzene, diphenylmethane, triphenylmethane, fluorene, etc., or a Cardo structure represented by the following chemical formula (ii).

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 hydrocarbon ring which may be substituted.)

In the case where the alkali-soluble resin has the cis-butene diimide structure represented by the general formula (iii), the hydrocarbon ring has a nitrogen atom, so the compatibility with the dispersant of the present invention is excellent, and the development residue is suppressed. The effect is improved. Specific examples of the hydrocarbon ring which may be substituted in R ^M of the general formula (iii) include the same as the specific examples of the hydrocarbon ring.

In the case where an aliphatic ring is contained as the 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. Moreover, when the Cardo structure shown by the said chemical formula (ii) is included, the hardening property of a colored layer improves and solvent resistance (NMP swelling suppression) improves, and it is especially preferable in this respect.

In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each constituent unit by using an acrylic copolymer containing a constituent unit having the above-mentioned hydrocarbon ring, which is different from the constituent unit having a carboxyl group, and increase the amount of the constituent unit having the above-mentioned hydrocarbon ring. It is easy to improve the function which the constituent unit has, and it is preferable in this respect. An 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 "other copolymerizable monomer". Examples of the ethylene-based unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, and (meth) Acrylic iso Esters, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, etc. are more effective in maintaining the cross-sectional shape of the colored layer after development even during the heat treatment. Preferred are cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, Styrene, particularly preferably styrene. Further, in terms of the effect of suppressing the development residue, as the aforementioned ethylenically unsaturated monomer having a hydrocarbon ring, a monomer having the above-mentioned maleimide structure is preferred, and styrene is particularly preferred. Preferable is styrene.

The alkali-soluble resin used in the present invention preferably has an ethylene-based double bond in a side chain. In the case of having a vinyl-based double bond, the alkali-soluble resin and the dispersant of the present invention described above can form a cross-linking bond during the hardening step of the resin composition at the time of manufacturing the color filter, and the alkali-soluble resin is mutually Or the alkali-soluble resin may form a cross-linking bond with a photopolymerizable compound or the like. Therefore, if an alkali-soluble resin having a vinyl-based double bond in a side chain is used in combination with the dispersant of the present invention, the film strength of the cured film can be further enhanced by a synergistic effect, so the brightness of the colored layer and ITO can be further improved The cracking property of the film further improves the development resistance, and also suppresses the thermal shrinkage of the cured film to make it excellent in adhesion to the substrate. The method of introducing an ethylene-based double bond into an alkali-soluble resin may be appropriately selected from methods known in the art. For example, a compound having an epoxy group and an ethylene-based double bond in the molecule, such as glycidyl (meth) acrylate, and the carboxyl group of an alkali-soluble resin can be added to introduce a side chain into an ethylene system. Method for double bond; or introducing a structural unit having a hydroxyl group into a copolymer in advance, and adding it to a compound having an isocyanate group and a vinyl double bond in the molecule, and introducing a vinyl double bond to the side chain Methods, etc.

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

The alkali-soluble resin used in the present invention is preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer including a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and more preferably a composition having a carboxyl group. Units, acrylic copolymers having a hydrocarbon ring constituting unit and acrylic double bonds constituting units, and acrylic resins such as styrene-acrylic copolymers.

The alkali-soluble resin can be an alkali-soluble resin having desired properties by appropriately adjusting the feeding amount of each constituent unit.

In terms of obtaining a good pattern, the feed amount of the carboxyl group-containing ethylene-based unsaturated monomer is preferably 5 mass% or more, more preferably 10 mass% or more, based on the total amount of the monomers. On the other hand, in terms of suppressing film roughness on the surface of the pattern after development, etc., the feeding amount of the carboxylic group-containing ethylenically unsaturated monomer is preferably 50% by mass or less relative to the total amount of the monomer, and more preferably It is 40% by mass or less. If the ratio of the ethylenically unsaturated monomer containing a carboxyl group is equal to or more than the above-mentioned lower limit value, the solubility of the obtained coating film to the alkaline developer is sufficient, and if the ratio of the ethylenically unsaturated monomer containing a carboxyl group is sufficient, When it is less than the above upper limit value, the developed pattern tends to be less likely to be peeled off from the substrate or roughened on the surface of the pattern during development using an alkaline developer.

In addition, acrylic resins such as acrylic copolymers containing styrene-acrylic copolymers and styrene-acrylic copolymers, which are more preferably used as alkali-soluble resins, include structural units having an ethylenic double bond. The amount of the compound to be bonded is preferably from 10% by mass to 95% by mass, and more preferably from 15% by mass to 90% by mass relative to the carboxyl group-containing ethylenically unsaturated monomer.

The preferable 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. If it exceeds 50,000, it may be difficult to form a pattern when developing with an alkaline developer. The 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 is preferably an epoxy (meth) acrylic acid obtained by reacting an epoxy compound and an unsaturated group-containing monocarboxylic acid reactant with an acid anhydride. Ester compound. The epoxy compound, the unsaturated monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used. The epoxy (meth) acrylate resin having a carboxyl group may be used singly or in combination of two or more kinds.

The alkali-soluble resin is preferably selected from those having an acid value of 50 mgKOH / g or more in terms of developability (solubility) of an alkaline aqueous solution used in a developer. The alkali-soluble resin is preferably an acid value of 70 mgKOH / g or more and 300 mgKOH / g in terms of developability (solubility) with respect to an alkaline aqueous solution used in a developing solution and adhesion with a substrate. Hereinafter, it is preferably 70 mgKOH / g or more and 280 mgKOH / g or less. The acid value of the alkali-soluble resin can be measured in accordance with JIS K 0070: 1992.

