KR20220033471A - Color material dispersion liquid, dispersant, photosensitive colored resin composition, cured product, color filter, display device - Google Patents

Abstract

A colorant dispersion comprising a colorant, a dispersing agent, and a solvent, wherein the dispersing agent is a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the graft At least one type of salt-type graft copolymer in which at least a part of the nitrogen moiety of the structural unit represented by the general formula (I) of the copolymer and a specific compound form a salt, in the following general formula (II), the Polymer is A colorant dispersion liquid is provided in which a polymer chain is shown and the structural unit of the polymer chain includes a structural unit represented by the following general formula (III). (Each symbol in the general formulas (I), (II) and (III) is as described in the specification.)

Description

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

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

With the recent development of personal computers, in particular, the development of portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (cell phones, smartphones, and tablet PCs) is also increasing, and the liquid crystal display market is gradually growing. In recent years, an organic light emitting display device such as an organic EL display with high visibility due to self-luminescence is also attracting attention as a next-generation image display device. In the performance of these image display apparatuses, further image quality improvement, such as improvement of contrast and color reproducibility, and reduction of power consumption are strongly calculated|required.

A color filter is used for these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, light passing through the color filter is directly colored in the color of each pixel constituting the color filter, and the light of these colors is combined to form a color image. As a light source in that case, in addition to the conventional cold-cathode tube, the organic light-emitting element of white light emission and the inorganic light-emitting element of white light emission may be used. In addition, in the organic light emitting display device, a color filter is used for color adjustment or the like.

Under such circumstances, also in color filters, demands such as higher luminance, higher contrast, and improved color reproducibility are increasing.

Here, the color filter generally has a transparent substrate, a coloring layer formed on the transparent substrate and including coloring patterns of three primary colors of red, green, and blue, and a light-shielding portion formed on the transparent substrate to partition each coloring pattern. .

As a pixel formation method in a color filter, the pigment dispersion method which has the characteristic excellent on average from viewpoints, such as a spectral characteristic, durability, pattern shape, precision, etc. especially, is employ|adopted most widely.

In the color filter which has a pixel formed using the pigment dispersion method, in order to implement|achieve high brightness-ization and high contrast-ization, refinement|miniaturization of a pigment is examined. It is thought that scattering of the light which permeate|transmits the color filter by a pigment particle is reduced by refining|miniaturizing a pigment, and high luminance-ization and high-contrast-ization are achieved.

However, since the refinement|miniaturized pigment particle was easy to aggregate, there existed a problem that dispersibility and dispersion stability fell.

It is known that the use of a dispersing agent is effective as a method of improving the dispersibility of the refined pigment. For example, in Patent Document 1, for the purpose of providing a radiation-sensitive composition for forming a colored layer that can form a pixel with a high contrast ratio and is also excellent in storage stability, as a pigment dispersant, a specific repeating unit having an ammonium base and an amino group A block having an A block including a specific repeating unit, and a B block including a specific repeating unit containing a carboxylate ester and a specific repeating unit containing an ethylene oxide group or a propylene oxide group in the alcohol-derived portion of the carboxylate ester A radiation-sensitive composition for forming a colored layer using a copolymer is disclosed.

Further, in Patent Document 2, for the purpose of providing a negative resist composition for color filters having excellent pigment dispersibility and excellent alkali developability, as a pigment dispersant, a nitrogen-containing monomer, a polymer chain and its terminal It is a graft copolymer containing a polymerizable oligomer containing a group having an ethylenically unsaturated double bond as a copolymerization component, and an amino group of the nitrogen-containing monomer and an organophosphoric acid compound represented by the following general formula (II) are salts A negative resist composition for color filters using the formed graft copolymer is disclosed. Patent Document 2 describes that alkali developability is improved when an amino group of the nitrogen-containing monomer and an organophosphoric acid compound represented by the following general formula (II) form a salt.

On the other hand, Patent Document 3 contains an oxime ester photoinitiator having a diphenyl sulfide skeleton as a photosensitive coloring composition capable of achieving high development resistance and high resolution even when the pigment content is high or the film thickness is large. The photosensitive coloring composition is disclosed.

[Patent Document 1] Japanese Patent No. 5540599 [Patent Document 2] Japanese Patent Laid-Open No. 2009-265649 [Patent Document 3] Japanese Patent Laid-Open No. 2012-177826

However, in recent color filters, the request|requirement of high concentration of the color material in the photosensitive resin composition is increasing by the request|requirement, such as high color gamut formation and thin film formation. When the ratio of the color material in the photosensitive resin composition increases, the binder component decreases relatively. Among the binder components, as the number of components related to the curability of the coating film, such as a polyfunctional monomer and a photoinitiator, decreases, the crosslinking density of the coating film decreases due to insufficient curing, and water stains occur or insufficient solvent resistance occurs in the coating film. In addition, when the components related to developability, such as alkali-soluble resin, decrease, development residues are generated or development time is delayed. Therefore, in order to achieve the high-concentration request|requirement of the color material in the photosensitive resin composition, the technique which solves the problem resulting from these binder component deficiency simultaneously is needed. Here, after alkali development, after rinsing with pure water, the water stain refers to the said phenomenon in which a trace like water is generated. Since such a water stain disappears after post-baking, there is no problem as a product, but it is detected as a non-uniformity abnormality in the appearance inspection of the patterned surface after development, and there arises a problem that a normal product and an abnormal product cannot be distinguished. For this reason, when the test|inspection sensitivity of an inspection apparatus is lowered in an external appearance test|inspection, as a result, it will cause the fall of the yield of the final color filter product, and it will become a problem.

The present invention has been made in view of the above circumstances, and it is to provide a colorant dispersion and dispersant capable of producing a photosensitive colored resin composition that simultaneously satisfies the suppression of the occurrence of development residues, the shortening of the development time, the suppression of the occurrence of water stains, and the excellent solvent resistance. For the purpose of 1. In addition, the present invention is to provide a photosensitive colored resin composition that simultaneously satisfies the suppression of the occurrence of development residues, the shortening of the development time, the suppression of the occurrence of water spots and the good solvent resistance, and a color filter and a display device formed using the photosensitive colored resin composition. for the first purpose.

As mentioned above, in order to achieve the request|requirement of the high concentration of the color material in the photosensitive resin composition, the technique which solves the problem originating in these binder component deficiency simultaneously is needed. Moreover, with the increase in concentration of a color material, the improvement of dispersion stability and contrast is also calculated|required.

Although the effect that solvent resistance becomes favorable also is described in patent document 3, only using the oxime ester type photoinitiator which has a diphenyl sulfide skeleton is still insufficient, and the further improvement of solvent resistance is calculated|required.

The present invention has been made in view of the above circumstances, and provides a photosensitive colored resin composition that simultaneously satisfies dispersion stability, high contrast, shortened development time and excellent solvent resistance, a color filter and a display device formed using the photosensitive colored resin composition to do it for the second purpose.

A color material dispersion according to a first aspect of the present invention for solving the first object is a color material dispersion containing a color material, a dispersing agent, and a solvent, wherein the dispersing agent comprises a structural unit represented by the following general formula (I) and the following general A graft copolymer having a structural unit represented by the formula (II), and at least a portion of the nitrogen moiety included in the structural unit represented by the general formula (I) of the graft copolymer, an organic acid compound, and a halogenated hydrocarbon At least one type selected from the group is at least one type of salt-type graft copolymer in which a salt is formed.

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

In the general formula (II), R ^1' is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer is a polymer chain, and the structural unit of the polymer chain is a structure represented by the following general formula (III) units are included.)

(in general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m is a number from 19 to 80 indicates.)

The dispersant according to the first present invention for solving the first object is a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and A salt-type graft copolymer in which at least a portion of the nitrogen moiety of the structural unit represented by the general formula (I) of the graft copolymer and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon form a salt at least one

The first photosensitive colored resin composition according to the present invention for solving the first object contains the dispersing agent, the colorant, the alkali-soluble resin, the polyfunctional monomer, the photoinitiator and the solvent according to the present invention.

The photosensitive colored resin composition according to the second present invention for solving the second object contains a colorant, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,

The photoinitiator contains an oxime ester-based photoinitiator having a diphenylsulfide skeleton,

The dispersant is a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the graft copolymer represented by the general formula (I) At least one kind of a salt-type graft copolymer in which at least a part of the nitrogen moiety of the structural unit and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons has formed a salt is contained.

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

In the general formula (II), R ^1' is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer is a polymer chain, and the structural unit of the polymer chain is represented by the following general formula (III") At least one structural unit selected from the group consisting of structural units and structural units represented by the following general formula (III') are included.)

(In the general formula (III"), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m" is 3 or more and 80 or less represents the number of

In the general formula (III'), R ^4' is a hydrogen atom or a methyl group, A ^3' is a divalent linking group, R ⁷ is an alkylene group having 1 to 10 carbon atoms, R ⁸ is an alkylene group having 3 to 7 carbon atoms, R ⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less.)

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

A display device according to the present invention has the color filter according to the present invention.

According to the first aspect of the present invention, it is possible to provide a color material dispersion and dispersant capable of producing a photosensitive colored resin composition that simultaneously satisfies the suppression of the occurrence of development residues, the shortening of the development time, the suppression of the occurrence of water stains, and the excellent solvent resistance. Moreover, according to this invention, this invention can provide the photosensitive colored resin composition which simultaneously satisfy|fills suppression of development residue generation|occurrence|production, shortening of developing time, suppression of water stain generation, and favorable solvent resistance. Moreover, according to this invention, the color filter and display apparatus formed using the said photosensitive colored resin composition can be provided.

ADVANTAGE OF THE INVENTION According to 2nd this invention, the photosensitive colored resin composition which satisfy|fills dispersion stability, high contrast, development time shortening, and excellent solvent resistance at the same time can be provided. Moreover, according to this invention, the color filter and display apparatus formed using the said photosensitive colored resin composition can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the color filter of this invention.
2 is a schematic diagram showing an example of a liquid crystal display device of the present invention.
3 is a schematic diagram illustrating an example of an organic light emitting display device of the present invention.
4 is a diagram schematically showing a part of an example of the structure of a graft copolymer used in the present invention.
It is a schematic diagram explaining the taper angle (theta) of the cross-sectional shape of the micropore in a colored layer.

Hereinafter, the color material dispersion liquid, the dispersant, the photosensitive colored resin composition, the color filter, and the display device according to the present invention will be sequentially described in detail.

Further, in the present invention, electromagnetic waves of wavelengths in the visible and invisible regions, and furthermore, radiation are included in light, and microwaves and electron beams are included in the radiation, for example. Specifically, it refers to electromagnetic waves and electron beams having a wavelength of 5 µm or less.

In this invention, (meth)acryloyl represents each of acryloyl and methacryloyl, (meth)acryl represents each of acryl and methacryl, and (meth)acrylate means an acrylate and methacryl. Each rate is indicated.

In the present specification, unless otherwise specified, the chromaticity coordinates x and y are in the XYZ color system according to JIS Z8701:1999 colorimetrically performed using a C light source.

In addition, in this specification, "to" which shows a numerical range is used in the meaning which includes the numerical value described before and behind it as a lower limit and an upper limit.

I. First Invention

I-1. Colorant dispersion according to the first invention

The color material dispersion according to the first aspect of the present invention is a color material dispersion containing a color material, a dispersing agent, and a solvent,

The dispersant is a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the graft copolymer represented by the general formula (I) At least one type of salt-type graft copolymer in which at least one member selected from the group consisting of an organic acid compound and a halogenated hydrocarbon with at least a portion of the nitrogen moiety of the structural unit has formed a salt.

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

In the general formula (II), R ^1' is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer is a polymer chain, and the structural unit of the polymer chain is a structure represented by the following general formula (III) units are included.)

(in general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m is a number from 19 to 80 indicates.)

The color material dispersion according to the first aspect of the present invention uses the specific graft copolymer or salt type graft copolymer as a dispersant. 4 is a view schematically showing a part of an example of the structure of the graft copolymer used in the first invention. In Fig. 4, the graft copolymer 110 contains a main chain portion 112 having a structural unit 121 represented by the general formula (I) and a structural unit 122 represented by the general formula (II). and at least one member (123) selected from the group consisting of at least a part of the nitrogen moiety of the structural unit (121) represented by the general formula (I) and an organic acid compound and a halogenated hydrocarbon may form a salt, The structural unit 122 represented by the general formula (II) is represented by the general formula (III) containing a polyethylene oxide chain or a polypropylene oxide chain 126 having a specific repeating number in the polymer chain 124 A structural unit 125 is included. In the specific graft copolymer used in the first invention, a structural unit having a polyethylene oxide chain or a polypropylene oxide chain having a specific number of repetitions in the structural unit of the polymer chain 124 grafted in this way ( 125) is included, and the grafted polymer chain 124 itself has a branched structure. Therefore, the photosensitive colored resin composition prepared using the dispersing agent according to the first present invention or the color material dispersion according to the first present invention has excellent solvent resistance and suppression of development residue generation, shortening of development time, suppression of occurrence of water stains, and excellent solvent resistance. can be satisfied at the same time. Although it has not yet been elucidated as an effect|action which exhibits such an effect, it is estimated as follows.

In the specific graft copolymer, a structural unit having a relatively long polyethylene oxide chain or polypropylene oxide chain is included in the structural unit of the grafted polymer chain, and the grafted polymer chain itself has a branched structure. is characterized. It is thought that the oxygen atom contained in a polyethylene oxide chain or a polypropylene oxide chain becomes easy to melt|dissolve in an alkali developing solution at the time of image development by hydrogen bonding with an alkali developing solution. In addition, the oxygen atom contained in the polyethylene oxide chain or the polypropylene oxide chain interacts with OH or CH such as a carboxy group of the alkali-soluble resin contained in the photosensitive resin composition by hydrogen bonding, so that only the alkali-soluble resin is produced at the time of development. It is thought that it can suppress that it melt|dissolves and a color material and a dispersing agent remain as a residue. Since the structural unit of the grafted polymer chain contains a structural unit having a relatively long polyethylene oxide chain or polypropylene oxide chain in a branched structure, the interaction by hydrogen bonding with an alkali developer or alkali-soluble resin is strong. I think it will In the graft copolymer, since the plurality of grafted polymer chains have a branched structure and become the solvent affinity portion of the dispersant, the specific surface area of the solvent affinity portion of the dispersant increases as compared to the block copolymer, and polyethylene oxide chains Alternatively, it is estimated that the action of the solvent affinity portion by the oxygen atom contained in the polypropylene oxide chain becomes remarkable, the effect of suppressing the occurrence of development residues is improved, and the development time is shortened.

On the other hand, when the number of repeating units of a polyethylene oxide chain|strand or polypropylene oxide chain|strand became large too much, it discovered that the development residue generation|occurrence|production inhibitory effect was not improved on the contrary. This is because, when the number of repeating units of polyethylene oxide chains or polypropylene oxide chains becomes too large, the affinity with the alkali developer becomes excessively greater than the pigment adsorption force, so that only the graft copolymer is dissolved in the alkali developer, and the pigment is left on the substrate. It is assumed that this is not

In addition, in the graft copolymer, since a plurality of grafted polymer chains become the solvent affinity portion of the dispersant, the specific surface area of the solvent affinity portion of the dispersant becomes large, so that penetration of the solvent into the coating film or reaching the color material is prevented. presumed to be suppressed. Therefore, when the dispersing agent of the present invention is used, it is estimated that solvent resistance and resistance (NMP resistance) to N-methylpyrrolidone (NMP) used as a solvent for production of an alignment film of a color filter can be improved.

Moreover, water absorption into a cured film is mentioned as a water stain cause of the cured film of the photosensitive resin composition. Since alkali-soluble resin in a cured film has acidic groups, such as a carboxy group, it is easy to absorb. Moreover, it is thought that water absorption becomes higher by the said acidic group forming a metal salt with the alkali metal typically contained in an alkali developing solution at the time of image development. The oxygen atom contained in the polyethylene oxide chain or the polypropylene oxide chain is captureable by complex-forming with metals, such as an alkali metal. As the number of repeating units of polyethylene oxide chains or polypropylene oxide chains increases, the complex formation constant increases and the ability to capture metal molecules increases, thereby suppressing the formation of alkali metal salts of alkali-soluble resins and reducing absorption into the cured film. It is assumed that it can be suppressed. In addition, the oxygen atom contained in the polyethylene oxide chain or the polypropylene oxide chain interacts with an acidic group such as a carboxy group of an alkali-soluble resin contained in the photosensitive resin composition by hydrogen bonding, thereby inhibiting the formation of an alkali metal salt of the acidic group, It is estimated that absorption into a cured film can be suppressed. In the graft copolymer, since a plurality of grafted polymer chains have a branched structure and become a metal trapping portion, the specific surface area of the metal trapping portion of the dispersant increases, and oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain It is estimated that the effect of metal trapping becomes remarkable, the effect of suppressing absorption is improved, and generation of water stains due to absorption can be suppressed. It is estimated that generation|occurrence|production of the water stain by water absorption can be suppressed by the absorption inhibitory action into these cured films.

The first colorant dispersion according to the present invention contains at least a colorant, a dispersing agent, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention.

Hereinafter, each component of the color material dispersion according to the first present invention will be described in detail sequentially from the first dispersing agent of the present invention.

<The first dispersant of the present invention>

In the first invention, as a dispersant, a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and the general formula of the graft copolymer At least one type of salt-type graft copolymer in which at least a part of the nitrogen moiety of the structural unit represented by (I) and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon form a salt is used.

First, the graft copolymer will be described.

(Constitutive unit represented by the general formula (I))

The structural unit represented by the said general formula (I) which comprises the main chain of a graft copolymer has basicity, and functions as an adsorption site|part with respect to a color material.

In the general formula (I), A ¹ is a divalent linking group. Examples of the divalent linking group include a straight-chain, branched or cyclic alkylene group, a hydroxyl group, a straight-chain, branched or cyclic alkylene group, an arylene group, a -CONH- group, a -COO- group, a -NHCOO- group, an ether group (- O- group), thioether group (-S- group), and combinations thereof. In addition, in this invention, the bonding direction of a bivalent coupling group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO is the carbon atom side of the main chain and -NH may be the nitrogen atom side of the side chain, conversely -NH is the carbon atom side of the main chain and -CO is the nitrogen atom side of the side chain The atomic side may be sufficient.

Among them, from the viewpoint of dispersibility, A ¹ in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and the number of -CONH- groups or -COO- groups and carbon atoms It is more preferable that it is a divalent coupling group containing the alkylene group of 1-10.

In R ² and R ³ , the hydrocarbon group in the hydrocarbon group which may contain a hetero atom includes, for example, 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 tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and the like, and the number of carbon atoms in the alkyl group is 1 -18 are preferable, and especially, it is more preferable that they are a methyl group or an ethyl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for the number of carbon atoms of an aralkyl group, 7-14 are more preferable.

Moreover, as an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. 6-24 are preferable and, as for the number of carbon atoms of an aryl group, 6-12 are more preferable. In addition, the number of carbon atoms of a substituent is not included in the said preferable number of carbon atoms.

The hydrocarbon group including a hetero atom has a structure in which a carbon atom in the hydrocarbon group is substituted with a hetero atom, or a structure in which a hydrogen atom in the hydrocarbon group is substituted with a substituent containing a hetero atom. As a hetero atom which the hydrocarbon group may contain, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc. are mentioned, for example.

Moreover, the hydrogen atom in a hydrocarbon group may be substituted by halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom.

That R ² and R ³ are mutually bonded to form a ring structure means that R ² and R ³ form a ring structure through a nitrogen atom. A hetero atom may be contained in the ring structure formed by R ² and R ³ . Although the ring structure is not specifically limited, For example, a pyrrolidine ring, a piperidine ring, a morpholine ring, etc. are mentioned.

In the present invention, among them, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ² and R ³ are bonded to each other to form a pyrrolidine ring, a piperidine ring, It is preferable to form a morpholine ring.

Examples of the monomer for deriving the structural unit represented by the general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl ( alkyl group-substituted amino group-containing (meth)acrylates such as meth)acrylate, and alkyl group-substituted amino group-containing (meth)acrylamide such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide. . Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used from the viewpoint of improving dispersibility and dispersion stability.

The structural unit represented by general formula (I) may contain 1 type, and may contain 2 or more types of structural units.

(constitutive unit represented by general formula (II))

When the said graft copolymer has the structural unit represented by the said General formula (II) which has a specific polymer chain, solvent affinity becomes favorable, and the dispersibility and dispersion stability of a color material become favorable. In addition, the graft copolymer has steric hindrance and increase in specific surface area due to a specific polymer chain contained in the structural unit represented by the general formula (II), and in particular, the structural unit of the polymer chain contains the above general formula (III). ), the interaction with the alkali-soluble resin, developer, or metal is good as described above, and the photosensitive resin composition suppresses the development of residues, shortens the development time, suppresses the occurrence of water stains, and has solvent resistance. to improve

In the general formula (II), A ² is a direct bond or a divalent linking group. There will be no restriction|limiting in particular as a ^divalent coupling group in A2, if the carbon atom and polymer chain derived from an ethylenically unsaturated double bond can be linked. Examples of the divalent linking group for A ² include the same divalent linking group for A ¹ .

In the said general formula (II), Polymer represents a polymer chain, and the structural unit represented by the said general formula (III) is contained in the structural unit of this polymer chain.

In the general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m is a number from 19 to 80 indicates

Examples of the divalent linking group for A ³ include the same divalent linking group for A ¹ . Among them, from the viewpoint of solubility in the organic solvent used for color filter applications, A ³ in general formula (III) is preferably a divalent linking group containing -CONH- group or -COO- group, -CONH- It is more preferably a group or -COO-group.

Said m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and although it shows a number 19 or more, it is preferable that it is 21 or more from the point of water stain generation|occurence|production suppression among them.

On the other hand, although the upper limit of m is 80 or less, it is preferable that it is 50 or less from the point of the solubility to the organic solvent used for a color filter use.

Examples of the hydrocarbon group for R ⁶ include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, and combinations thereof such as an aralkyl group and an alkyl-substituted aryl group.

The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, n-nonyl group, n-lauryl group. , n-stearyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl-substituted adamantyl group, and the like. 1-12 are preferable and, as for carbon number of an alkyl group, 1-6 are more preferable.

The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. Although there is no limitation on the position of the double bond of an alkenyl group, It is preferable that a double bond exists at the terminal of the alkenyl group from the point of the reactivity of the obtained polymer. 2-12 are preferable and, as for carbon number of an alkenyl group, 2-8 are more preferable.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.

Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, You may have a substituent further. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.

Moreover, a C1-C30 linear or branched alkyl group may couple|bond with aromatic rings, such as said aryl group and an aralkyl group, as a substituent.

Among them, the hydrocarbon group for R ⁶ is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and arral having 7 to 14 carbon atoms which may be substituted by an alkyl group from the viewpoint of dispersion stability. It is preferably at least one selected from the group consisting of a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, n-nonyl group, n-lauryl group, n-stearyl group, alkyl group It is preferable that is at least one selected from the group consisting of an optionally substituted phenyl group and benzyl group.

The said polymer chain WHEREIN: Although 1 type may be sufficient as the structural unit represented by the said General formula (III), 2 or more types may be mixed.

From the viewpoint of the effect of the present invention, in the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, when the total structural units of the polymer chain is 100% by mass, the general formula ( It is preferable that it is 1 mass % or more, and, as for the total ratio of the structural unit represented by III), it is more preferable that it is 2 mass % or more, It is still more preferable that it is 4 mass % or more. The total proportion of the structural units represented by the general formula (III) may be 100% by mass when the total structural units of the polymer chain are 100% by mass, but from the standpoint of suppressing the occurrence of water stains, it is 75% by mass or less It is preferable, and it is more preferable that it is 65 mass % or less, and it is still more preferable that it is 50 mass % or less from a solvent re-solubility point.

In the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, a structural unit represented by the following general formula (IV) different from the structural unit represented by the general formula (III) It is preferable from the point of the dispersibility and dispersion stability of a color material that is further included.

(In formula (IV), R ^4″ is a hydrogen atom or a methyl group, A ⁴ is a divalent linking group, and R ¹⁰ is a hydrogen atom or a hydrocarbon group which may contain a hetero atom.)

Examples of the divalent linking group for A ⁴ include the same divalent linking group for A ¹ . Among them, from the viewpoint of solubility in the organic solvent used for color filter applications, A ⁴ in general formula (IV) is preferably a divalent linking group containing -CONH- group or -COO- group, -CONH- It is more preferably a group or -COO-group.

In R ¹⁰ , the hydrocarbon group in the hydrocarbon group which may contain a hetero atom includes, for example, an alkyl group, an alkenyl group, an aryl group, and combinations thereof such as an aralkyl group and an alkyl-substituted aryl group. Examples of the hydrocarbon group in the hydrocarbon group that may contain a hetero atom for R ¹⁰ include the same hydrocarbon group as the hydrocarbon group for R ⁶ .

As a hetero atom which the hydrocarbon group may contain, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc. are mentioned, for example. As the hydrocarbon group which may contain a hetero atom, for example, in the carbon chain of the hydrocarbon group, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO- , -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O- The structure in which coupling groups, such as NH-, are contained is mentioned.

In addition, the hydrocarbon group may have a substituent in a range that does not interfere with the dispersion performance of the graft copolymer, etc. As the substituent, for example, a halogen atom, a hydroxyl group, a carboxy group, an alkoxy group, a nitro group, a cyano group, an epoxy group, an isocyanate group a group, a thiol group, etc. are mentioned.

Further, the hydrocarbon group which may contain a hetero atom for R ¹⁰ may be a structure in which a polymerizable group such as an alkenyl group is added to the terminal through a linking group containing a hetero atom in the hydrocarbon group. For example, the structure in which the structural unit represented by general formula (IV) made glycidyl (meth)acrylate react with the structural unit derived from (meth)acrylic acid may be sufficient. That is, the structure of -A ⁴ -R ¹⁰ in the general formula (IV) is represented by -COO-CH ₂ CH(OH)CH ₂ -OCO-CR=CH ₂ (wherein R is a hydrogen atom or a methyl group) Any structure that can be Moreover, the structural unit represented by general formula (IV) may have a structure in which 2-isocyanatoalkyl (meth)acrylate was made to react with the structural unit derived from hydroxyalkyl (meth)acrylate. That is, R ¹⁰ in the general formula (IV) is -R'-OCONH-R"-OCO-CR=CH ₂ (wherein R' and R" are each independently an alkylene group, and R is a hydrogen atom or a methyl group) A structure represented by .

Examples of the monomer for deriving the structural unit represented by the general formula (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate , Phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid, 2-methacryloyloxyethyl succinate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy- 3-phenoxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate, phenoxy in which the number of repeating units of the ethylene oxide chain is less than 19 It is preferable to have a structural unit derived from ethylene glycol (meth)acrylate etc. However, it is not limited to these.

In the present invention, as R ¹⁰ , it is preferable to use one having excellent solubility with an organic solvent, which will be described later, and may be appropriately selected according to the organic solvent used for the color material dispersion liquid. Specifically, for example, when organic solvents such as ether alcohol acetate, ether, ester and alcohol which are generally used as organic solvents for colorant dispersion are used as the organic solvent, methyl group, ethyl group, isobutyl group, n -Butyl group, 2-ethylhexyl group, benzyl group, cyclohexyl group, dicyclopentanyl group, hydroxyethyl group, phenoxyethyl group, adamantyl group, methoxy polyethylene glycol group, methoxy polypropylene glycol group, polyethylene glycol group etc. are preferable.

The said polymer chain WHEREIN: Although 1 type may be sufficient as the structural unit represented by the said General formula (IV), 2 or more types may be mixed.

From the viewpoint of dispersibility and dispersion stability of the color material, in the polymer chain, the total ratio of the structural units represented by the general formula (IV) is 25 mass% when the total structural units of the polymer chain is 100% by mass. % or more, and more preferably 35 mass% or more. On the other hand, from the viewpoint of suppressing the occurrence of water stains by introduction of the general formula (III), in the polymer chain, the total ratio of the structural units represented by the general formula (IV) is the total structural units of the polymer chain. When it is set as 100 mass %, it is preferable that it is 99 mass % or less, and it is more preferable that it is 98 mass % or less.

In the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the structural unit represented by the general formula (IV), among others, a configuration represented by the following general formula (IIIa) It is preferable that the unit is further included in that the effect of suppressing the development residue is improved.

(in the general formula (IIIa), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m' is a number of 10 or less indicate.)

R ⁴ , A ³ , R ⁵ , and R ⁶ in the general formula (IIIa) may be the same as R ⁴ , A ³ , R ⁵ , and R ⁶ in the general formula (III), respectively.

Although m' in the said General formula (IIIa) shows a number of 10 or less, It is preferable that it is 2 or more, and, as for m', it is more preferable that it is 3 or more from the point of development residue generation|occurrence|production suppression. Moreover, it is preferable that it is 9 or less from a solvent re-solubility point, and, as for m', it is more preferable that it is 8 or less.

The said polymer chain WHEREIN: Although 1 type may be sufficient as the structural unit represented by the said General formula (IIIa), 2 or more types may be mixed.

From the viewpoint of improving the effect of suppressing development residues, in the polymer chain, the total proportion of the structural units represented by the general formula (IIIa) is 20% by mass, when all the structural units of the polymer chain are 100% by mass. more preferably. On the other hand, from the viewpoint of solvent re-solubility, in the polymer chain, the total ratio of the structural units represented by the general formula (IIIa) is 80% by mass or less when all the structural units of the polymer chain are 100% by mass. It is preferable, and it is more preferable that it is 60 mass % or less.

Further, in the polymer chain, the mixing ratio of the structural unit represented by the general formula (III) and the structural unit represented by the general formula (IIIa) is an improvement in the effect of inhibiting the occurrence of development residues, and thus the general formula When the total of the structural unit represented by (III) and the structural unit represented by the general formula (IIIa) is 100 parts by mass, the structural unit represented by the general formula (III) is preferably 3 parts by mass or more, 6 It is more preferable that it is more than mass part, It is preferable that it is 80 mass parts or less, It is more preferable that it is 60 mass parts or less.

The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer includes the structural unit represented by the general formula (III) and the structural unit represented by the general formula (IIIa). In addition to the structural unit represented by the general formula (IV), other structural units may be included.

As the other structural unit, a structural unit derived from a monomer having an unsaturated double bond copolymerizable with a monomer derived from the structural unit represented by the general formula (III) or a monomer derived from the structural unit represented by the formula (IV). can be heard

Examples of the monomer that induces other structural units include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as phenyl vinyl ether.

In the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the total ratio of the other structural units is the effect of the present invention, so that the total structural units of the polymer chain are 100 mass When it is set as %, it is preferable that it is 30 mass % or less, and it is more preferable that it is 10 mass % or less.

The mass average molecular weight (Mw) of the polymer chain in the polymer is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, and 15000 or less from the viewpoint of dispersibility and dispersion stability of the color material. It is more preferable, and it is still more preferable that it is 12000 or less.

By being within the above range, sufficient steric repulsion effect as a dispersing agent can be maintained, and as the specific surface area of the solvent affinity portion of the dispersant increases, the interaction by the oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain is remarkable. Thus, it is possible to improve the effect of suppressing the occurrence of development residues, shorten the development time, and improve the solvent resistance.

Moreover, it is preferable that the solubility in 23 degreeC is 20 (g/100g solvent) or more with respect to the organic solvent used in combination as a reference|standard as for the polymer chain in Polymer.

The solubility of the polymer chain may be based on the fact that the raw material into which the polymer chain is introduced when preparing the graft copolymer has the solubility. For example, in the case of using a polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal in order to introduce a polymer chain into the graft copolymer, the polymerizable oligomer may have the above solubility. . In addition, after the copolymer is formed by a monomer containing a group having an ethylenically unsaturated double bond, when the polymer chain is introduced using a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer, the reactive group A polymer chain containing a group of

(graft copolymer)

In the said graft copolymer, it is preferable that the structural unit represented by the said general formula (I) is contained in the ratio of 3-60 mass %, 6-45 mass % is more preferable, 9-30 mass % is more preferable. When the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the color material in the graft copolymer is appropriate, and the decrease in solubility in organic solvents can be suppressed. For this reason, the adsorption property with respect to a color material becomes favorable, and the outstanding dispersibility and dispersion stability can be acquired.