In terms of obtaining the effect of improving the film strength of the cured film, improving the development resistance, and excellent adhesion to the substrate, the equivalent of an ethylenically unsaturated bond when the side chain of the alkali-soluble resin has an ethylenically unsaturated group A range of 100 to 2000 is preferred, and a range of 140 to 1500 is particularly preferred. When this vinyl-based unsaturated bond equivalent is 100 or more, it is excellent in developability and adhesiveness. Moreover, if it is 2000 or less, since the ratio of other structural units, such as the said structural unit which has a carboxyl group, or the structural unit which has a hydrocarbon ring, can be relatively increased, it is excellent in developability or heat resistance. In addition, in terms of excellent synergistic effect when combined with the dispersant, and further improving the brightness of the colored layer and the ITO crack resistance, it is preferred that the dispersant is in a block copolymer before salt formation. The (meth) acrylfluorenyl equivalent contained in the side chain is in the above-mentioned preferred range, and the ethylenically unsaturated bond equivalent in the alkali-soluble resin is in the above-mentioned preferred range. Here, the so-called ethylene-based unsaturated bond equivalent is a weight average molecular weight per mole of the ethylene-based unsaturated bond in the alkali-soluble resin, and is expressed 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 mole number (mol) of the ethylene-based double bond contained in the alkali-soluble resin W (g)).

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

The alkali-soluble resin used in the photosensitive coloring resin composition for color filters may be used singly or in combination of two or more kinds. The content thereof is not particularly limited. Compared with photosensitive resins for color filters, The total amount of solid components of the coloring resin composition is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass of the alkali-soluble resin. When the content of the alkali-soluble resin is at least the above-mentioned lower limit, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is at or below the above-mentioned upper limit, film roughness or pattern defects can be suppressed during development.

<Polyfunctional monomer>

The polyfunctional monomer used in the photosensitive coloring resin composition for a color filter is not particularly limited as long as it can be polymerized by the following photoinitiator, and usually two or more vinyl-based resins are used. The compound having an unsaturated double bond is particularly preferably a polyfunctional (meth) acrylate having two or more acrylfluorenyl groups or methacrylfluorenyl groups. As such a polyfunctional (meth) acrylate, what is necessary is just to select suitably and use it from a well-known person. Specific examples include those described in Japanese Patent Laid-Open No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. In the case where the photosensitive coloring resin composition for a color filter of the present invention is required to have excellent photohardenability (high sensitivity), the polyfunctional monomer preferably has three (trifunctional) or more polymerizable polymers. For double bonds, poly (meth) acrylates of polyhydric alcohols of three or more types or dicarboxylic acid modified products thereof are preferred, and specifically, trimethylolpropane tri (meth) acrylic acid is preferred. Ester, pentaerythritol tri (meth) acrylate, succinic acid modification of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (pentaerythritol) ) Acrylate, succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. The content of the above-mentioned polyfunctional monomer used in the photosensitive colored resin composition for a color filter is not particularly limited. The polyfunctional monomer is relative to the total solid content of the photosensitive colored resin composition for a color filter. The volume is preferably within a range of 5 to 60% by mass, and more preferably within a range of 10 to 40% by mass. If the content of the polyfunctional monomer is less than the above-mentioned lower limit, the photo-hardening cannot be performed sufficiently, and the exposed portion may be dissolved during development. In addition, if the content of the polyfunctional monomer is more than the above-mentioned upper limit, the The alkali developability may be reduced.

<Photoinitiator>

The photoinitiator used in the colored resin composition for a color filter of the present invention is not particularly limited, and it may be used singly or in combination of two or more of various known initiators. Examples of the photoinitiator include aromatic ketones, benzoin ethers, and halomethyl Diazole compounds, α-amino ketones, biimidazoles, N, N-dimethylaminobenzophenones, halomethyl-S-tris Compounds, 9-oxysulfur Wait. Specific examples of the photoinitiator include benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and the like. Aromatic ketones, benzoin ethers such as benzoin methyl ether, 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 compounds, 2- (4-butoxy-naphthalen-1-yl) -4,6-bis-trichloromethyl-S-tri Isohalomethyl-S-tri Compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2- Porphyrinacetone, 1,2-benzyl-2-dimethylamino-1- (4- (Phenylphenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, diphenylethylenedione, benzophenone benzoic acid, methyl benzophenone benzoate, 4-benzylidene- 4'-methyldiphenyl sulfide, biphenylstilbene 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-benzylidene-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4- Phenyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Phenyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzyl) phosphine oxide, 2- Methyl-1- [4- (methylthio) phenyl] -2- (4- Phenyl) -1-acetone and the like. Among them, 2-methyl-1- [4- (methylthio) phenyl] -2- is preferably used Linylpropane-1-one, 2-benzyl-2- (dimethylamino) -1- (4- (Phenylphenyl) -1-butanone, 4,4'-bis (diethylamino) benzophenone, diethyl-9-oxosulfan . Furthermore, in terms of sensitivity adjustment, suppression of water permeation, and improvement of development resistance, it is preferable to use 2-methyl-1- [4- (methylthio) phenyl] -2- Α-Aminoacetophenone-based initiators of phosphonopropane-1-one and diethyl-9-oxosulfone 9-oxysulfur Department of initiator combination. Using an α-aminoacetophenone-based initiator with 9-oxysulfur In the case of the initiator, the total content is preferably 5 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 number of sublimates in the manufacturing process is reduced, which is preferable. When the starting dose is 5% by mass or more, development resistance such as water seepage is improved.

In the present invention, the photoinitiator preferably contains an oxime ester-based photoinitiator in terms of improving sensitivity. In addition, by using an oxime ester-based photoinitiator, unevenness in line width in a plane can be easily suppressed when forming a thin line pattern. Furthermore, the use of an oxime ester-based photoinitiator tends to increase the residual film rate and increase the effect of suppressing water permeation. The term "water permeation" refers to the use of a component that enhances alkali developability, and after washing with pure water after alkali development, traces such as water permeation are generated. This kind of water will disappear after post-baking, so there is no problem as a product, but after development, it will be detected as an uneven abnormality in the visual inspection of the patterned surface, which causes a problem that the normal product and the abnormal product cannot be distinguished. Therefore, if the inspection sensitivity of the inspection device is reduced during the appearance inspection, as a result, the yield of the final color filter product is lowered and becomes a problem. As the oxime ester-based photoinitiator, in terms of reducing contamination of the colored resin composition for color filters or contamination of the device caused by decomposition products, among them, those having an aromatic ring are preferred, and more preferably Those having a condensed ring including an aromatic ring, and more preferably having a condensed ring including a benzene ring and a heterocyclic ring. As the oxime ester-based photoinitiator, 1,2-octanedione-1- [4- (phenylthio)-, 2- (O-benzylideneoxime)], ethyl ketone, 1- [ 9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime), Japanese Patent Laid-Open No. 2000-80068, The oxime ester photoinitiator described in JP 2001-233842, JP 2010-527339, JP 2010-527338, JP 2013-041153 and the like is appropriately selected. As commercially available products, Irgacure OXE-01, Adeka Arkls NCI-930, di-phenyl sulfide skeleton, TR-PBG-345, TR-PBG-304 with carbazole skeleton, and TR- with fluorene skeleton can also be used. PBG-365, TR-PBG-3057 with diphenyl sulfide skeleton (the above is made by Changzhou Qiangli Electronic New Materials Co., Ltd.), etc. Especially in terms of brightness, it is preferable to use an oxime ester-based photoinitiator having a diphenylsulfide skeleton or a fluorene skeleton. Moreover, it is preferable to use the oxime ester type photoinitiator which has a carbazole skeleton from a high sensitivity. In addition, the use of two or more oxime ester-based photoinitiators in combination is preferable in that it is easy to improve the brightness, the residual film rate, and the effect of suppressing water leakage is high. In particular, in terms of high brightness and high heat resistance, it is preferable to use two kinds of oxime ester-based photoinitiators having a diphenylsulfide skeleton in combination or use oxime ester-based photooxidants having a diphenylsulfide skeleton in combination Initiator and oxime ester photoinitiator with fluorene skeleton. In terms of excellent sensitivity and brightness, it is preferred to use an oxime ester-based photoinitiator having a carbazole skeleton and an oxime ester-based photoinitiator having a fluorene skeleton or an oxime ester system having diphenylsulfide. Light initiator.

Moreover, it is preferable to use a photoinitiator which has a tertiary amine structure in combination with the oxime ester photoinitiator from the point of suppressing water penetration and improving sensitivity. The reason is that the photo-initiator having 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 sensitivity can be improved. Examples of the commercially available photoinitiator having a tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2- Porphyrin-1-one (for example, Irgacure907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4- Phenylphenyl) -1-butanone (for example, Irgacure369, manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (for example, HiCure ABP, manufactured by Kawaguchi Pharmaceutical), and the like. In addition, p-oxime ester-based photoinitiator combination 9-oxysulfur The series initiator is preferable in terms of sensitivity adjustment, suppression of water penetration, and improvement of development resistance. Two or more oxime ester-based photoinitiators and 9-oxysulfur are used. The system-based initiator combination is preferable in terms of improving brightness, residual film rate, easy sensitivity adjustment, high effect of suppressing water permeation, and improving development resistance.

The content of the light initiator used in the colored resin composition for a color filter of the present invention is generally about 0.01 to 100 parts by mass, and preferably 5 parts by mass, relative to 100 parts by mass of the above-mentioned polyfunctional monomer. ~ 60 parts by mass. If the content is above the lower limit value, sufficient light hardening is performed to suppress the elution of the exposed portion during development. On the other hand, if the content is below the upper limit value, the yellowing of the obtained colored layer can be suppressed from weakening. The resulting reduction in brightness. In addition, as a light initiator used in the colored resin composition for a color filter of the present invention, the total content of two or more oxime ester-based light initiators is relative to the solid form of the colored resin composition for a color filter. The total amount of the material components is preferably from 0.1% by mass to 12.0% by mass, and more preferably from 1.0% by mass to 8.0% by mass, in terms of fully exerting the combined effect of these photoinitiators.

Regarding the binder component used in the colored resin composition for a color filter of the present invention, the total content thereof is preferably 35% by mass relative to the total solid component content of the colored resin composition for a color filter. 97% by mass, more preferably blended at a ratio of 40% to 96% by mass. If it is more than the said lower limit value, the colored layer which is excellent in hardness or adhesiveness with a board | substrate can be obtained. Moreover, when it is below the said upper limit, it is excellent in developability, and also suppresses generation | occurrence | production of the fine wrinkle by thermal contraction.

<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 discoloration of a color material, and improving brightness. The antioxidant may be appropriately selected from those known in the art. Specific examples of the antioxidant include, for example, hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and are preferably used in terms of heat resistance. Hindered phenolic antioxidants. It may be a latent antioxidant as described in International Publication No. 2014/021023.

Examples of the hindered phenol-based antioxidant include pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF Corporation), 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3 , 5-Di-tert-butylbenzyl) mesitylene (trade name: IRGANOX 1330, manufactured by BASF), 2,2'-methylenebis (6-third-butyl-4-cresol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis (2-third butyl-4-cresol) (trade name: IRGANOX1081, manufactured by BASF), 3,5-di-tert-butyl Diethyl-4-hydroxybenzylphosphonic acid (trade name: Irgamod 195, manufactured by BASF) and the like. Among them, in terms of heat resistance and light resistance, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, BASF Corporation) is preferred. Manufacturing).

When the photosensitive colored resin composition for a color filter of the present invention contains the oxime ester-based photoinitiator and an antioxidant in combination, the synergistic effect improves the brightness and the residual film rate. When forming a thin line pattern, the linearity is further improved, or the ability to form a thin line pattern is improved as in the design of a mask line width.