On the other hand, in the said graft copolymer, it is preferable that the structural unit represented by the said general formula (II) is contained in the ratio of 40-97 mass %, 55-94 mass % is more preferable, 70-91 mass % is more preferable. Mass % is more preferable. When the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent-affinity part in the graft copolymer becomes appropriate, and a sufficient steric repulsion effect as a dispersant can be maintained, and the dispersant As the specific surface area of the solvent affinity part of It can work well.

In addition, the content rate of the said structural unit is computed from the injection amount at the time of synthesizing the graft copolymer which has the structural unit represented by general formula (I) and the structural unit represented by general formula (II).

The graft copolymer used in the present invention has other constitutions other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), within the range not impairing the effects of the present invention. You may have more units. As the other structural unit, an ethylenically unsaturated double bond-containing monomer copolymerizable with an ethylenically unsaturated double bond-containing monomer or the like that induces the structural unit represented by the general formula (I) is appropriately selected and copolymerized to introduce another structural unit can do.

As another structural unit copolymerized with the structural unit represented by the general formula (I), for example, a structural unit represented by the general formula (III) in the structural unit of the polymer chain of the structural unit represented by the general formula (II) A structural unit having a graft chain different from that of the structural unit represented by the general formula (II) or a structural unit having a different structural unit from the structural unit represented by the general formula (II) or the general formula (IV) and structural units represented by .

Moreover, it is preferable that it is 4000 or more from the point of dispersibility and dispersion stability, and, as for the mass average molecular weight (Mw) of the said graft copolymer, it is more preferable that it is 6000 or more, It is still more preferable that it is 8000 or more. On the other hand, from the point of solvent re-solubility, it is preferable that it is 50000 or less, and it is more preferable that it is 30000 or less.

In addition, in this invention, a mass average molecular weight (Mw) is the value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol/liter lithium bromide was added, and the polystyrene standard for calibration curve was Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (made by coating agent), and the measurement column was TSK-GEL ALPHA-M x 2 copies (made by coating agent) it was done

In addition, the amine titer of the graft copolymer before salt formation is not particularly limited, but from the viewpoint of color material dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH/g or more, and more preferably 50 mgKOH/g or more, It is still more preferable that it is 60 mgKOH/g or more. Moreover, as an upper limit, it is preferable that it is 140 mgKOH/g or less, It is more preferable that it is 130 mgKOH/g or less, It is still more preferable that it is 120 mgKOH/g or less. Dispersion stability is more excellent as it is more than the said lower limit. Moreover, compatibility with another component will be excellent as it is below the said upper limit, and solvent re-solubility will become favorable.

In the present invention, the amine value of the graft copolymer before salt formation refers to the mass (mg) of potassium hydroxide that is equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the graft copolymer before salt formation, It is a value measured by the method described in JISK7237:1995.

It is preferable that it is 18 mgKOH/g or less, and, as for the acid value of the graft copolymer before salt formation, it is more preferable that it is 12 mgKOH/g or less at the point which image development adhesiveness and solvent re-solubility become favorable. In addition, the acid value of the graft copolymer before salt formation may be less than 1 mgKOH/g from the point of improving solvent re-solubility and image development adhesiveness more, and the point of dispersion stability. On the other hand, from the viewpoint of the inhibitory effect of the image development residue, it is preferable that it is 1 mgKOH/g or more, and it is more preferable that it is 2 mgKOH/g or more.

The acid value of the graft copolymer before salt formation indicates the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the graft copolymer, measured by the method described in JIS K 0070:1992 is the value

(Method for producing graft copolymer)

In the present invention, as a method for producing the graft copolymer, a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) can be produced What is necessary is just a method, and it does not specifically limit. When preparing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), for example, a monomer represented by the following general formula (Ia) and the polymer chain and a method for preparing a graft copolymer by copolymerizing a polymerizable oligomer (macromonomer) containing a group having an ethylenically unsaturated double bond at the terminal thereof as a copolymerization component.

If necessary, other monomers may be additionally used, and a graft copolymer may be prepared using a known polymerization means.

(In general formula (Ia), R ¹ , A ¹ , R ² and R ³ are the same as in general formula (I).)

In the case of producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), the monomer represented by the general formula (Ia) and other ethylene After addition polymerization of a monomer containing a group having a sexually unsaturated double bond to form a copolymer, the polymer chain may be introduced using a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer. Specifically, for example, after synthesizing a copolymer having a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, and a hydrogen bond forming group, a polymer chain containing a functional group that reacts with the substituent is reacted with a polymer chain. It is also good to introduce

For example, a polymer chain having a carboxyl group at the terminal is reacted with a copolymer having a glycidyl group in the side chain, or a polymer chain having a hydroxyl group at the terminal is reacted with a copolymer having an isocyanate group in the side chain to introduce a polymer chain. can

In the polymerization, additives generally used for polymerization, such as polymerization initiators, dispersion stabilizers, chain transfer agents, and the like may be used.

(at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons)

In the present invention, the dispersant comprises at least a part of the nitrogen moiety of the structural unit represented by the general formula (I) of the graft copolymer, an organic acid compound, and a halogenated hydrocarbon from the viewpoint of improving the dispersibility of the color material. A salt-type graft copolymer in which at least one selected from the group formed a salt may be used.

The organic acid compound is preferably a compound represented by the following general formula (1) and a compound represented by the following general formula (3), and among them, the halogenated hydrocarbon is a compound represented by the following general formula (2) This is preferable. That is, as at least 1 type selected from the group which consists of the said organic acid compound and a halogenated hydrocarbon, 1 or more types of compounds selected from the group which consists of following General formula (1) - (3) can be used preferably.

(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 benzyl group optionally having a substituent, or -OR ^e , and R ^e is a carbon number Represents a (meth)acryloyl group via a 1 to 20 linear, branched or cyclic alkyl group, a vinyl group, an optionally substituted phenyl or benzyl group, or an alkylene group having 1 to 4 carbon atoms. In 2), R ^b , R ^{b '} and R ^{b "} are each independently a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent Represents optionally a vinyl group, optionally substituted phenyl or benzyl group, or -OR ^f , R ^f is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms optionally having a substituent, or optionally having a substituent A vinyl group, a optionally substituted phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, X represents a chlorine atom, a bromine atom or an iodine atom. In 3), R ^c and R ^d are each independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -OR ^e and R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group optionally having a substituent, or (meth)acrylo via an alkylene group having 1 to 4 carbon atoms. a diary, provided that at least one of R ^c and R ^d contains a carbon atom.)

(at least one compound selected from the group consisting of the general formulas (1) to (3))

In the above general formulas (1) to (3), R ^a , R ^b , R ^{b '} , R ^{b "} , R ^c , R ^d , R ^e and R ^f are straight or branched chains having 1 to 20 carbon atoms. Alternatively, the cyclic alkyl group may be either linear or branched, and may contain a cyclic structure, specifically methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, isobutyl group. group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, dodecyl group, cyclopentyl group, cyclohexyl group, tetradecyl group, octadecyl group, etc. Preferably, a C1-C15 linear, branched or cyclic alkyl group is mentioned, More preferably, a C1-C8 group is mentioned. a straight-chain, branched-chain or cyclic alkyl group.

In addition, in R ^a , R ^c , R ^d and ^Re , examples of the substituent of the optionally substituted phenyl group or benzyl group include an alkyl group having 1 to 5 carbon atoms, an acyl group, and an acyloxy group. there is.

In R ^b , R ^{b '} , R ^{b "} and R ^f , as the substituent of the optionally substituted phenyl group or benzyl group, for example, an acidic group or an ester group thereof, an alkyl group having 1 to 5 carbon atoms, an acyl group, An acyloxy group etc. are mentioned.

In addition, in R ^b , R ^{b '} , R ^{b "} and R ^f , a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent or a vinyl group as a substituent is an acidic group or an ester group thereof. , a phenyl group, an acyl group, an acyloxy group, and the like.

In R ^b , R ^{b '} , R ^{b "} and R ^f , the acidic group refers to a group that releases a proton in water and exhibits acidity. Specific examples of the acidic group include a carboxy group (-COOH), a sulfo group (-SO ₃ H) , phosphono group (-P(=O)(OH) ₂ ), phosphinico group (>P(=O)(OH)), boronic acid group (-B(OH) ₂ ), borin acid group (>BOH) and the like, and may be an anion in which a hydrogen atom is dissociated, such as a carboxylato group (-COO- ⁾ , or an acid salt in which a salt is formed with an alkali metal ion such as a sodium ion or potassium ion.

In addition, as an ester group of an acidic group, carboxylate ester (-COOR), sulfonic acid ester (-SO ₃ R), phosphoric acid ester (-P(=O)(OR) ₂ ), (>P(=O)( OR)), boronic acid ester (-B(OR) ₂ ), and boronic acid ester (>BOR). Especially, as an ester group of an acidic group, it is preferable from the point of dispersibility and dispersion stability that it is a carboxylate ester (-COOR). Here, R is a hydrocarbon group, and although it is not specifically limited, It is preferable that it is a C1-C5 alkyl group especially from the point of dispersibility and dispersion stability, and it is more preferable that it is a methyl group or an ethyl group.

The compound of the general formula (2) is selected from a carboxy group, a boronic acid group, a boric acid group, an anion thereof, and an alkali metal salt thereof and an ester thereof from the viewpoint of dispersibility, dispersion stability, alkali developability and development residue suppression It is preferable to have one or more kinds of functional groups, and among them, those having a functional group selected from a carboxyl group, a carboxylato group, a carboxylate group and a carboxylate group are more preferable.

When the compound of the general formula (2) has an acidic group and an ester group thereof (hereinafter referred to as an acidic group or the like), the nitrogen moiety at the end of any hydrocarbon on the side of the acidic group and the like and the halogen atom of the compound Although it can form a salt with a salt, it is estimated that the nitrogen site at the terminal and the hydrocarbon on the halogen atom side form a salt stably compared to the case where the nitrogen moiety and acidic group at the terminal form a salt. And, it is estimated that the dispersibility and dispersion stability are improved by adsorbing the color material to the stably existing salt formation site.

When the compound of the said General formula (2) has the said acidic group etc., you may have 2 or more of the said acidic groups etc. When it has two or more of the said acidic group etc., the said acidic group etc. which exist in multiple may be same or different. It is preferable that it is 1-3, as for the number of the said acidic group etc. which the compound of the said General formula (2) has, It is more preferable that it is 1-2, It is still more preferable that it is 1.

R ^a in the general formula (1), at least one of R ^b , R ^{b '} and R ^{b "} in the general formula (2), and at least one of R ^c and R ^d in the general formula (3) When it has an aromatic ring, affinity between the skeletons of the color material mentioned later improves, it becomes a thing excellent in the dispersibility and dispersion stability of a color material, and it is preferable at the point that the coloring composition excellent in contrast can be obtained.

The molecular weight of the at least one compound selected from the group consisting of the general formulas (1) to (3) is preferably 1000 or less from the viewpoint of improving colorant dispersibility, particularly preferably 50 to 800, and 50 to It is still more preferable that it is 400, It is still more preferable that it is 80-350, It is most preferable that it is 100-330.

Examples of the compound represented by the general formula (1) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, and monon-propylsulfuric acid. Also, a hydrate such as p-toluenesulfonic acid monohydrate may 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, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, Hexadecyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α-chlorophenyl acetic acid, α-bromophenyl acetic acid, α-iodophenyl acetic acid, 4-chloromethylbenzoic acid, 4- and bromomethylbenzoic acid, 4-iodophenylbenzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, α-bromophenylacetate methyl, 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, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like. can be heard

In terms of particularly excellent dispersion stability, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutyl phosphoric acid, methyl chloride, methyl bromide, methyl iodide, benzyl chloride, benzyl bromide, vinyl sulfonic acid and At least one selected from the group consisting of p-toluenesulfonic acid monohydrate is preferable, and among them, one selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl chloride, benzyl bromide and p-toluenesulfonic acid monohydrate It is preferable to use the above.

In addition, since the effect of inhibiting development residues is improved by combination with the specific graft copolymer, a compound represented by the general formula (2) having an acidic group and an ester group thereof is also preferably used, and among them, α-chloro At least one selected from the group consisting of phenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid and 4-iodophenylbenzoic acid is also preferably used.

In the salt-type graft copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons forms a salt with the nitrogen moiety at the terminal of the structural unit represented by the general formula (I). , It is preferable that the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0.01 mol or more, and 0.05 mol or more with respect to the nitrogen moiety at the terminal of the structural unit represented by the general formula (I) It is more preferable to set it as 0.1 mol or more, and it is especially preferable to set it as 0.2 mol or more. If it is more than the said lower limit, the color material dispersibility improvement effect by salt formation is easy to be acquired. Similarly, it is preferable to set it as 1 mol or less, It is more preferable to set it as 0.8 mol or less, It is further more preferable to set it as 0.7 mol or less, It is especially preferable to set it as 0.6 mol or less. It can be set as the thing excellent in image development adhesiveness and solvent re-solubility as it is below the said upper limit.

In addition, at least 1 type selected from the group which consists of an organic acid compound and a halogenated hydrocarbon may be used individually by 1 type, and may combine 2 or more types. When combining 2 or more types, it is preferable that the total content exists in the said range.

As a method for preparing the salt-type graft copolymer, at least one selected from the group consisting of the above organic acid compound and halogenated hydrocarbon is added to a solvent in which the graft copolymer before salt formation is dissolved or dispersed, stirred, and if necessary A heating method, etc. are mentioned.

In addition, at least one selected from the group consisting of the nitrogen moiety at the terminal of the structural unit represented by the general formula (I) of the graft copolymer and the organic acid compound and halogenated hydrocarbon forms a salt, and the The ratio can be confirmed, for example, by a known method such as NMR.

The amine titer of the obtained salt-type graft copolymer becomes smaller by the amount of salt formation compared with the graft copolymer before salt formation. However, since the salt formation site becomes an enhanced color material adsorption site similarly to the nitrogen site at the terminal corresponding to the amino group, or rather, the color material dispersibility and color material dispersion stability tend to be improved by salt formation. Moreover, when there are too many salt formation sites similarly to an amino group, a bad influence will be exerted on solvent re-solubility. Therefore, in this invention, the amine value of the graft copolymer before salt formation can be made into the parameter|index for making color material dispersion stability and solvent re-solubility favorable. As an amine value of the obtained salt type graft copolymer, it is preferable that it is 0-130 mgKOH/g, It is more preferable that it is 10-120 mgKOH/g, It is still more preferable that it is 20-110 mgKOH/g.

It is excellent in compatibility with another component as it is below the said upper limit, and solvent re-solubility becomes favorable.

In addition, among the salt-type graft copolymers, the amine value of the salt-type graft copolymer in which a salt is formed with the compound represented by the general formula (2) may be a value measured by the method described in JIS K 7237:1995. there is. In the compound of the general formula (2), the nitrogen moiety at the terminal of the structural unit represented by the general formula (I) and the hydrocarbon on the halogen atom side form a salt. It is because the amine number can be measured without causing it.

On the other hand, among the salt-type graft copolymers, the amine value of the salt-type graft copolymer in which a salt is formed with the compound represented by the general formula (1) or (3) is determined from the amine value of the graft copolymer before salt formation. It can be calculated|required by calculating as follows. Since the compound represented by the general formula (1) or (3) forms a salt with the nitrogen moiety and the acidic group at the terminal of the structural unit represented by the general formula (I), the amine value of the salt-type graft copolymer is This is because, when it is measured by the method described in JIS K 7237:1995, the salt formation state is changed and an accurate value cannot be measured.