The blending amount of the antioxidant is preferably 0.1 to 10.0 parts by mass, and more preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the total solids component in the colored resin composition. 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 below the said upper limit, the colored resin composition of this invention can be made into the photosensitive resin composition of high sensitivity.

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

<Arbitrarily added ingredients>

In the photosensitive colored resin composition for a color filter of the present invention, in addition to the above-mentioned antioxidant, various additives may be optionally contained. Examples of the additives include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, a defoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter. Specific examples of the surfactant and the plasticizer include those described in Japanese Patent Laid-Open No. 2013-029832.

Examples of the silane coupling agent include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, and KBE. -403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicones), and the like. Among these, in terms of the adhesiveness of the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 having methacrylfluorene and acrylfluorenyl groups are preferred.

The content of 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 relative to 100 parts by mass of the total solid content in the photosensitive colored resin composition. Mass parts or less. When it is at least the above lower limit value and not more than the above upper limit value, the substrate is excellent in adhesiveness.

<The blending ratio of each component in the photosensitive coloring resin composition for color filters>

Regarding the total content of the color material, it is preferably blended at a ratio of 3 to 65% by mass, more preferably 4 to 60% by mass, relative to the total solid content of the photosensitive coloring resin composition for a color filter. If it is more than the said lower limit, the coloring layer when apply | coating the photosensitive coloring resin composition for color filters to predetermined film thickness (usually 1.0-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, the colored layer which is excellent in storage stability, has sufficient hardness, or has adhesiveness with a board | substrate can be obtained. Especially in the case of forming a coloring layer having a high color material concentration, the content of the color material is preferably 15 to 65% by mass based on the total solid content of the photosensitive coloring resin composition for color filters. It is preferably formulated at a ratio of 25 to 60% by mass. The content of the dispersant is not particularly limited as long as it can disperse the color material uniformly. For example, it can be 1 to 40 masses based on the total solid component content of the photosensitive colored resin composition for a color filter. % Ratio used. Furthermore, it is preferable to mix | blend in the ratio of 2-30 mass% with respect to the total amount of solid content of the photosensitive coloring resin composition for color filters, and it is more preferable to mix | blend in the ratio of 3-25 mass%. If it is at least the above lower limit value, the dispersibility and dispersion stability of the color material will be excellent, and the storage stability of the photosensitive colored resin composition for a color filter will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a colored layer having a high color material concentration, the content of the dispersant is preferably 2 to 25% by mass based on the total solid content of the photosensitive coloring resin composition for color filters. It is preferably blended at a ratio of 3 to 20% by mass. The mass of the dispersant in the case of a salt-type block copolymer is the total mass of the block copolymer and the organic acid compound before the salt is formed. The content of the solvent may be appropriately set within a range in which a colored layer can be formed with high accuracy. The total amount of the photosensitive coloring resin composition for a color filter containing the solvent is usually preferably in a range of 55 to 95% by mass, and more preferably in a range of 65 to 88% by mass. When the content of the solvent is within the above range, it is possible to obtain an excellent coating property.

<Manufacturing method of the photosensitive coloring resin composition for color filters>

The method for producing the photosensitive colored resin composition for a color filter of the present invention is not particularly limited. For example, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and If necessary, other components are obtained by mixing them using a known mixing method.

III. Color Filter

The color filter of the present invention includes at least a substrate and a coloring layer provided on the substrate, and at least one of the colored 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 a color filter of the present invention. According to FIG. 1, a color filter 10 according to the present invention includes 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 a colored layer of a cured product of the photosensitive colored resin composition for a color filter of the present invention. The colored layer is usually formed in an opening portion of a light-shielding portion on a substrate described below, and usually contains a colored pattern of three or more colors. The arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. The width, area, and the like of the colored layer can be arbitrarily set. The thickness of the colored layer is appropriately controlled by adjusting the coating method and the solid content concentration or viscosity of the photosensitive colored resin composition for a color filter, 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, the color filter for the above-mentioned color filter of the present invention is photosensitively colored using coating methods such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, and a die coating method. The resin composition is applied on a substrate described below to form a wet coating film. Among them, a spin coating method and a die coating method can be preferably used. Then, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed through a mask with a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, and the like are subjected to a photopolymerization reaction to produce a cured coating film. Examples of the light source used for the exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, and electron beams. The exposure amount is appropriately adjusted according to the light source used, the thickness of the coating film, and the like. Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition for a color filter used, the thickness of the coating film, and the like.

Next, by performing a development process using a developing solution, the unexposed portion is dissolved and removed, and a coating film is formed in a desired pattern. As the developing solution, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. An appropriate amount of a surfactant can also be added to the alkaline solution. Moreover, a general method can be used as a developing method. After the development process, the developing solution is usually washed, and the cured coating film of the photosensitive colored resin composition for a color filter is dried to form a colored layer. After the development treatment, a heat treatment may be performed to sufficiently harden the coating film. The heating conditions are not particularly limited, and are appropriately selected depending on the application of the coating film.

<Shading section>

The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate described below, and can be the same as a light-shielding portion used in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include shapes such as a stripe shape and a matrix shape. The light-shielding portion may be a metal thin film such as chromium obtained by a sputtering method, a vacuum evaporation 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 the 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 by using an inkjet ink containing light-shielding particles, and Methods of thermal transfer.

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

<Substrate>

As the substrate, a transparent substrate, a silicon substrate described below, and an aluminum, silver, silver / copper / palladium alloy thin film, or the like formed on the transparent substrate or the silicon substrate are used. It is also possible to form other color filter layers, resin layers, transistors such as TFTs, and circuits on these substrates. The transparent substrate used as the color filter of the present invention is not particularly limited as long as it is a substrate that is transparent to visible light, and a transparent substrate used for general color filters can be used. Specifically, non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent and flexible materials having flexibility such as transparent resin films, optical resin plates, and flexible glass can be cited. Sex material. The thickness of the transparent substrate is not particularly limited, and for example, one of about 100 μm to 1 mm can be used according to the application of the color filter of the present invention. Furthermore, the color filter of the present invention may be formed with an outer coating layer or a transparent electrode layer, for example, an alignment film or a columnar spacer, in addition to the substrate, the light-shielding portion, and the coloring layer.

IV. Display device

The display device of the present invention is characterized by having the color filter of the present invention. In the present invention, the structure of the display device is not particularly limited, and can be appropriately selected from display devices known in the art, and examples thereof include a liquid crystal display device and an organic light emitting display device.

[Liquid crystal display device]

Examples of the liquid crystal display device of the present invention include a liquid crystal display device including 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 a liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate, and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30. It should be noted that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2 and may be a generally known configuration 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 a liquid crystal display device can be adopted. Examples of such a driving method include a twisted nematic (TN) method, an in-plane switching (IPS) method, an optically compensated birefringence (OCB) method, and many more. Multi-Domain Vertical Alignment (MVA). In the present invention, any of these methods can be preferably used. The counter substrate may be appropriately selected and used according to a 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 a mixture of these can be used according to the driving method of the liquid crystal display device of the present invention.

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

[Organic light-emitting display device]

Examples of the organic light emitting display device of the present invention include an organic light emitting display device including the color filter and the organic light emitting body of the present invention. 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 an 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 includes a color filter 10 and an organic light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitting body 80.

As a method for stacking the organic light-emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transmission layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 may be sequentially formed on the upper surface of the color filter. Method; or a method of attaching the organic light emitting body 80 formed on another substrate to the inorganic oxide film 60, and the like. The transparent anode 71, the hole injection layer 72, the hole injection layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light emitting body 80 can be appropriately known to other structures. The organic light-emitting display device 100 manufactured in this way can be applied to, for example, an organic EL display in a passive driving manner, or to an organic EL display in an active driving manner. The organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3, and may be a structure generally known as an organic light emitting display device using a color filter.

[Example]

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

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

A 500 mL round bottom four-neck separable flask equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer was added with 250 parts by mass of THF and 0.6 parts by mass of lithium chloride, and fully replaced with nitrogen. After the reaction flask was cooled to -60 ° C, 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. Using a funnel for addition, dropwise add 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 12.1 parts by mass of 2-ethylhexyl methacrylate (EHMA), and monomers for 60 minutes using an addition funnel. 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) as a monomer for the A block was added dropwise over 20 minutes. After 30 minutes of reaction, 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. The solution was 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 performed for 7 hours, and the constituent units derived from EEMA were deprotected to produce constituent units 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 again dissolved in 400 parts by mass of PGMEA. 5.3 parts by mass of isocyanate A (2-isocyanatoethyl methacrylate, trade name: Karenz MOI, manufactured by Showa Denko), dibutyltin (trade name: Neostann U-100, manufactured by Nitto Chemical Co., Ltd.) 0.008 Part by mass, after heating to 80 ° C, reacting for 2 hours to obtain an A block having a constitutional unit represented by the general formula (I), a constitutional unit represented by the general formula (B1), and a carboxyl group-derived monomer The block copolymer A-1 'solution of the B block of the constituent unit (solid content 20% by mass).

A 100 mL round bottom flask was charged with 50 parts by mass of the obtained block copolymer A-1 'solution, and 1.27 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) was added as a compound represented by the general formula (3). (PPA is 0.5 mol with respect to 1 mol of DMMA unit of block copolymer A-1 ′), and stirred at a reaction temperature of 30 ° C. for 20 hours, thereby obtaining a salt-type block copolymer having a solid content of 20% by mass. A-1 solution. The acid value of the salt-type block copolymer A-1 after salt formation is the same as that of the block copolymer A-1 'before salt formation. Specifically, the amine value after salt formation is calculated as follows. 1 g of a solution obtained by mixing 9 parts by mass of salt-type block copolymer A-1 (solid matter after reprecipitation) and 191 parts by mass of deuterated chloroform-D191 for NMR was added to an NMR sample tube, using a nuclear magnetic resonance apparatus ( Nippon Electronics Manufacturing, FT NMR, JNM-AL400), and the 13C-NMR spectrum was measured under the conditions of room temperature and 10,000 cumulative times. In the obtained spectral data, the ratio is calculated based on the ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom that is not salt-formed to the terminal nitrogen site (amine group) to the peak of the carbon atom adjacent to the nitrogen atom that is salt-formed. It was confirmed that the ratio of the number of amine groups to the total number of amine groups for salt formation was the same as the theoretical salt formation ratio (all phenylphosphonic acid forms a salt with the nitrogen site at the terminal DMMA of the block copolymer A-1 ′).

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

In Example 1, the material of the A block was changed to the content shown in Table 1, and the material of the B block was changed to the type and content shown in Table 1. Otherwise, the salt type was the same as that of Example 1. In the same manner as the block copolymer A-1, a salt type block copolymer A-2 to A-14 solution was obtained. In addition, 1-ethoxyethyl methacrylate (EEMA) uses a molar amount equivalent to that of MAA in Table 1. In Table 1, the amount of the organic acid compound or halogenated hydrocarbon used as the salt-forming compound is 1 mole of the nitrogen site (DMMA) of the structural unit represented by the general formula (I). Morse number. Furthermore, 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'-methylpropylamine) was added. Group] carboxyamino) ethyl ester, Karenz MOI-BM, manufactured by Showa Denko) 12.0 parts by mass, 0.01 parts by mass of dibutyltin dilaurate, and heated at 130 ° C for 2 hours, thereby obtaining a compound having the general formula (I) A block of the structural unit represented by Block A, and a block copolymer A-2 'solution (solid content component 20) containing the structural unit represented by the general formula (B1) and the B block derived from the structural unit derived from a carboxyl group-containing monomer Mass%).