First, by the method described above, the amine number of the graft copolymer before salt formation is determined. Next, the 13C-NMR spectrum of the salt-type graft copolymer was measured using a nuclear magnetic resonance apparatus, and in the obtained spectrum data, in the nitrogen site at the terminal of the structural unit represented by the general formula (I), salt formation The terminal of the structural unit represented by the general formula (I) of the salt-type graft copolymer from the ratio of the integral of the peak of a carbon atom adjacent to a nitrogen atom that has not been formed and a peak of a carbon atom adjacent to a nitrogen atom in which a salt is formed With respect to the nitrogen moiety of , the reaction rate of at least one compound selected from the group consisting of the general formula (1) or (3) (the ratio of the nitrogen moiety at the salt-formed terminal) is measured. The nitrogen moiety at the terminal of the structural unit represented by the general formula (I) formed as a salt by at least one compound selected from the group consisting of the general formula (1) or (3) has an amine value of 0, ( Calculated by the amine number of the graft copolymer before salt formation measured by the method described in JIS K 7237:1995 x (ratio (%)/100) of the nitrogen site at the salt-formed terminal calculated from the 13 C-NMR spectrum , can be calculated|required by subtracting the amine value consumed by salt formation from the amine value of the graft copolymer before salt formation.

Amine value of the salt-type graft copolymer = {Amine number of the graft copolymer before salt formation measured by the method described in JIS K 7237: 1995}-{Graft before salt formation measured by the method described in JIS K 7237: 1995 Amine value of the copolymer} × {Ratio of nitrogen sites at the salt-formed terminal calculated from 13 C-NMR spectrum (%)/100}

Further, in the present invention, the hydroxyl value of the dispersant is preferably 120 mgKOH/g or less, more preferably 60 mgKOH/g or less, and still more preferably 30 mgKOH/g or less, from the viewpoint of solvent re-solubility, It is preferably 0 mgKOH/g.

On the other hand, it is preferable that it is 5 mgKOH/g or more from a developable point, and, as for the hydroxyl value of a dispersing agent, it is more preferable that it is 15 mgKOH/g or more.

In the present invention, the hydroxyl value represents the mass (mg) of KOH required to neutralize the acetic acid bound to the acetylated product obtained from 1 g of the solid content, and refers to a value obtained by potentiometric titration in accordance with JIS K 0070:1992. .

The content rate (mol%) of each structural unit in the graft copolymer in the dispersing agent can be calculated|required from the injection amount of a raw material at the time of manufacture, and can also be measured using analyzers, such as NMR. In addition, the structure of a dispersing agent can be measured using NMR, various mass spectrometry, etc. In addition, the decomposition product obtained by decomposing the dispersing agent by thermal decomposition or the like, if necessary, can be obtained using high performance liquid chromatography, gas chromatograph mass spectrometry, NMR, elemental analysis, XPS/ESCA, TOF-SIMS, or the like.

In the color material dispersion according to the present invention, at least one of the graft copolymer and the salt type graft copolymer is used as the dispersing agent, and the content thereof is determined by the type of the color material to be used, and the solid content concentration in the photosensitive colored resin composition to be described later. etc. are appropriately selected.

Content of a dispersing agent is 3-45 mass parts with respect to 100 mass parts of total solids in a color material dispersion, More preferably, it is preferable to mix|blend in the ratio of 5-35 mass parts. It is excellent in the dispersibility and dispersion stability of a color material as it is more than the said lower limit, and it is more excellent in the storage stability of the photosensitive colored resin composition. Moreover, the image development residue becomes favorable as it is below the said upper limit.

In particular, when forming a coating film or a colored layer having a high colorant concentration, the content of the dispersant is 3 to 35 parts by mass, more preferably 5 to 25 parts by mass, with respect to 100 parts by mass of the total solid content in the colorant dispersion. it is preferable

In addition, in this invention, solid content is all things other than the solvent mentioned above, The monomer etc. which are melt|dissolved in the solvent are also contained.

<Color material>

In the present invention, the color material is not particularly limited as long as a desired color can be developed when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, salt-forming compounds of dyes, etc., It can be used individually or in mixture of 2 or more types. Especially, since the color development property is high and heat resistance is also high, an organic pigment is used preferably. Examples of the organic pigment include compounds classified as pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically those to which the following color index (CI) numbers are assigned. there is.

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155 , 156, 166, 168, 175, 185 and CI Derivative pigments of Pigment Yellow 150;

C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;

C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32 , 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57 :1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104 , 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180 , 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 272 , 291;

C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60;

C.I. Pigment Green 7, 36, 58, 59, 62, 63;

C.I. Pigment Brown 23, 25;

C.I. Pigment Black 1,7.

Further, specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, bengala (red iron (III) oxide), cadmium red, ultramarine blue, blue blue, Chromium oxide rust, cobalt rust, amber, titanium black, synthetic iron black, carbon black, etc. are mentioned.

For example, when a pattern of a light-shielding layer is formed by using the color material dispersion according to the present invention as a photosensitive coloring resin composition to be described later on a color filter substrate, a black pigment having high light-shielding property is blended in the ink. As a black pigment with high light-shielding property, for example, inorganic pigments, such as carbon black and iron tetraoxide, or organic pigments, such as cyanine black, can be used.

As said dispersible dye, the dye which became dispersible by providing various substituents to dye, or using it in combination with the solvent with low solubility is mentioned.

As a salt-forming compound of a dye, it refers to a compound in which the dye forms a salt with a counter ion, for example, a salt-formation compound of a basic dye and an acid, and an acid-dye-base salt-formation compound are mentioned, The dye soluble in a solvent is a well-known lake formation. The lake pigment insolubilized in a solvent is also included using the (salt-forming) method.

In the present invention, the dispersibility and dispersion stability of the color material can be improved by using the color material containing at least one selected from dyes and dye-forming compounds of the present invention in combination with the dispersing agent of the present invention.

As said dye, it can select suitably from conventionally well-known dye. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.

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 can be determined that the dye is dispersible in the solvent (or mixed solvent).

Among them, the color material is at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salt formation compounds of these dyes. When containing, the effect of suppressing sublimation or precipitation of the color material by using the dispersing agent is high, and it is preferable in that a colored layer of high brightness can be formed. Moreover, as said color material, it is preferable to contain at least 1 sort(s) selected from the group which consists of a diketopyrrolopyrrole pigment, a quinophthalone pigment, a copper phthalocyanine pigment, a zinc phthalocyanine pigment, and a quinophthalone dye among them.

Examples of the diketopyrrolopyrrole pigment include CI Pigment Red 254, 255, 264, 272, 291 and the diketopyrrolopyrrole pigment represented by the following general formula (i). Among them, CI Pigment Red 254, 272 , 291 and at least one selected from diketopyrrolopyrrole pigments in which R ²¹ and R ²² are each a 4-bromophenyl group in the following general formula (i) are preferable.

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

As the quinophthalone pigment, for example, C.I. Pigment Yellow 138 etc. are mentioned.

As the copper phthalocyanine pigment, for example, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, C.I. Pigment Green 7, 36 and the like, and among them, C.I. Pigment Blue 15:6 is preferred.

As the zinc phthalocyanine pigment, for example, C.I. Pigment green 58, 59, etc. are mentioned.

As the quinophthalone dye, for example, C.I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. Solvent Yellow 114, 157, etc. are mentioned, and 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 a desired color can be developed in the case of a colored layer of a color filter. It is preferable, and it is more preferable that it is 15-60 nm. When the average primary particle diameter of the color material is within the above range, a display device with a color filter manufactured using the color material dispersion according to the present invention can be made of high contrast and high quality.

The average dispersed particle diameter of the color material in the color material dispersion liquid also varies depending on the type of color material used, but is preferably in the range of 10 to 100 nm, more preferably in the range of 15 to 60 nm.

The average dispersed particle size of the color material in the color material dispersion liquid is the dispersed particle size of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. For the measurement of the particle size by a laser light scattering particle size distribution meter, the color material dispersion is appropriately diluted with a solvent used for the color material dispersion to a concentration that can be measured by a laser light scattering particle size distribution meter (for example, 1000 times), and the laser light scattering particle size distribution is performed. It can measure at 23 degreeC by the dynamic light scattering method using a system (for example, the Nanotrac particle size distribution measuring apparatus UPA-EX150 manufactured by Nikiso Corporation). The average distributed particle diameter here is a volume average particle diameter.

The color material used in the present invention may be manufactured by a known method such as a recrystallization method or a solvent salt milling method. Moreover, you may use a commercially available color material after refinement|miniaturization process.

In the colorant dispersion according to the present invention, the content of the colorant is not particularly limited. Content of the color material is 5-80 mass parts with respect to 100 mass parts of total solids in a color material dispersion liquid from the point of dispersibility and dispersion stability, It is preferable to mix|blend in the ratio of 8-70 mass parts more preferably.

In particular, when forming a coating film or a colored layer having a high colorant concentration, it is preferably blended in an amount of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass with respect to 100 parts by mass of the total solid content in the colorant dispersion.

<solvent>

It does not react with each component in a color material dispersion liquid as a solvent used for this invention, What is necessary is just an organic solvent which can melt|dissolve or disperse|distribute these, and is not specifically limited. A solvent can be used individually or in combination of 2 or more types.

As a specific example of a solvent, Alcohol solvents, such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyrate ester solvents such as butyl, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; carbitol acetate-based solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butylcarbitol acetate (BCA); diacetates of propylene glycol diacetate and 1,3-butylene glycol diacetate; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc. of glycol ether solvents; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; Cyclic ether solvents, such as tetrahydrofuran; unsaturated hydrocarbon-based solvents such as benzene, 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, are mentioned. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are suitably used from the viewpoint of solubility of other components. Among them, examples of the solvent used in the present invention include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, and lactic acid. It is preferable that it is 1 or more types selected from the group which consists of ethyl and 3-methoxybutyl acetate from the point of the solubility of another component, and application|coatability.

The color material dispersion according to the present invention contains the above solvent, with respect to the total amount of the color material dispersion containing the solvent, usually in the range of 55 to 95 mass%, and among them, preferably in the range of 65 to 90 mass%. and it is more preferable to exist in the range of 70-88 mass %. When there are too few solvents, a viscosity will rise and dispersibility will fall easily. Moreover, when there are too many solvents, the color material density|concentration will fall and it may be difficult to achieve the target chromaticity coordinate.

<Other ingredients>

As long as the effects of the present invention are not impaired, the colorant dispersion according to the present invention may further contain a dispersion auxiliary resin and other components as needed.

As dispersion auxiliary resin, alkali-soluble resin illustrated by the photosensitive colored resin composition mentioned later is mentioned, for example. Due to the steric hindrance of the alkali-soluble resin, it becomes difficult to contact the color material particles, and there are cases in which dispersion is stabilized, or there is an effect of reducing the dispersant by the dispersion stabilization effect.

In addition, other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-repellent agent, an antioxidant, an anti-aggregation agent, and a UV absorber.

The color material dispersion liquid which concerns on this invention is used as a preliminary preparation for preparing the photosensitive colored resin composition mentioned later. That is, the color material dispersion liquid is a color material dispersion liquid having a high ratio (mass of the color material component in the composition) / (mass of the solid content other than the color material component in the composition) that is preliminarily prepared in a step before preparing the photosensitive colored resin composition to be described later. Specifically, (mass of color material component in composition)/(mass of solid content other than color material component in composition) ratio is usually 1.0 or more. By mixing a color material dispersion liquid and each component mentioned later, the photosensitive colored resin composition excellent in dispersibility can be prepared.

<Method for producing color material dispersion>

In the present invention, the method for producing the color material dispersion is not particularly limited as long as the color material is a method capable of obtaining a color material dispersion in which the color material is dispersed in a solvent by the dispersant of the graft copolymer or salt type graft copolymer. Especially, it is preferable to set it as either of the following two manufacturing methods from the point which is excellent in the dispersibility and dispersion stability of a color material.

That is, the first method for producing a color material dispersion according to the present invention includes a step of preparing a dispersing agent for the graft copolymer or salt-type graft copolymer, and a step of dispersing the color material in the presence of the dispersing agent in a solvent. will be.

In addition, in the second method for preparing a color material dispersion according to the present invention when using a dispersing agent that is a salt-type graft copolymer, a solvent, the graft copolymer, an organic acid compound, etc. are mixed with a color material, and the general formula (I) is It has a step of dispersing the color material while forming a salt with at least a part of the nitrogen moiety at the terminal of the represented structural unit and an organic acid compound or the like.

In the case of using a salt-type graft copolymer, according to the first production method, after preparing the salt-type graft copolymer, the salt-type graft copolymer is used as a dispersant to disperse the color material, so the graft before salt formation It is preferable from the point of being able to accurately confirm the reaction end point and reaction rate of the copolymer and the organic acid compound.

In addition, according to the second production method, since the color material is dispersed while preparing the dispersing agent for the salt-type graft copolymer, the salt-type graft copolymer does not self-aggregate, and the color material dispersion can be efficiently prepared, In addition, dispersibility can be improved.

In the first manufacturing method and the second manufacturing method, the color material may be dispersed using a conventionally known disperser.

Specific examples of the disperser include roll mills such as two rolls and three rolls, ball mills such as ball mills and vibrating ball mills, paint conditioners, bead mills such as continuous disk bead mills and continuous annular bead mills. As preferable dispersion conditions of the bead mill, the bead diameter used is preferably 0.03 to 3.0 mm, more preferably 0.05 to 2.0 mm.

Specifically, preliminary dispersion with 2.0 mm zirconia beads having a relatively large bead diameter and full-scale dispersion with 0.1 mm zirconia beads having a relatively small bead diameter are mentioned. Furthermore, it is preferable to filter with a filter of 0.5-2 micrometers after dispersion|distribution.

<Use>

The color material dispersion and dispersant according to the first present invention can produce a photosensitive colored resin composition that simultaneously satisfies the suppression of the occurrence of development residues, the shortening of the development time, the suppression of the occurrence of water stains, and the excellent solvent resistance. can be used readily.

I-2. 1st photosensitive colored resin composition according to the present invention

The photosensitive colored resin composition according to the first aspect of the present invention contains the dispersant, the colorant, the alkali-soluble resin, the polyfunctional monomer, the photoinitiator and the solvent according to the first aspect of the present invention.

Since the photosensitive colored resin composition of the first present invention contains the dispersant, the colorant, and the solvent according to the first present invention, as in the color material dispersion according to the first present invention, the generation of development residue is suppressed and the development time Shortening, suppression of occurrence of water stains, and excellent solvent resistance can be satisfied at the same time.

The first photosensitive colored resin composition of the present invention contains at least a dispersing agent, a colorant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent, within a range that does not impair the effects of the present invention, other components may be further contained That's good. Hereinafter, each component contained in the photosensitive colored resin composition of the first present invention will be described. However, the dispersant, the color material and the solvent are the same as those described for the color material dispersion according to the first aspect of the present invention, so here A description of will be omitted.

<Alkali-soluble resin>

The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and can be appropriately selected from among those soluble in the alkali developer used for pattern formation.

In the present invention, alkali-soluble resin can be based on an acid value of 40 mgKOH/g or more.

Preferred alkali-soluble resins in the present invention are resins having an acid group, usually a carboxy group, and specifically, acrylic resins such as acrylic copolymers having a carboxy group and styrene-acrylic copolymers having a carboxy group, and epoxy having a carboxy group (meth ) acrylate resins and the like. Among these, those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. It is because the film strength of the cured film formed by containing a photopolymerizable functional group improves. In addition, you may use these acrylic-type copolymers, acrylic resins, such as a styrene-acrylic-type copolymer, and epoxy acrylate resin, 2 or more types mixing.

Acrylic resins, such as an acrylic copolymer having a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group, include, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, other monomers copolymerizable by a known method (co- ) is a (co)polymer obtained by polymerization.

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, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone mono (meth)acrylate, etc. can also be used. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as the precursor of the carboxyl group. Among them, (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and glass transition temperature.