(Comparative Examples 1 to 2: Comparative Synthesis of Salt Block Copolymers AC-1 to AC-2)

In Example 1, the material of the A block was changed to the content shown in Table 1, and the material of the B block was changed to the type and content shown in Table 1. Otherwise, the salt type was the same as that of Example 1. In the same manner as the block copolymer A-1 solution, comparative salt-type block copolymer AC-1 to AC-2 solutions were obtained. Further, in Comparative Example 1, a purified comparative block copolymer AC-1 "was not reacted with an isocyanate compound to obtain a comparative salt-type block copolymer AC-1 solution. In Comparative Example 2, acrylic acid was (3-ethyloxetane-3-yl) methyl ester is added together with monomers for B blocks such as EEMA to obtain a comparative block copolymer AC-2 ", which does not copolymerize the purified comparative block The complex AC-2 "was reacted with an isocyanate compound to obtain a comparative salt-type block copolymer AC-2 solution.

Salts of 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 Table 1 shows the acid value, amine value, hydroxyl value, and weight average molecular weight (Mw) before and after salt formation. The amine value after the salt formation of the salt-type block copolymer is calculated by subtracting the amine value of the DMMA unit from the amine value before the 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)

A 500 ml four-neck separable flask was decompressed and dried, and then replaced with Ar (argon). While flowing Ar, 100 parts by mass of dehydrated THF, 2.0 parts by mass of methyltrimethylsilyldimethylketal, and 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB) were added 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). When the reaction progressed, heat was generated, so the temperature was kept below 40 ° C by cooling with an ice bath. After 1 hour, 25.3 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After 1 hour of reaction, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain a 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) was added. : 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 a compound containing a general formula ( I) A block of the structural unit represented by the block A, and a block copolymer A-18 'solution (solid form) containing the structural unit represented by the general formula (B1) and the B block derived from the carboxyl group-containing monomer unit (20% by mass). In Example 1, except that the block copolymer A-18 'solution was used instead of the block copolymer A-1' solution, in the same manner as in Example 1, a salt type having 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 the block copolymers A-15 to A-17 and the salt-type block copolymer A-18 obtained in Examples 15 to 18 are shown in Table 1.

Here, each abbreviation in the table is 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- (bispropenyloxymethyl) ethyl isocyanate (trade name: Karenz BEI, manufactured by Showa Denko)

Isocyanate D: 2-Methacryloxyethoxyethyl 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)

300 parts by mass of PGMEA was added to the polymerization tank, and the temperature was raised to 100 ° C in a nitrogen atmosphere, and then 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, and methacrylic acid were continuously added dropwise over 1.5 hours. (MAA) 36 parts by mass, Perbutyl O (manufactured by Nippon Oil Corporation) 6 parts by mass, and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan). Thereafter, the reaction was continued at 100 ° C. After 2 hours from 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, add 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound, and raise the temperature to 110 ° C, then add 0.8 parts by mass of triethylamine, and proceed at 110 ° C for 15 minutes. The addition reaction was carried out for one hour to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH / g, and solid content 40% by mass). The method for measuring the weight average molecular weight described above uses polystyrene as a standard substance, THF as an eluent, and the weight average molecular weight is measured by Shodex GPC System-21H. The method for measuring the acid value is measured based on JIS K 0070: 1992.

(Example 21)

(1) Manufacturing of color material dispersion liquid G1

14.8 parts by mass of the salt-type 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 diameter of 2.0 mm were placed in a mayonnaise bottle as pre-crushing After shaking with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour, the zirconia beads with a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads with a particle diameter of 0.1 mm were added. Dispersion was performed in a paint shaker for 4 hours to obtain a color material dispersion liquid G1.

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

Add 43.8 parts by mass of the color material dispersion liquid G1 obtained in (1) above, 6.3 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, and a polyfunctional monomer (trade name Aronix M-403, Toa Synthetic Co., Ltd. 5.9 parts by mass of oxime ester-based initiator (made by ADEKA Corporation, "Adeka arkls NCI-930") as a photoinitiator, 0.92 parts by mass, of oxime ester-based 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, 0.11 parts by mass of a hindered phenol-based antioxidant (IRGANOX 1010, manufactured by BASF), 3-methacryloxypropyltrimethoxy 0.4 parts by mass of silane (trade name: KBM503, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 0.04 parts by mass of Megafac F-559 (manufactured by DIC), and 41.4 parts by mass of PGMEA as a solvent, and then mixed until uniform, to obtain color A photosensitive colored resin composition G1 for a filter.

(3) Formation of colored layer

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

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

(1) Manufacturing of color material dispersion liquids G2 to G18, comparative color material dispersion liquids GC1 to GC2

In Example 21 (1), instead of the salt-type block copolymer A-1 solution, as shown in Table 2, respectively, the solid content was changed to the same mass part as that of the salt-type block copolymer A-1. The salt-type block copolymers A-2 to A-14 solutions of Examples 2 to 14, the block copolymers A-15 to A-17 and the salt-type block copolymers A-18 of Examples 15 to 18 were used respectively. 2. The comparative salt type block copolymers AC-1 to AC-2 solutions of Comparative Examples 1 to 2 were adjusted to the total amount of PGMEA so as to be 100 parts by mass, and were the same as those in Example 21 (1) except Method to obtain color material dispersion liquids G2 to G18 and comparative color material dispersion liquids GC1 to GC2.

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

In Example 21 (2), the color material dispersion liquids G2 to G18 and the comparative color material dispersion liquids GC1 to GC2 were used instead of the color material dispersion liquid G1, respectively. In the same manner, photosensitive coloring resin compositions G2 to G18 for color filters and comparative coloring resin compositions GC1 to GC2 for color filters were obtained.

(3) Formation of colored layer

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

(Example 41)

(1) Manufacturing of color material dispersion R1

In Example 21 (1), 13 parts by mass of a pyrrolopyrrole dione pigment (Irgaphor RED S 3621CF, manufactured by BASF) 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), a color material dispersion liquid R1 was obtained in the same manner as in (1) of Example 21.

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

In the same manner as in Example 21 (2), except that the color material dispersion liquid R1 obtained above was used in place of the color material dispersion liquid R1 obtained in (2) of Example 21, a photosensitive agent for a color filter was obtained. A coloring resin composition R1.

(3) Formation of colored layer

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

(Example 42)

(1) Manufacturing of color material dispersion B1

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

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

In Example 21 (2), the color material dispersion liquid B1 obtained above was used in place of the color material dispersion liquid G1, and a photosensitive agent for a color filter was obtained in the same manner as in Example 21 (2). Sexually colored resin composition B1.

(3) Formation of colored layer

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

(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 Jiwa Chemical) was used in place of 10.4 parts by mass of CI Pigment Green 58 (PG58) and CI Pigment Yellow 138 (PY138) 2.6 Except for mass parts, a color material dispersion liquid Y1 was obtained in the same manner as in (1) of Example 21.

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

In the same manner as in Example 21 (2), except that the color material dispersion liquid Y1 obtained above was used in place of the color material dispersion liquid G1 in Example 21 (2), a photosensitive agent for a color filter was obtained. Sexually colored resin composition Y1.

(3) Formation of colored layer

A colored layer Y1 was obtained in the same manner as in Example 21 (3) except that the colored resin composition Y1 was used instead of the colored resin composition G1 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 was measured immediately after preparation and after storage at 25 ° C for 30 days, and the viscosity change rate was calculated from the viscosity before and after storage to evaluate the viscosity stability. Viscosity measurement uses a vibratory viscometer to measure viscosity at 25.0 ± 0.5 ° C. The results are shown in Tables 2 and 3.

(Evaluation criteria for viscosity stability)

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

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

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

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

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

Here, the viscosity of the color material dispersion liquid is a value when the color material is 13% by mass relative to the total mass including the solvent of the color material dispersion liquid. Even if the evaluation result is C, the color material dispersion liquid can be used in practical applications. If the evaluation result is B, the color material dispersion liquid is more favorable. If the evaluation result is A, the color material dispersion liquid has excellent dispersion stability.

<Evaluation of ITO crack resistance>

Using a spin coater, the photosensitive colored resin composition for color filters obtained in the examples and comparative examples was applied to a thickness of 0.7 mm and 100 mm × 100 mm so that the film thickness after baking was about 2.5 μm. Glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35"). Thereafter, it was dried on a hot plate at 80 ° C for 3 minutes. An ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 40 mJ / cm ² without a photomask, and then baked in a clean oven at 230 ° C. for 30 minutes to obtain a cured film (colored film). An ITO film having a thickness of 120 nm was formed on the obtained cured film by a sputtering device (manufactured by ULVAC, CS-200). After the film was immersed in N-methylpyrrolidone at 25 ° C for 120 minutes, it was visually observed whether the substrate had cracked on the ITO film.

(Evaluation criteria for ITO crack resistance)

AA: No cracking

A: The number of cracks is less than 5

B: Cracks on the entire surface

C: A crack is generated on the entire surface, and the ITO is partially peeled off.

If the 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 Development Adhesion>

The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each applied to a glass substrate having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm using a spin coater (manufactured by NH Techno Glass Co., Ltd., " NA35 ″), and then dried at 80 ° C. for 3 minutes using a hot plate, thereby forming a colored layer having a thickness of 2.5 μm. An ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 60 mJ / cm ² through a mask having a mask opening width of 2 to 80 μm through the colored layer. The glass plate on which the above-mentioned colored layer was formed was subjected to spray development using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developing solution. The developed substrate was observed with an optical microscope, and the presence or absence of a colored layer with respect to the line width of the mask opening was observed. The results are shown in Tables 2 and 3.

(Development adhesion evaluation criteria)

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

A: A colored layer is observed in a portion where the mask opening line width is 10 μm or more and less than 20 μm.

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

C: A colored layer is observed in a portion where the mask opening line width is 50 μm or more and less than 80 μm

D: No colored layer was observed in the part where the opening width of the mask was 80 μm or less

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

<Evaluation of Development Residue>

The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each applied to a glass substrate having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm using a spin coater (manufactured by NH Techno Glass Co., Ltd., " NA35 ″), and then dried at 60 ° C. for 3 minutes using a hot plate, thereby forming a colored layer having a thickness of 2.5 μm. The glass plate on which the above-mentioned colored layer was formed was subjected to spray development using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developing solution. After visually observing the unexposed part (50 mm × 50 mm) of the glass substrate after the formation of the colored layer, the lens cleaner (manufactured by Toray, trade name Toraysee MK Clean Cloth) containing ethanol was used to sufficiently wipe, and the lens was visually observed The degree of coloration of the cleaner. The results are shown in Tables 2 and 3.

(Development residue evaluation criteria)

A: The lens cleaner is completely uncolored by visually observing the development residue.

B: The color of the lens cleaner was slightly confirmed by visually observing no developing residue.

C: The development residue was slightly confirmed by visual inspection, and the color of the lens cleaner was slightly confirmed.

D: The development residue was slightly visually confirmed, and the color of the lens cleaner was confirmed.

E: The development residue was visually confirmed, and the color of the lens cleaner was confirmed.

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

<Evaluation of solvent resolubility>

The front end of the glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for a color filter obtained in the examples and comparative examples, and applied to a 1 cm portion of the glass substrate. The lifted glass substrate was placed in a constant temperature and humidity machine such that the glass surface became horizontal, and was dried at a temperature of 23 ° C. and a humidity of 80% RH for 30 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dried coating film was visually determined and evaluated. The results are shown in Tables 2 and 3.