It is preferable that alkali-soluble resin further has a hydrocarbon ring at the point which is excellent in the adhesiveness of a colored layer. By having a hydrocarbon ring which is a bulky group in alkali-soluble resin, the knowledge that the solvent resistance of the obtained colored layer, especially swelling of a colored layer is suppressed was acquired. Although the action has not yet been elucidated, it is presumed that the inclusion of bulky hydrocarbon rings in the colored layer suppresses the movement of molecules in the colored layer, thereby increasing the strength of the coating film and suppressing the swelling by the solvent. .

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, and even if the hydrocarbon ring has a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group, or an amide group good night. Especially, when an aliphatic ring is included, while the heat resistance and adhesiveness of a colored layer improve, the brightness|luminance of the obtained colored layer improves.

Specific examples of the hydrocarbon ring include aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane) and adamantane; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; and a cardo structure represented by the following general formula (ii); and the like.

Moreover, it is also preferable that alkali-soluble resin has a maleimide structure represented by the following general formula (iii).

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

When the alkali-soluble resin has a maleimide structure represented by the above general formula (iii), since it has a nitrogen atom in the hydrocarbon ring, the compatibility with the dispersant of the present invention is very good, and the effect of suppressing the development residue is improved. .

As a specific example of the hydrocarbon ring which may be substituted in R ^M in the said general formula (iii), the thing similar to the specific example of the said hydrocarbon ring is mentioned.

When an aliphatic ring is included as a hydrocarbon ring, while the heat resistance and adhesiveness of a colored layer improve, it is preferable at the point which the brightness|luminance of the obtained colored layer improves.

Moreover, when it contains the cardo structure represented by the said general formula (ii), it is especially preferable at the point that sclerosis|hardenability of a colored layer improves and solvent resistance (NMP swelling suppression) improves.

In the alkali-soluble resin used in the present invention, separately from the structural unit having a carboxy group, it is easy to adjust the amount of each structural unit by using an acrylic copolymer having a structural unit having the hydrocarbon ring, and having the hydrocarbon ring It is preferable in that it is easy to improve the function which the said structural unit has by increasing the amount of a structural unit.

The structural unit having a carboxy group and the acrylic copolymer having a hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned “other monomers capable of copolymerization”.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) ) acrylate, phenoxyethyl (meth) acrylate, styrene, etc., and since the effect of maintaining the cross-sectional shape of the colored layer after development is large even in heat treatment, cyclohexyl (meth) acrylate, dicyclo Fentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and styrene are preferable.

It is preferable that the alkali-soluble resin used in the present invention also has an ethylenic double bond in the side chain. When it has an ethylenic double bond, in the hardening process of the resin composition at the time of color filter manufacture, the said alkali-soluble resin and the dispersing agent of this invention mentioned above can form a crosslink, and the said alkali-soluble resin A crosslink can be formed between each other or the alkali-soluble resin and the photopolymerizable compound. Therefore, when the alkali-soluble resin having an ethylenic double bond in the side chain and the dispersing agent of the present invention are used in combination, the film strength of the cured film is further improved by a synergistic effect, so the luminance of the colored layer and the crack resistance of the ITO film are more It can improve, and image development tolerance improves further, the heat shrink of a cured film is suppressed, and it becomes excellent in adhesiveness with a board|substrate.

The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of introducing an ethylenic double bond into the side chain by adding a compound having an epoxy group and an ethylenic double bond in the molecule to the carboxyl group of the alkali-soluble resin, such as glycidyl (meth)acrylate, or a hydroxyl group The structural unit which has is introduce|transduced into a copolymer, the method of adding the compound provided with the isocyanate group and ethylenic double bond in a molecule|numerator, and introduce|transducing an ethylenic double bond into a side chain, etc. are mentioned.

The alkali-soluble resin used in the present invention may further contain other structural units such as structural units having an ester group, such as methyl (meth)acrylate and ethyl (meth)acrylate. The structural unit which has an ester group functions not only as a component which suppresses alkali solubility of the photosensitive colored resin composition, but also functions as a component which improves the solubility with respect to a solvent, and also 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 having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring, and a structural unit having a carboxyl group and a hydrocarbon ring It is more preferable that it is an acrylic resin, such as an acryl-type copolymer and a styrene-acrylic copolymer which has a structural unit which has and has a structural unit which has an ethylenic double bond.

Alkali-soluble resin can be set as alkali-soluble resin which has desired performance by appropriately adjusting the injection amount of each structural unit.

The injection amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5 mass % or more, more preferably 10 mass % or more, based on the total amount of the monomer from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film degradation of the pattern surface after development, etc., the injection amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50 mass% or less, and more preferably 40 mass% or less, based on the total amount of the monomer.

If the ratio of the carboxyl group-containing ethylenically unsaturated monomer is equal to or greater than the lower limit, the solubility of the resulting coating film in the alkali developer is sufficient, and the ratio of the carboxyl group-containing ethylenically unsaturated monomer is below the upper limit, at the time of development with an alkali developer, There exists a tendency for the formed pattern to fall off from the board|substrate or film deterioration of the pattern surface hardly occurs.

In addition, in acrylic resins such as acrylic copolymers and styrene-acrylic copolymers having a structural unit having an ethylenic double bond, which are more preferably used as alkali-soluble resins, compounds having an epoxy group and an ethylenic double bond together are, It is preferable that they are 10 mass % - 95 mass % with respect to the injection amount of a carboxyl group-containing ethylenically unsaturated monomer, and it is more preferable that they are 15 mass % - 90 mass %.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may significantly decrease, and if it exceeds 50,000, it may become difficult to form a pattern during development with an alkali developer.

In addition, the said weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by Shodex GPC System-21H using polystyrene as a standard material and THF as an eluent.

Although it does not specifically limit as epoxy (meth)acrylate resin which has a carboxy group, The epoxy (meth)acrylate compound obtained by making the reaction product of an epoxy compound and an unsaturated group containing monocarboxylic acid react with an acid anhydride is suitable.

An epoxy compound, an unsaturated group-containing monocarboxylic acid, and an acid anhydride can be appropriately selected from known ones and used. The epoxy (meth)acrylate resin which has a carboxy group may be used individually by 1 type, respectively, and may use 2 or more types together.

It is preferable that alkali-soluble resin selects and uses an acid value 50 mgKOH/g or more from the point of developability (solubility) with respect to the aqueous alkali solution used for a developing solution. The alkali-soluble resin preferably has an acid value of 60 mgKOH/g or more and 300 mgKOH/g or less, from the viewpoint of developability (solubility) with respect to the aqueous alkali solution used for the developer and adhesiveness to the substrate, and among them, 70 mgKOH/g It is preferable that it is more than 200 mgKOH/g or less.

In addition, the acid value of alkali-soluble resin can be measured according to JISK0070:1992.

The ethylenically unsaturated bond equivalent in the case of having an ethylenically unsaturated group in the side chain of alkali-soluble resin is 100 to from the point of obtaining the effect that the film strength of a cured film improves, image development tolerance improves, and it is excellent in adhesiveness with a board|substrate. It is preferable that it is the range of 2000, and it is especially preferable that it is the range of 140-1500. When the said ethylenically unsaturated bond equivalent is 100 or more, it is excellent in image development tolerance and adhesiveness. Moreover, if it is 2000 or less, since the ratio of other structural units, such as the structural unit which has the said carboxyl group, and the structural unit which has a hydrocarbon ring, can be relatively increased, it is excellent in developability and heat resistance.

Here, the ethylenically unsaturated bond equivalent means a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Equation (1) Ethylenically unsaturated bond equivalent (g/mol)=W(g)/M(mol)

(In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenic double bonds contained in the alkali-soluble resin W (g).)

You may calculate the said ethylenically unsaturated bond equivalent by measuring the number of ethylenic double bonds contained per 1 g of alkali-soluble resin based on the test method of iodine number described in JISK0070:1992, for example.

Alkali-soluble resin used in the photosensitive colored resin composition may be used individually by 1 type, and may be used in combination of 2 or more type, Although there is no restriction|limiting in particular as the content, With respect to the solid content whole amount of the photosensitive colored resin composition The alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass. When content of alkali-soluble resin is more than the said lower limit, sufficient alkali developability can be acquired, and if content of alkali-soluble resin is less than the said upper limit, film deterioration and pattern loss at the time of image development can be suppressed.

<Multifunctional Monomer>

The polyfunctional monomer used in the photosensitive colored resin composition is not particularly limited, as long as it can be polymerized with a photoinitiator described later, and a compound having two or more ethylenically unsaturated double bonds is usually used, especially an acryloyl group or meta It is preferable that it is a polyfunctional (meth)acrylate which has two or more acryloyl groups.

As such a polyfunctional (meth)acrylate, what is necessary is just to select and use it suitably from a conventionally well-known thing. As a specific example, the thing of Unexamined-Japanese-Patent No. 2013-029832, etc. are mentioned.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. Further, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional monomer preferably has three (trifunctional) or more polymerizable double bonds, and a trivalent or higher polyhydric alcohol of poly(meth)acrylates or dicarboxylic acid-modified products thereof are preferred, and specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Succinic acid modified product of acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate A succinic acid modified product, dipentaerythritol hexa(meth)acrylate, etc. are preferable.

Although there is no restriction|limiting in particular as content of the said polyfunctional monomer used in the photosensitive colored resin composition, Preferably the polyfunctional monomer is 5-60 mass % with respect to solid content whole amount of the photosensitive colored resin composition, More preferably, 10-40 It is in the range of mass %. If the content of the polyfunctional monomer is less than the lower limit, photocuring does not proceed sufficiently, and the exposed portion may elute during development. If the content of the polyfunctional monomer is higher than the upper limit, alkali developability may decrease. There are concerns.

<Photoinitiator>

There is no restriction|limiting in particular as a photoinitiator used in the photosensitive colored resin composition of this invention, It can use 1 type or in combination of 2 or more types among various conventionally known initiators.

Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and the like. can be heard Specific examples of the photoinitiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone, and 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoinmethyl ether, and ethylbenzo Benzoin such as phosphorus, biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-trichloromethyl-5-(p-methoxystyryl)-1 Halomethyloxadiazole compounds such as ,3,4-oxadiazole and halo such as 2-(4-butoxy-naphtho-1-yl)-4,6-bis-trichloromethyl-S-triazine Methyl-S-triazine compound, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone , 1,2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoylbenzoic acid, methylbenzoylbenzoate, 4- Benzoyl-4'-methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoate isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2 -(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( 4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4- (methylthio)phenyl]-2-(4-morpholinyl)-1-propanone and the like.

Among them, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl) -1-butanone, 4,4'-bis(diethylamino)benzophenone, and diethylthioxanthone are preferably used. In addition, an α-aminoacetophenone-based initiator such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and a thioxanthone-based initiator such as diethylthioxanthone It is preferable from the viewpoint of sensitivity adjustment, water unevenness suppression, and development resistance improvement.

As for these total content in the case of using (alpha)-aminoacetophenone type|system|group initiator and a thioxanthone type initiator, 5 mass % - 15 mass % are preferable with respect to solid content whole quantity of a colored resin composition. It is preferable that the amount of initiator is 15 mass % or less, since sublimation in a manufacturing process is reduced. When the amount of the initiator is 5 mass % or more, development tolerance, such as a water stain, improves.

In the present invention, the photoinitiator preferably contains an oxime ester-based photoinitiator from the viewpoint of improving sensitivity among them. Moreover, when forming a thin wire|wire pattern by using an oxime ester type|system|group photoinitiator, it is easy to suppress in-plane linewidth nonuniformity. Furthermore, by using an oxime ester type photoinitiator, the residual film rate is improved and there exists a tendency for the water stain generation|occurrence|production suppression effect to become high. Here, when a component that improves alkali developability is used, the water stain means that a trace like water is generated after alkali development and after rinsing with pure water. Since such water stain disappears after post-baking, there is no problem as a product. However, it is detected as a non-uniformity abnormality in the appearance inspection of the patterned surface after development, and there arises a problem that a normal product and an abnormal product cannot be distinguished. Therefore, when the inspection sensitivity of an inspection apparatus is lowered in an external appearance inspection, as a result, the yield fall of the final color filter product will be caused and it will become a problem.

As said oxime ester-type photoinitiator, from the point of reducing the contamination of the photosensitive colored resin composition by a decomposition product, and contamination of an apparatus, it is especially preferable to have an aromatic ring, It is more preferable to have a condensed ring containing an aromatic ring, It is more preferable to have a condensed ring containing a benzene ring and a hetero ring.

Examples of the oxime ester photoinitiator include 1,2-octadione-1-[4-(phenylthio)-, 2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methyl) Benzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Application Laid-Open No. 2001-233842, Japanese Patent Publication No. 2010-527339, Japanese Patent It can select suitably from the oxime ester type photoinitiator described in publication 2010-527338, JP 2013-041153, etc. As a commercial product, Irgacure OXE-01, Adecarkles NCI-930 having a diphenyl sulfide skeleton, TR-PBG-345, TR-PBG-304 having a carbazole skeleton, TR-PBG having a fluorene skeleton -365, TR-PBG-3057 (above, manufactured by Changzhou Chiang Ridians New Chailao Co., Ltd.) etc. which have a diphenyl sulfide skeleton may be used. In particular, it is preferable from the viewpoint of luminance to use an oxime ester-based photoinitiator having a diphenylsulfide skeleton or a fluorene skeleton. In addition, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.

Moreover, it is preferable to use two or more types of oxime ester type photoinitiators together at the point which a brightness|luminance and a film remaining rate improve easily, and the water stain generation|occurence|production suppression effect is high. In particular, the combination of two types of oxime ester-based photoinitiators having a diphenyl sulfide skeleton or the use of an oxime ester-based photoinitiator having a diphenyl sulfide skeleton and an oxime ester-based photoinitiator having a fluorene skeleton in combination has high luminance and heat resistance. It is preferable in that it is high. In addition, it is preferable to use together an oxime ester-based photoinitiator having a carbazole skeleton, and an oxime ester-based photoinitiator having a fluorene skeleton or an oxime ester-based photoinitiator having diphenyl sulfide, from the viewpoint of excellent sensitivity and luminance.

In addition, it is preferable to use in combination with an oxime ester type|system|group photoinitiator and the photoinitiator which has a tertiary amine structure from the point of water stain suppression and a sensitivity improvement. This is because the photoinitiator having a tertiary amine structure has a tertiary amine structure serving as an oxygen quencher in the molecule, and therefore radicals generated from the initiator are less likely to be deactivated by oxygen, thereby improving the sensitivity. Commercially available products of the photoinitiator having the tertiary amine structure include, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (eg, Irgacure 907, manufactured by BASF); 2-Benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4'-bis(diethylamino)benzo Phenone (for example, Haicure ABP, the Kawaguchi Yakuhin make) etc. are mentioned.

In addition, combining the thioxanthone-based initiator with the oxime ester-based photoinitiator is preferable in terms of sensitivity adjustment, water stain suppression, and development resistance improvement, and combining two or more types of oxime ester-based photoinitiators with a thioxanthone-based initiator It is preferable at the point that a brightness|luminance and a film remaining rate improve, it is easy to make a sensitivity adjustment, the water unevenness generation|occurrence|production suppression effect is high, and image development tolerance improves.

Content of the photoinitiator used in the photosensitive colored resin composition of this invention is 0.01 mass part - about 100 mass parts normally with respect to 100 mass parts of said polyfunctional monomers, Preferably they are 5 mass parts - 60 mass parts. If this content is more than the said lower limit, photocuring fully advances and it suppresses that the exposed part elutes at the time of image development, On the other hand, if it is below the said upper limit, yellowing property of the colored layer obtained becomes weak and it can suppress that a brightness|luminance falls.

Moreover, as a photoinitiator used in the photosensitive colored resin composition of this invention, the total content of 2 or more types of oxime ester type photoinitiators is 0.1 mass % - 12.0 mass % with respect to the solid content whole amount of the photosensitive colored resin composition, More preferably, 1.0 It is preferable that it exists in the range of mass % - 8.0 mass % at the point which fully exhibits the combined effect of these photoinitiators.

As for the binder component used in the photosensitive colored resin composition of this invention, 35 mass % - 97 mass % are preferable with respect to the solid content whole quantity of these total content of the photosensitive colored resin composition, The ratio of 40 mass % - 96 mass % It is more preferable to mix with If it is more than the said lower limit, the colored layer excellent in hardness and adhesiveness with a board|substrate can be obtained. Moreover, it is excellent in developability as it is below the said upper limit, and generation|occurrence|production of the microwrinkle by heat shrink is also suppressed. In particular, when forming a colored layer having a high colorant concentration, the binder component is preferably 20 to 90 mass% of the total content of the binder component with respect to the total solid content of the photosensitive colored resin composition, and is blended in a proportion of 25 to 80 mass%. It is more preferable to

<Antioxidant>

It is preferable that the photosensitive colored resin composition of this invention contains antioxidant further at the point which heat resistance improves, fading of a color material is suppressed, and a brightness|luminance improves. The antioxidant may be appropriately selected from those known in the art. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hydrazine-based antioxidants. desirable. A latent antioxidant as described in International Publication No. 2014/021023 may be used.

Examples of the hindered phenol antioxidant include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF), 1, 3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxyl) -3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilisa) MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-tert-butyl and diethyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF). Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable. .

When the photosensitive colored resin composition of the present invention contains the oxime ester-based photoinitiator and antioxidant in combination, the luminance is improved by a synergistic effect, the remaining film rate is improved, and the linearity is further improved when forming a thin line pattern Alternatively, it is preferable in that the ability to form a thin line pattern according to the design of the mask line width is improved.

As a compounding quantity of antioxidant, it is preferable that they are 0.1 mass parts - 10.0 mass parts of antioxidant with respect to 100 mass parts of total solids in a colored resin composition, and it is more preferable that they are 0.5 mass parts - 5.0 mass parts. If it is more than the said lower limit, it is 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 a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the oxime ester photoinitiator, the blending amount of the antioxidant is preferably 1 to 250 parts by mass, and 3 parts by mass to the total amount of 100 parts by mass of the oxime ester photoinitiator. It is more preferable that it is 80 mass parts, and it is still more preferable that they are 5 mass parts - 45 mass parts. If it is in the said range, the effect of the said combination is excellent.

<Optional additional ingredients>

The photosensitive colored resin composition of this invention may contain various additives other than the said antioxidant as needed.

Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion promoter, and the like.

As a specific example of surfactant and a plasticizer, the thing of Unexamined-Japanese-Patent No. 2013-029832 is mentioned.

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, KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (made by Shin-Etsu Silicon) etc. are mentioned. Among these, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 which have a methacryl group and an acryl group from the point of the adhesiveness of a SiN substrate are preferable.

As content of a silane coupling agent, it is preferable that they are 0.05 mass parts or more and 10.0 mass parts or less of a silane coupling agent with respect to 100 mass parts of total solids in the photosensitive colored resin composition, and it is more preferable that they are 0.1 mass parts or more and 5.0 mass parts or less. It is excellent in board|substrate adhesiveness as it is more than the said lower limit and below the said upper limit.

<The blending ratio of each component in the photosensitive colored resin composition>

Total content of a color material is 3-65 mass % with respect to solid content whole quantity of the photosensitive colored resin composition, It is preferable to mix|blend in the ratio of 4-60 mass % more preferably. If it is more than the said lower limit, the colored layer at the time of apply|coating the photosensitive colored resin composition with a predetermined|prescribed film thickness (normally 1.0-5.0 micrometers) has sufficient color density. Moreover, while being excellent in storage stability as it is below the said upper limit, the colored layer which has sufficient hardness and adhesiveness with a board|substrate can be obtained. In particular, when forming a colored layer having a high colorant concentration, the content of the colorant is preferably 15 to 75 mass%, more preferably 25 to 70 mass% with respect to the total solid content of the photosensitive colored resin composition. .

In addition, as content of a dispersing agent, if a color material can be disperse|distributed uniformly, it will not specifically limit, For example, It can use in the ratio of 1-40 mass % with respect to the solid content whole amount of a photosensitive colored resin composition. Moreover, it is preferable to mix|blend in the ratio of 2-30 mass % with respect to the solid content whole quantity of the photosensitive colored resin composition, and it is especially preferable to mix|blend in the ratio of 3-25 mass %. It is excellent in the dispersibility and dispersion stability of a color material as it is more than the said lower limit, and it is more excellent in the storage stability of the photosensitive colored resin composition. Moreover, developability becomes favorable as it is below the said upper limit. In particular, when forming a colored layer having a high colorant concentration, the content of the dispersant is 2 to 25% by mass, more preferably 3 to 20% by mass relative to the total solid content of the photosensitive colored resin composition. . Here, in the case of a salt-type graft copolymer, the mass of the dispersant is the total mass of the graft copolymer and an organic acid compound before salt formation.

In addition, what is necessary is just to set content of a solvent suitably in the range which can form a colored layer accurately. It is preferable to exist in the range of 55-95 mass % normally with respect to the photosensitive colored resin composition whole quantity containing the said solvent, and it is more preferable to exist in the range which is 65-88 mass % especially. When content of the said solvent is in the said range, it can be set as the thing excellent in applicability|paintability.

<The manufacturing method of the photosensitive colored resin composition>

The method for producing the photosensitive colored resin composition of the present invention is not particularly limited, and, for example, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator and, if necessary, other components are added to the color material dispersion according to the present invention, and a known mixing means It can be obtained by mixing using

<Use>

Since the photosensitive colored resin composition according to the first aspect of the present invention can simultaneously satisfy the suppression of the occurrence of development residues, the shortening of the development time, the suppression of the occurrence of water stains and the excellent solvent resistance, it can be preferably used for color filter applications.

I-3. Color filter according to the first invention

A color filter according to the first aspect of the present invention is a color filter comprising at least a substrate and a colored layer formed on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the first aspect of the present invention. am.

The color filter according to the present invention will be described with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the color filter of this invention. According to FIG. 1 , a color filter 10 of the present invention includes a substrate 1 , a light shielding portion 2 , and a colored layer 3 .

<Colored layer>

The colored layer used for the color filter of this invention is a colored layer whose at least one is the hardened|cured material of the said photosensitive colored resin composition which concerns on this invention.

The colored layer is usually formed in an opening of a light-shielding portion on a substrate to be described later, and is usually composed of 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, and a four-pixel arrangement type can be used. In addition, the width|variety, an area, etc. of a colored layer can be set arbitrarily.

Although the thickness of the said colored layer is suitably controlled by adjusting a coating method, solid content concentration, a viscosity, etc. of the photosensitive colored resin composition, it is preferable that it is the range of 1-5 micrometers normally.

The colored layer can be formed, for example, by the following method.

First, the photosensitive colored resin composition of the present invention described above is applied on a substrate to be described later using an application means 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. , to form a wet coating film. Among them, a spin coating method and a die coating method can be preferably used.

Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask of a predetermined pattern, and an alkali-soluble resin and polyfunctional monomer are photopolymerized to obtain a cured coating film. Examples of the light source used for exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted according to the light source to be used, the thickness of the coating film, and the like.

Moreover, you may heat-process after exposure in order to accelerate|stimulate a polymerization reaction. Heating conditions are suitably selected according to the compounding ratio of each component in the photosensitive colored resin composition to be used, the thickness of a coating film, etc.

Then, a coating film is formed in a desired pattern by developing using a developing solution to melt|dissolve and remove an unexposed part. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. In addition, a general method can be employ|adopted as a developing method.

After the developing treatment, washing of the developer and drying of the cured coating film of the photosensitive colored resin composition are usually performed to form a colored layer. Further, after the developing treatment, heat treatment may be performed in order to sufficiently harden the coating film. There is no limitation in particular as heating conditions, According to the use of a coating film, it selects suitably.

<Light-shielding part>

The light-shielding part in the color filter of this invention is formed in the pattern form on the board|substrate mentioned later, and can be made similar to what is used as a light-shielding part in a general color filter.

It does not specifically limit as a pattern shape of the said light-shielding part, For example, shapes, such as a stripe type and a matrix type, are mentioned. The light-shielding portion may be a thin metal film such as chromium by sputtering, vacuum deposition, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, and the like.

The 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 is set to about 0.5 to 2 µm in the case of a black pigment dispersed or dissolved in a binder resin.

<substrate>

As a board|substrate, what formed the aluminum, silver, silver/copper/palladium alloy thin film etc. on the transparent substrate, a silicon substrate, and a transparent substrate mentioned later or a silicon substrate is used. On these board|substrates, another color filter layer, a resin layer, transistors, such as TFT, a circuit, etc. may be formed.

As a transparent substrate in the color filter of this invention, what is necessary is just a base material transparent with respect to visible light, It does not specifically limit, A transparent substrate used for a general color filter can be used. Specific examples include transparent rigid materials without flexibility such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials with flexibility such as transparent resin films, optical resin plates, and flexible glass. can

Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, for example, a thing of about 100 micrometers - 1 mm can be used.

Further, the color filter of the present invention may be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, and the like in addition to the substrate, the light-shielding portion and the colored layer.

I-4. Display device according to the first invention

A display device according to a first aspect of the present invention includes the color filter according to the first aspect of the present invention. In the first aspect of the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device.

[Liquid crystal display device]

As a liquid crystal display device of this invention, the liquid crystal display device which has the color filter which concerns on this invention mentioned above, a counter board|substrate, and the liquid crystal layer formed between the said color filter and the said counter board|substrate is mentioned, for example as a liquid crystal display device.

The liquid crystal display device of this invention is demonstrated, referring drawings. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As illustrated in FIG. 2 , the liquid crystal display device 40 of the present invention includes a color filter 10 , a counter substrate 20 including a TFT array substrate, and the like, and the color filter 10 and the counter substrate 20 . ) has a liquid crystal layer 30 formed between them.

In addition, the liquid crystal display device of this invention is not limited to the structure shown in said FIG. 2, In general, it can be set as the structure well-known as a liquid crystal display device in which the color filter was used.

It does not specifically limit as a drive method of the liquid crystal display device of this invention, The drive method generally used for a liquid crystal display device is employable. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.

Moreover, as a counter substrate, it can select and use suitably according to the driving method of the liquid crystal display device of this invention, etc.

Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention and the like.

As a formation method of a liquid crystal layer, the method generally used as a manufacturing method of a liquid crystal cell can be used, For example, a vacuum injection system, a liquid crystal dropping system, etc. are mentioned. After forming a liquid crystal layer by the said method, the enclosed liquid crystal can be orientated by slowly cooling a liquid crystal cell to room temperature.

[Organic light emitting display device]

As an organic light emitting display device of the present invention, for example, an organic light emitting display device including the color filter according to the present invention and an organic light emitting body described above.

The organic light emitting display device of the present invention will be described with reference to the drawings. 3 is a schematic diagram illustrating an example of an organic light emitting display device of the present invention. As illustrated in FIG. 3 , the organic light emitting diode display 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 of laminating the organic light emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter. A method of sequentially forming the light emitting diodes, a method of pasting the organic light emitting body 80 formed on another substrate on the inorganic oxide film 60, and the like are mentioned. In the organic light-emitting body 80 , the transparent anode 71 , the hole injection layer 72 , the hole transport layer 73 , the light emitting layer 74 , the electron injection layer 75 and the cathode 76 , and other configurations are known. can be used appropriately. The organic light emitting display device 100 manufactured in this way is applicable to, for example, a passive driving type organic EL display and an active driving type organic EL display.

In addition, the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3 , and may have a generally known configuration as an organic light emitting display device using a color filter.

II. second invention

Hereinafter, the photosensitive colored resin composition, the color filter, the liquid crystal display device and the organic light emitting display device according to the second aspect of the present invention will be sequentially described in detail.

The photosensitive colored resin composition according to the second aspect of the present invention contains a colorant, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,

The photoinitiator contains an oxime ester-based photoinitiator having a diphenylsulfide skeleton,

The dispersant is a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the graft copolymer represented by the general formula (I) At least one kind of a salt-type graft copolymer in which at least a part of the nitrogen moiety of the structural unit and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons has formed a salt is contained.

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

In the general formula (II), R ^1' is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer is a polymer chain, and the structural unit of the polymer chain is represented by the following general formula (III") At least one structural unit selected from the group consisting of structural units and structural units represented by the following general formula (III') are included.)

(in the general formula (III"), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m" is 3 or more and 80 or less represents the number of

In the general formula (III'), R ^4' is a hydrogen atom or a methyl group, A ^3' is a divalent linking group, R ⁷ is an alkylene group having 1 to 10 carbon atoms, R ⁸ is an alkylene group having 3 to 7 carbon atoms, R ⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less.)

The photosensitive colored resin composition according to the second aspect of the present invention uses the specific graft copolymer or salt type graft copolymer as a dispersant and contains an oxime ester-based photoinitiator having a diphenyl sulfide skeleton as the photoinitiator. Dispersion stability, high contrast, shortening of development time, and excellent solvent resistance can be simultaneously satisfied. Although it has not yet been elucidated as an effect|action which exhibits such an effect, it is estimated as follows.

In the said specific graft copolymer, the structural unit which has a polyethylene oxide chain, a polypropylene oxide chain, or an ester chain is contained in the structural unit of the grafted polymer chain. It is thought that the oxygen atom contained in a polyethylene oxide chain, a polypropylene oxide chain, or an ester chain becomes easy to melt|dissolve in an alkali developing solution at the time of image development by hydrogen bonding with an alkali developing solution.

In addition, in the graft copolymer, since a plurality of grafted polymer chains become the solvent affinity portion of the dispersant, the specific surface area of the solvent affinity portion of the dispersant becomes large, so that penetration of the solvent into the coating film or reaching the color material is prevented. presumed to be suppressed. In the specific graft copolymer, a structural unit having a polyethylene oxide chain, a polypropylene oxide chain or an ester chain is included in the structural unit of the grafted polymer chain, whereby the oxygen atoms contained in these structural units are photosensitive colored resin composition By interacting with acidic groups, such as a carboxyl group of alkali-soluble resin contained in it, by hydrogen bond, it is estimated that penetration into the cured coating film of a solvent can be suppressed more. Furthermore, by containing the oxime ester type|system|group photoinitiator which has a diphenyl sulfide skeleton as a photoinitiator, sclerosis|hardenability of a coating film improves. Due to these synergistic effects, when a combination of the specific graft copolymer and an oxime ester-based photoinitiator having a diphenyl sulfide skeleton as a photoinitiator are used in combination, the cured product of the photosensitive colored resin composition has solvent resistance, color filter alignment film production It is estimated that resistance to N-methylpyrrolidone (NMP) used as a solvent (NMP resistance) can be improved.

Moreover, in the specific graft copolymer, a structural unit having a polyethylene oxide chain, polypropylene oxide chain or ester chain of an appropriate length is included in the structural unit of the grafted polymer chain, so that the action of the solvent affinity part is good. Thus, it is estimated that the dispersion stability and contrast of the color material are improved.

Moreover, as for the photosensitive colored resin composition of 2nd this invention, the tendency which generation|occurrence|production of the image development residue was suppressed was seen so that it may show in the Example mentioned later. In the specific graft copolymer, the oxygen atoms contained in the polyethylene oxide chain, polypropylene oxide chain or ester chain interact with OH or CH such as a carboxyl group of the alkali-soluble resin contained in the photosensitive resin composition by hydrogen bonding, It is thought that only alkali-soluble resin melt|dissolves at the time of image development, and it can suppress that a color material and a dispersing agent remain as a residue. On the other hand, when the number of repeating units of a polyethylene oxide chain, a polypropylene oxide chain, or an ester chain became large too much, it discovered that the development residue generation|occurrence|production suppression effect did not improve on the contrary. This means that when the number of repeating units of polyethylene oxide chains, polypropylene oxide chains or ester chains becomes too large, the affinity with the alkali developer becomes excessively greater than the pigment adsorption force, so that only the graft copolymer is dissolved in the alkali developer, and the pigment is deposited on the substrate. It is presumed that it is not because it is left in the

The second photosensitive colored resin composition according to the present invention contains at least a colorant, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, within a range that does not impair the effects of the present invention, further containing other components, also good

Hereinafter, each component of the photosensitive colored resin composition according to the second present invention will be sequentially described in detail from the dispersing agent and photoinitiator, which are the characteristic combinations of the second present invention.