(Evaluation criteria for solvent resolubility)

AA: The dry coating film is completely dissolved

A: A thin film of a dry coating film is generated in a solvent, and the thin film dissolves soon

B: A thin coating film is produced in the solvent, and the solution is colored

C: A thin film is produced in the solvent, the solution is not colored

D: No flakes of dry coating film in the solvent, the solution is not colored

When the development residue evaluation criterion 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.

<Color Sublimation Evaluation>

Using a spin coater, each of the photosensitive coloring compositions for color filters obtained in Examples and Comparative Examples was coated on a glass substrate having a thickness of 0.7 mm, and heated and dried on a heating plate at 80 ° C for 3 minutes. Thereby, a colored layer having a thickness of 2.5 μm was formed. An ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 40 mJ / cm ^{2 to} the mask with a striped pattern in which 80 μm lines and spaces were drawn on the colored layer. Thereafter, the glass plate on which the above-mentioned colored layer was formed was subjected to spray development using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developing solution, and then washed with ultrapure water for 60 seconds. A glass substrate was arranged on the 0.7 mm upper surface of the obtained glass substrate on which the colored pattern was formed, and heated on a heating plate at 230 ° C. for 30 minutes. The presence or absence of sublimation of the glass substrate on the upper surface was visually confirmed, and was used as an evaluation of the sublimation property of the color material.

(Color Sublimation Evaluation Criteria)

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

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

C: On the upper surface of the glass substrate, there is a color produced by the sublimation, and the precipitate is also confirmed.

<Evaluation of substrate adhesion>

The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater. . Then, after heating and drying on a heating plate at 80 ° C. for 3 minutes, ultraviolet rays of 60 mJ / cm ^{2 were} irradiated with an ultra-high pressure mercury lamp. Thereafter, it was baked in a clean oven at 230 ° C. for 30 minutes to obtain a colored film having a film thickness of 2.5 μm. After using the utility knife to cut out the grid-like slits on the obtained colored film, adhesive tape is attached to it, and it is quickly peeled 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.

(Standard for evaluating substrate adhesion)

AA: No peeling was confirmed at all

A: Slight peeling was confirmed along the grid-like slit

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

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

<Evaluation of optical performance>

The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each applied to a glass substrate having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm using a spin coater (manufactured by NH Techno Glass Co., Ltd., " NA35 "), and then dried at 80 ° C for 3 minutes using a hot plate to form a colored layer. The colored layer was irradiated with ultraviolet light of 60 mJ / cm ² using an ultra-high pressure mercury lamp. Next, the colored substrate was 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 a microscope spectrophotometer OSP-SP200 manufactured by Olympus. ). The results are shown in Tables 2 and 3 together. In addition, a C light source is used as the light source.

[Summary of results]

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

Claims (11)

A color material dispersion for a color filter, which contains a color material, a dispersant, and a solvent, and the dispersant contains a block copolymer of an A block and a B block, and the A block includes the following A structural unit represented by formula (I), the B block contains at least one selected from a structural unit represented by the following general formula (B1) and a 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 which may contain a hetero atom, and R ² and R ³ may (Bonded to each other to form a ring structure) (In the general formula (B1), A ¹ represents a divalent linking group, R ¹¹ represents an aliphatic hydrocarbon group or a carbon atom of two, three or four valences of oxygen atoms, 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 di-, tri-, or tetra-valent linking group, and R ¹³ represents that it may contain at least one selected from an oxygen atom and a nitrogen atom. A divalent hydrocarbon group, R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group which 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 means 0, ¹ , 2 or 3, n ² means 0 or 1, n ³ means 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 means 1, 2 or 3, m ² means 0, 1 or 2, and m ¹ + m ² is 1, 2 or 3).     The color material dispersion for a color filter according to 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 a color filter according to claim 1 or 2, wherein the dispersant contains at least a part of a terminal nitrogen site of the structural unit represented by the general formula (I), and is selected from organic compounds. At least one of the group consisting of an acid compound and a halogenated hydrocarbon forms a salt-type block copolymer.         The color material dispersion liquid for a color filter according to claim 1 or 2, wherein the hydroxyl value of the dispersant is 120 mgKOH / g or less.         The color material dispersion for a color filter according to claim 1 or 2, wherein the color material contains a material selected from the group consisting of pyrrolopyrrole dione pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone. At least one of dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes.     A dispersant, which is a block copolymer containing an A block and a B block, the A block includes a structural unit represented by the following general formula (I), and the B block includes a member selected from the following general formula ( At least one of a structural unit represented by B1) and a 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 which may contain a hetero atom, and R ² and R ³ may (Bonded to each other to form a ring structure) (In the general formula (B1), A ¹ represents a divalent linking group, R ¹¹ represents an aliphatic hydrocarbon group or a carbon atom of two, three or four valences of oxygen atoms, 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 di-, tri-, or tetra-valent linking group, and R ¹³ represents that it may contain at least one selected from an oxygen atom and a nitrogen atom. A divalent hydrocarbon group, R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group which 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 means 0, ¹ , 2 or 3, n means 0 or 1, n ³ means 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 means 1, 2 or 3, m ² means 0, 1 or 2, and m ¹ + m ² is 1, 2 or 3).     A photosensitive colored resin composition for a color filter, comprising the color material dispersion for a color filter according to any one of claims 1 to 5, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.         The photosensitive colored resin composition for a color filter according to claim 7, wherein the photoinitiator contains an oxime ester.         The photosensitive colored resin composition for a color filter according to claim 7, wherein the photoinitiator contains at least two oxime esters and further contains an antioxidant.         A color filter, which is provided with at least a substrate and a coloring layer provided on the substrate, characterized in that at least one of the coloring layers is a color filter for use in any one of the above claims 7 to 9. A cured product of a photosensitive colored resin composition.         A display device having the color filter of the above-mentioned claim 10.