<Dispersing agent used in the second invention>

In the second invention, as a dispersant, a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and the general formula of the graft copolymer At least one type of salt-type graft copolymer in which at least a part of the nitrogen moiety of the structural unit represented by (I) and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon form a salt is used.

First, the graft copolymer will be described.

In the dispersing agent used in the second invention, the structural unit represented by the general formula (I) is the same as the structural unit represented by the general formula (I) in the dispersing agent of the first invention. Because it is good, the description here is abbreviate|omitted.

(Constituting unit represented by general formula (II))

When the graft copolymer used in the second invention has a structural unit represented by the general formula (II) having a specific polymer chain, the solvent affinity becomes good, and the dispersibility and dispersion stability of the color material this becomes good. In addition, the graft copolymer is, from the group consisting of a structural unit represented by the general formula (III") and a structural unit represented by the general formula (III') in the structural unit represented by the general formula (II). Since the at least 1 sort(s) of structural unit selected is contained, as above-mentioned, the development time shortening of the photosensitive resin composition and the solvent resistance of the hardened|cured material of the photosensitive colored resin composition become favorable.

In the general formula (II), A ² is a direct bond or a divalent linking group. There is no restriction|limiting in particular as a ^divalent coupling group in A2, if the carbon atom derived from an ethylenically unsaturated double bond and a polymer chain can be connected. Examples of the divalent linking group for A ² include the same divalent linking group for A ¹ .

Among them, from the viewpoint of dispersibility, A ² in General Formula (II) is preferably a divalent linking group containing -CONH- or -COO-, and is preferably a -CONH- or -COO- group of a carbon atom. It is more preferable that it is a divalent coupling group containing a number 1-10 alkylene group.

In the general formula (II), Polymer represents a polymer chain, and the structural unit of the polymer chain consists of a structural unit represented by the general formula (III″) and a structural unit represented by the general formula (III′). At least one structural unit selected from the group is included.

In the formula (III"), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m" is 3 or more and 80 or less represents the number of

Examples of the divalent linking group for A ³ include the same divalent linking group for A ¹ . Among them, from the viewpoint of solubility in the organic solvent used for color filter applications, A ³ in general formula (III") is preferably a divalent linking group containing -CONH- group or -COO- group, -CONH -group or -COO-group is more preferable.

Said m" represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 3 or more, but among them, from the viewpoint of suppressing the occurrence of water stains, it is preferably 19 or more, and more preferably 21 or more. As the cause of water stain of the cured film of the resin composition, absorption into the cured film is mentioned.The alkali-soluble resin in the cured film has an acidic group such as carboxyl group, so it is easily absorbed.In addition, the acidic group is formed in an alkali developer By forming a metal salt with the alkali metal typically contained in , it is thought that the water absorption becomes higher.The oxygen atom contained in the polyethylene oxide chain or polypropylene oxide chain can be captured by complexing with a metal such as an alkali metal. As the number of repeating units of the chain or polypropylene oxide chain increases, the complex formation constant increases and the ability to capture metal molecules increases, thereby suppressing the formation of alkali metal salts of alkali-soluble resins and suppressing absorption into the cured film. In addition, the oxygen atom contained in the polyethylene oxide chain or the polypropylene oxide chain interacts with an acidic group, such as a carboxyl group, of the alkali-soluble resin contained in the photosensitive resin composition by hydrogen bonding, so that an alkali metal salt of an acidic group It is estimated that formation can be suppressed and absorption in a cured film can be suppressed.

When m" is 19 or more, similarly to the dispersant of the first present invention, as shown in FIG. 4 , the graft copolymer 110 is a structural unit of the grafted polymer chain 124 . In, the structural unit 125 having a polyethylene oxide chain or polypropylene oxide chain having a specific repetition number is included, and the grafted polymer chain 124 itself has a branched structure, so that the absorption inhibitory effect is improved, It is preferable in that it can suppress the generation|occurrence|production of water stain by absorption.

On the other hand, although the upper limit of m" is 80 or less, it is preferable that it is 50 or less from the point of solubility to the organic solvent used for a color filter use.

Examples of the hydrocarbon group for R ⁶ include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, and combinations thereof such as an aralkyl group and an alkyl-substituted aryl group.

The hydrocarbon group for R ⁶ may be the same as R ⁶ in the structural unit represented by the general formula (III) in the first dispersing agent of the present invention.

In addition, in the said general formula (III'), as a divalent linking group of A ^3' , the same thing as the divalent linking group in said A ¹ is mentioned, for example. Especially, from the viewpoint of solubility in the organic solvent used for color filter use, it is preferable that A ^3' in general formula (III') is a divalent coupling group containing -CONH- group or -COO- group, - It is more preferably a CONH- group or a -COO- group.

In the said general formula (III'), although R< ⁷ > is a C1-C10 alkylene group, it is preferable especially that it is a C2-C8 alkylene group from a solvent re-solubility point.

Although R< ⁸ > is a C3-C7 alkylene group, Especially, it is preferable at the point of base-material adhesiveness that it is a C3-C5 alkylene group and a C5 alkylene group.

R ⁹ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group for R ⁹ may be the same as the hydrocarbon group for R ⁶ .

In the general formula (III'), n represents the number of repeating units of the ester chain and represents a number of 1 or more. Among them, it is preferable that the n is 2 or more from the viewpoint of simultaneously satisfying shortening of development time and excellent solvent resistance. and 3 or more is more preferable.

On the other hand, although the upper limit of n is 40 or less, it is preferable that it is 20 or less from the point of the solubility to the organic solvent used for a color filter use.

In the polymer chain, at least one structural unit selected from the group consisting of a structural unit represented by the general formula (III″) and a structural unit represented by the following general formula (III′) may be alone, but , two or more types may be mixed.

In the polymer chain, it is preferable that the structural unit represented by the general formula (III″) is included in that the action of the solvent affinity moiety by the oxygen atom becomes more remarkable.

In the said polymer chain, it is preferable from the point of the water stain suppression effect that the structural unit represented by the said general formula (III") whose m" is 19 or more and 80 or less is contained.

Among them, in the structural unit of the polymer chain in the structural unit represented by the general formula (II), m" is 19 At least one selected from the group consisting of a structural unit represented by the general formula (III"), which is 80 or more, and a structural unit represented by the general formula (III"), wherein m" is 3 or more and 10 or less. It is more preferable to contain in combination of at least one type of It is more preferable to contain in combination of at least 1 sort(s) selected from the group which consists of structural units represented by the said general formula (III") below.

In the structural unit of the polymer chain in the structural unit represented by the general formula (II), at least one selected from the group consisting of structural units represented by the general formula (III”) in which m" is 19 or more and 80 or less is contained. In this case, when m" is 19 or more and 80 or less, the total ratio of the structural units represented by the general formula (III") is 1 It is preferable that it is mass % or more, It is more preferable that it is 2 mass % or more, and it is still more preferable that it is 4 mass % or more, On the other hand, it is preferable that it is 75 mass % or less from the point of solvent re-solubility and water stain suppression effect, and it is 65 mass %. % or less is more preferable, and it is still more preferable that it is 50 mass% or less.

At least one member selected from the group consisting of structural units represented by the general formula (III"), wherein m" is 19 or more and 80 or less, in the structural unit of the polymer chain in the structural unit represented by the general formula (II), and m In the case of containing in combination at least one member selected from the group consisting of structural units represented by the general formula (III”), which is 3 or more and 10 or less, m” is 3 or more and 10 or less, represented by the general formula (III”) It is preferable that the total ratio of the structural unit used is 20 mass % or more, when all the structural units of the said polymer chain are 100 mass %. On the other hand, from the viewpoint of solvent re-solubility, in the polymer chain, the total ratio of the structural units represented by the general formula (III") where m" is 3 or more and 10 or less is 100 mass % of the total structural units of the polymer chain. When it is set as , it is preferable that it is 80 mass % or less, and it is more preferable that it is 60 mass % or less.

Further, in the polymer chain, the structural unit represented by the general formula (III") in which m" is 19 or more and 80 or less, and the structural unit represented by the said general formula (III") in which m" is 3 or more and 10 or less are mixed The ratio is, in terms of improving the effect of inhibiting development residues, the structural unit represented by the general formula (III") in which m" is 19 or more and 80 or less, and the general formula (III") in which m" is 3 or more and 10 or less. When the total of the structural units to be formed is 100 parts by mass, the total of the structural units represented by the general formula (III") in which m" is 19 or more and 80 or less is preferably 3 parts by mass or more, and more preferably 6 parts by mass or more, , It is preferable that it is 80 mass parts or less, and it is more preferable that it is 60 mass parts or less.

In terms of simultaneously satisfying dispersion stability, high contrast, reduction in development time and excellent solvent resistance, when the total structural units of the polymer chain is 100% by mass, the structural unit represented by the general formula (III”) and the The total ratio of at least one structural unit selected from the group consisting of structural units represented by the general formula (III') is preferably 1 mass % or more, more preferably 2 mass % or more, and 4 mass % or more It is even more preferable. The total ratio of at least one structural unit selected from the group consisting of the structural unit represented by the general formula (III") and the structural unit represented by the general formula (III') is the solvent re-solubility In terms of, when the total structural units of the polymer chain are 100 mass %, it is preferably 80 mass % or less, more preferably 70 mass % or less, and still more preferably 60 mass % or less.

In the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the structural unit represented by the general formula (III″) and the structural unit represented by the general formula (III′) It is preferable from the viewpoint of the dispersibility and dispersion stability of a color material that the structural unit represented by the following general formula (IV) different from that is further included.

As a structural unit represented by the following general formula (IV), you may be similar to the said general formula (IV) in the said 1st dispersing agent of this invention.

(In formula (IV), R ^4″ is a hydrogen atom or a methyl group, A ⁴ is a divalent linking group, and R ¹⁰ is a hydrogen atom or a hydrocarbon group which may contain a hetero atom.)

The said polymer chain WHEREIN: Although 1 type may be sufficient as the structural unit represented by the said General formula (IV), 2 or more types may be mixed.

From the viewpoint of dispersibility and dispersion stability of the color material, in the polymer chain, the total ratio of the structural units represented by the general formula (IV) is 25 mass% when the total structural units of the polymer chain is 100% by mass. % or more, and more preferably 35 mass% or more. On the other hand, in the point of simultaneously satisfying dispersion stability, high contrast, reduction in development time and excellent solvent resistance, in the polymer chain, the total ratio of the structural units represented by the general formula (IV) is the total proportion of the polymer chain. When a structural unit is 100 mass %, it is preferable that it is 99 mass % or less, and it is more preferable that it is 98 mass % or less.

In the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the structural unit represented by the general formula (III″), the structural unit represented by the general formula (III′) , In addition to the structural unit represented by the general formula (IV), other structural units may be included.

Examples of other structural units include a monomer derived from the structural unit represented by the general formula (III″), a monomer derived from the structural unit represented by the formula (III′), and a configuration represented by the formula (IV). Structural units derived from a monomer having an unsaturated double bond copolymerizable with a monomer that induces the unit.

Examples of the monomer that induces other structural units include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as phenyl vinyl ether.

In the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the total ratio of the other structural units is the effect of the present invention, so that the total structural units of the polymer chain are 100 mass When it is set as %, it is preferable that it is 30 mass % or less, and it is more preferable that it is 10 mass % or less.

The mass average molecular weight (Mw) of the polymer chain in the polymer may be the same as the mass average molecular weight (Mw) of the polymer chain in the structural unit represented by the general formula (II) in the dispersing agent of the first invention. .

Moreover, it is preferable that the solubility in 23 degreeC is 20 (g/100g solvent) or more with respect to the organic solvent used in combination as a reference|standard as for the polymer chain in Polymer.

(graft copolymer)

The graft copolymer WHEREIN: It is preferable that the structural unit represented by the said general formula (I) is contained in the ratio of 3-60 mass %, 6-45 mass % is more preferable, 9-30 mass % % is more preferable. When the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the color material in the graft copolymer is appropriate, and the decrease in solubility in organic solvents can be suppressed. For this reason, the adsorption property with respect to a color material becomes favorable, and the outstanding dispersibility and dispersion stability can be acquired.

On the other hand, in the graft copolymer, the structural unit represented by the general formula (II) is preferably contained in a proportion of 40 to 97 mass%, more preferably 55 to 94 mass%, and 70 to 91 mass % is more preferable. When the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent-affinity part in the graft copolymer becomes appropriate, and a sufficient steric repulsion effect as a dispersant can be maintained, and the dispersant As the specific surface area of the solvent affinity part of can

The graft copolymer used in the second present invention may contain, within a range not impairing the effects of the present invention, in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). , may further have other structural units. As the other structural unit, an ethylenically unsaturated double bond-containing monomer copolymerizable with an ethylenically unsaturated double bond-containing monomer or the like that induces the structural unit represented by the general formula (I) is appropriately selected and copolymerized to introduce another structural unit can do.

As another structural unit copolymerized with the structural unit represented by the said general formula (I), the structural unit of the polymer chain of the structural unit represented by the said general formula (IV) or the structural unit represented by the said general formula (II), for example. At least one structural unit selected from the group consisting of a structural unit represented by the general formula (III") and a structural unit represented by the general formula (III') is not included, and the general formula (IV) and a structural unit having a polymer chain different from that of the structural unit represented by the general formula (II), including the structural unit represented by .

In addition, the content rate of the said structural unit is, at the time of manufacture, at the time of synthesizing a graft copolymer, the structural unit represented by the said general formula (I), the structural unit represented by the said general formula (II), and the said general It is computed from the injection amount of the monomer which derives the structural unit represented by formula (III"), the structural unit represented by the said general formula (III'), etc.

Moreover, it is preferable that it is 4000 or more from the point of dispersibility and dispersion stability, and, as for the mass average molecular weight (Mw) of the said graft copolymer, it is more preferable that it is 6000 or more, It is still more preferable that it is 8000 or more. On the other hand, from the point of solvent re-solubility, it is preferable that it is 50000 or less, and it is more preferable that it is 30000 or less.

In addition, the amine titer of the graft copolymer before salt formation is not particularly limited, but from the viewpoint of color material dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, 60 It is still more preferable that it is mgKOH/g or more. Moreover, as an upper limit, it is preferable that it is 140 mgKOH/g or less, It is more preferable that it is 130 mgKOH/g or less, It is still more preferable that it is 120 mgKOH/g or less. Dispersion stability is more excellent as it is more than the said lower limit. Moreover, compatibility with another component will be excellent as it is below the said upper limit, and solvent re-solubility will become favorable.

It is preferable that it is 18 mgKOH/g or less, and, as for the acid value of the graft copolymer before salt formation, it is more preferable that it is 12 mgKOH/g or less at the point which image development adhesiveness and solvent re-solubility become favorable. In addition, the acid value of the graft copolymer before salt formation may be less than 1 mgKOH/g from the point of improving solvent re-solubility and image development adhesiveness more, and the point of dispersion stability. On the other hand, from the point of the image development residue suppression effect, it is preferable that it is 1 mgKOH/g or more, and it is more preferable that it is 2 mgKOH/g or more.

(Method for producing graft copolymer)

In the second invention, as the method for producing the graft copolymer, a graft copolymer having the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is prepared. It may be a method that can be used, and it is not particularly limited. Specifically, for example, it may be the same as the method for producing the graft copolymer in the dispersing agent of the first aspect of the present invention.

(at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons)

In the second aspect of the present invention, the dispersant comprises at least a part of the nitrogen moiety contained in the structural unit represented by the general formula (I) of the graft copolymer, and an organic acid compound and halogenation agent, from the viewpoint of improving the dispersibility of the color material. A salt-type graft copolymer in which at least one selected from the group consisting of hydrocarbons has formed a salt may be used.

The organic acid compound is preferably a compound represented by the following general formula (1) and a compound represented by the following general formula (3), and among them, the halogenated hydrocarbon is a compound represented by the following general formula (2) This is preferable. That is, as at least 1 type selected from the group which consists of the said organic acid compound and a halogenated hydrocarbon, 1 or more types of compounds selected from the group which consists of following General formula (1) - (3) can be used preferably.

At least one compound selected from the group consisting of the following general formulas (1) to (3) is 1 selected from the group consisting of the general formulas (1) to (3) in the dispersing agent of the first present invention It may be the same as more than one kind of compound.

(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 benzyl group optionally having a substituent, or -OR ^e , and R ^e is a carbon number Represents a (meth)acryloyl group via a 1 to 20 linear, branched or cyclic alkyl group, a vinyl group, an optionally substituted phenyl or benzyl group, or an alkylene group having 1 to 4 carbon atoms. In 2), R ^b , R ^{b '} and R ^b" are each independently a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent Represents optionally a vinyl group, optionally substituted phenyl or benzyl group, or -OR ^f , R ^f is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms optionally having a substituent, or optionally having a substituent A vinyl group, a optionally substituted phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, X represents a chlorine atom, a bromine atom or an iodine atom. In 3), R ^c and R ^d are each independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -OR ^e and R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group optionally having a substituent, or (meth)acrylo via an alkylene group having 1 to 4 carbon atoms. a diary, provided that at least one of R ^c and R ^d contains a carbon atom.)

In the salt-type graft copolymer, the content of at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon forms a salt with the nitrogen moiety at the terminal of the structural unit represented by the general formula (I), It is preferable that the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons be 0.01 mol or more, and 0.05 mol or more with respect to the nitrogen moiety at the terminal of the structural unit represented by the general formula (I). It is more preferable to set it as 0.1 mol or more, and it is still more preferable to set it as 0.1 mol or more, and it is especially preferable to set it as 0.2 mol or more. If it is more than the said lower limit, the color material dispersibility improvement effect by salt formation is easy to be acquired. Similarly, it is preferable to set it as 1 mol or less, It is more preferable to set it as 0.8 mol or less, It is further more preferable to set it as 0.7 mol or less, It is especially preferable to set it as 0.6 mol or less. It can be set as the thing excellent in image development adhesiveness and solvent re-solubility as it is below the said upper limit.

In addition, at least 1 type selected from the group which consists of an organic acid compound and a halogenated hydrocarbon may be used individually by 1 type, and may combine 2 or more types. When combining 2 or more types, it is preferable that the total content exists in the said range.

The preparation method of the salt-type graft copolymer may be the same as the preparation method of the salt-type graft copolymer in the dispersing agent of the first present invention.

In addition, the amine value of the obtained salt-type graft copolymer and its measuring method may be the same as that of the amine value of the salt-type graft copolymer in the dispersing agent of the said 1st this invention and its measuring method.

Moreover, in 2nd this invention, the hydroxyl value of a dispersing agent may be the same as the hydroxyl value in the dispersing agent of said 1st this invention.

Furthermore, in the second present invention, the method for determining the content ratio (mol%) of each structural unit in the graft copolymer in the dispersant is in the graft copolymer in the dispersing agent of the first present invention. It may be similar to the method of calculating|requiring the content rate (mol%) of each structural unit.

In the second invention, at least one of the above-mentioned graft copolymer and salt-type graft copolymer is used as the dispersant, and the content thereof is determined by the type of the color material to be used, the solid content concentration in the photosensitive colored resin composition described later, etc. Therefore, it is appropriately selected.

It is preferable to mix|blend content of a dispersing agent at 2 mass % - 30 mass % with respect to solid content whole quantity of the photosensitive colored resin composition, and it is especially preferable to mix|blend in the ratio of 3 mass % - 25 mass %. It is excellent in the dispersibility and dispersion stability of a color material as it is more than the said lower limit, and it is more excellent in the storage stability of the photosensitive colored resin composition. Moreover, developability becomes favorable as it is below the said upper limit. When forming a colored layer with especially high colorant concentration, content of a dispersing agent is 2 mass % - 25 mass % with respect to the solid content whole amount of the photosensitive colored resin composition, More preferably, it mix|blends in the ratio of 3 mass % - 20 mass % It is preferable to do

In addition, in this invention, solid content is all things other than the solvent mentioned later, The monomer etc. which are melt|dissolved in the solvent are also contained.

<Photoinitiator used in the second invention>

The photoinitiator in the photosensitive colored resin composition of 2nd this invention contains the oxime ester type photoinitiator which has diphenyl sulfide frame|skeleton. Since the oxime ester type photoinitiator which has a diphenyl sulfide skeleton is contained, when sclerosis|hardenability of a coating film improves, it is thought that the solvent resistance of the hardened|cured material of the photosensitive colored resin composition becomes favorable by the synergistic effect with the said specific dispersing agent.

(Oxime ester-based photoinitiator having a diphenyl sulfide skeleton)

Although the oxime ester type photoinitiator which has a diphenyl sulfide skeleton used for 2nd this invention is not specifically limited, From a point which a sensitivity improves, the oxime ester compound represented by the following general formula (a) is mentioned.

(In the general formula (a), X ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, and the alkyl group, the cycloalkyl group and the phenyl group are each a halogen atom. , may be substituted with a substituent selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms and a phenyl group, X ² is a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group X ³ is each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, a heteroaryl group, an ester group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. group, nitro group, carboxy group or -CO-X ⁴ , wherein the alkyl group, cycloalkyl group, aryl group, heteroaryl group, ester group and alkoxy group each consist of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group. may be substituted with a substituent selected from the group X ⁴ represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, or a heteroaryl group, and the above alkyl group, cycloalkyl group, or aryl group , the heteroaryl group may each be substituted with a substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group, j represents an integer from 0 to 1, and k represents an integer from 0 to 5 indicate.)

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms in X ¹ , X ² , and X ³ include a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. can be heard

Examples of the cycloalkyl group having 3 to 20 carbon atoms in X ¹ and X ³ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group. can

The cycloalkyl group for X ² may be the same as the cycloalkyl group having 3 to 20 carbon atoms, and a cyclopentyl group and a cyclohexyl group are preferable.

As said C1 ^- C20 alkyl group in X2, in addition to the said C1-C12 linear or branched alkyl group, n-tetradecyl, n-hexadecyl, n-octadecyl group, etc. are mentioned.

As said aryl group in X< ³ >, a C6-C12 aryl group is mentioned, For example, a phenyl group, a naphthyl group, etc. are mentioned.

As said heteroaryl group in X< ³ >, a C4-C10 heteroaryl group is mentioned, For example, a furanyl group, a thiophenyl group, a benzofuranyl group, a benzothiophenyl group, an indole group, etc. are mentioned.

As said C1-C6 ester group (-COORa) in X3, the case where said R ^{<a> is} the said C1 ^- C6 alkyl group is mentioned.

Examples of the alkoxy group having 1 to 6 carbon atoms for X ³ include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group and the like.

A fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned as a halogen atom which may be substituted by the said alkyl group, a cycloalkyl group, and a phenyl group in ^X1 , X3, ^and an aryl group and heteroaryl group.

The alkoxy group having 1 to 6 carbon atoms which may be substituted with an alkyl group, a cycloalkyl group and a phenyl group for X ¹ and X ³ and an aryl group or a heteroaryl group may be the same as the alkoxy group having 1 to 6 carbon atoms for X ³ . good night.

In the general formula (a), as X ¹ , a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group is preferable from the viewpoint of improving the sensitivity, and an alkyl group having 1 to 10 carbon atoms is preferable. Or a phenyl group is preferable.

In the general formula (a), X ² is preferably an alkyl group having 1 to 16 carbon atoms or a cycloalkyl group substituted with an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group from the viewpoint of solvent solubility or compatibility, and is an alkyl group having 1 to 8 carbon atoms or a carbon number A C1-C14 alkyl group substituted with a 5-6 cycloalkyl group is more preferable.

j represents an integer of 0 to 1.

k represents the integer of 0-5. From the point of solvent solubility and compatibility, k may be 1 or more, and 3 or less, 2 or less, and 1 or less are preferable from the point of developability and a brightness|luminance. In terms of developability and luminance, k is 0, that is, it is not necessary to have a substituent.

In 2nd this invention, it is preferable that the said oxime ester type photoinitiator which has a diphenyl sulfide skeleton is an oxime ester compound represented by the following general formula (A) from the point of image development residue suppression effect.

(In the general formula (A), Z ¹ , Z ³ , Z ⁴ and Z ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or a phenyl group having 3 to 20 carbon atoms. , the alkyl group, cycloalkyl group and phenyl group may each be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group, Z ² is an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group indicate.)

In the general formula (A), the linear or branched alkyl group having 1 to 12 carbon atoms and the cycloalkyl group having 3 to 20 carbon atoms in Z ¹ , Z ³ , Z ⁴ and Z ⁵ are each represented by the general formula (a) may be the same as described in

In addition, in Z ¹ , Z ³ , Z ⁴ and Z ⁵ , the halogen atom and the alkoxy group having 1 to 6 carbon atoms which may be substituted with the alkyl group, the cycloalkyl group and the phenyl group are those described in the general formula (a) above, respectively. may be the same

In addition, in Z2, the C1 ^- C20 alkyl group substituted by the cycloalkyl group may be the same as what was demonstrated by the said General formula (a).

In the general formula (A), Z ¹ is preferably an alkyl group or phenyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or a phenyl group, and still more preferably a methyl group, from the viewpoint of improving the sensitivity.

Moreover, ⁱⁿ general formula ( ^A ), as Z3, ^Z4 , and Z5, a hydrogen atom, a methyl group, an ethyl group, n-propyl group, or i-propyl group is preferable from a luminance point.

In the general formula (A), as Z ² , an alkyl group having 1 to 14 carbon atoms substituted with a cycloalkyl group having 5 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is preferable from the viewpoint of a favorable effect of suppressing development residues. A substituted alkyl group having 1 to 10 carbon atoms is more preferable, a cyclohexylmethyl group or a cyclopentylmethyl group is still more preferable, and a cyclohexylmethyl group is particularly preferable.

Examples of the oxime ester-based photoinitiator having a diphenyl sulfide skeleton include an oxime ester compound represented by the following formula (A-1), 1,2-octadione, 1-[4-(phenylthio)phenyl]-, 2 -(o-benzoyloxime] (such as Irgacure OXE01, manufactured by BASF), 1,2-propanedione, 3-cyclopentyl-1-[4-(phenylthio)phenyl]-, 2-(o-benzoyl) oxime] (for example, TR-PBG-305, manufactured by Changzhou Qiangli Diens New Chailao Co., Ltd.), 1,2-propanedione, 3-cyclopentyl-1-[4-[(2-hydroxyethoxy)phenylthio] phenyl]-, 2-(o-acetyloxime], 1-pentanone, 1-[4-[4-(2-benzofuranylcarbonyl)phenylthio]phenyl]-4-methyl, 1-(o- Acetyloxime), commercially available products include TR-PBG-3057 (manufactured by Changzhou Chiang Lidians Shinchailao Co., Ltd.), ADEKACLES NCI-930 (manufactured by ADEKA), Irgacure OXE04 (manufactured by BASF), and the like. .

The oxime ester compound represented by the above formula (A-1) and 1,2-propanedione, 3-cyclopentyl-1-[4-(phenylthio)phenyl]-, 2 At least one selected from the group consisting of -(o-benzoyloxime] is preferable, and from the viewpoint that solvent resistance is more easily improved, the oxime ester-based photoinitiator having the diphenylsulfide skeleton is represented by the above formula (A-1) It is preferable that it is an oxime ester compound represented by In addition, the oxime ester compound represented by the formula (A-1) is a polyethylene oxide chain, a polypropylene oxide chain or Also in combination with a dispersing agent having a relatively short ester chain, it is preferable at the point that it is easy to improve the water stain suppression effect by a synergistic effect.

The oxime ester photoinitiator having a diphenyl sulfide skeleton is, for example, referring to Japanese Patent Publication No. 2012-526185, using diphenyl sulfide or a derivative thereof, and depending on the material used, a solvent, reaction temperature, reaction time, It can synthesize|combine by selecting a purification method etc. suitably. Moreover, you may acquire and use a commercial product suitably.

(Other photoinitiators)

Although the photoinitiator in the photosensitive colored resin composition of 2nd this invention contains the oxime ester type photoinitiator which has a diphenyl sulfide frame|skeleton, From the point which adjusts a sensitivity more favorably, the oxime ester which has a diphenyl sulfide frame|skeleton. You may further contain a photoinitiator different from a system photoinitiator. In addition, what is called a so-called sensitizer other than a photoinitiator is contained in the other photoinitiator used for the photosensitive colored resin composition of this invention.

Among them, the photoinitiator in the photosensitive colored resin composition of the second invention is, in addition to the oxime ester-based photoinitiator having a diphenylsulfide skeleton, an α-aminoketone-based photoinitiator, an oxime ester-based photoinitiator having a carbazole skeleton, and Biimi When it further contains at least one selected from the group consisting of a dazole-based photoinitiator, a thioxanthone-based photoinitiator, and a benzophenone-based photoinitiator, when forming desired micropores in the colored layer at the same time during patterning of the colored layer, micropores It is preferable in that the cross-sectional shape of That is, when a more sensitive photoinitiator is used for forming the colored layer, the radicals migrate to the unexposed portion after radical generation, and the shape of the unexposed portion inside the exposed portion is maintained, and the dimensional accuracy of the unexposed portion peripheral portion deteriorates. It is difficult to form without becoming. At least one selected from the group consisting of an α-aminoketone-based photoinitiator, an oxime ester-based photoinitiator having a carbazole skeleton, a biimidazole-based photoinitiator, a thioxanthone-based photoinitiator, and a benzophenone-based photoinitiator is selected from the middle to the deep portion of the coating film ), and it is easy to suppress hardening only on the surface of a coating film.

Therefore, in addition to the oxime ester-based photoinitiator having a diphenyl sulfide skeleton, an α-aminoketone-based photoinitiator, an oxime ester-based photoinitiator having a carbazole skeleton, a biimidazole-based photoinitiator, a thioxanthone-based photoinitiator, and a benzophenone-based photoinitiator When at least one member selected from the group consisting of is further contained in combination, it becomes possible to cure the coating film with a good balance from the surface to the deep part while maintaining good sensitivity, and it becomes possible to control the cross-sectional shape of the micropores, and the cross section of the micropores The taper angle [theta] (refer FIG. 5) of a shape becomes less than 90 degrees, and it becomes favorable.

In addition, in addition to the oxime ester-based photoinitiator having a diphenylsulfide skeleton, an α-aminoketone-based photoinitiator, an oxime ester-based photoinitiator having a carbazole skeleton, a biimidazole-based photoinitiator, a thioxanthone-based photoinitiator, and a benzophenone-based photoinitiator When it further contains in combination of at least 1 sort(s) selected from the group, it becomes possible to control the sensitivity of an unexposed part favorably, and the image development residue suppression effect will become high.

As the α-amino ketone-based photoinitiator, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (eg Irgacure 907, manufactured by BASF), 2-benzyl-2 -(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (eg, Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF) and the like.

As the α-aminoketone-based photoinitiator, it may be used alone or in combination of two or more types, and among them, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and 2- Benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone is more preferable at the point of making the cross-sectional shape of micropores favorable.

Examples of the oxime ester-based photoinitiator having a carbazole skeleton include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (For example, Irgacure OXE02, manufactured by BASF), methanone, [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]- 11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6-trimethylphenyl) (such as Irgacure OXE-03, manufactured by BASF), ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), methanone , (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl] -, o-acetyloxime, 1-propanone, 3-Cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (such as TR-PBG-304, Changzhou (manufactured by Chiangri Diens Shinchailao), 1-propanone, 3-cyclopentyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(o-acetyl oxime), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinyloxy)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), ethanone, 2- Cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), 1-octanone, 1-[4-[3- [1-[(acetyloxy)imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)thio]-2-methylbenzoyl]-9H-carbazol-9-yl ]phenyl]-, 1-(o-acetyloxime) (eg, EXTA-9, manufactured by Union Chemical), commercially available products include ADEKA OPT-N-1919 (made by ADEKA), ADEKA ACLES NCI-831 (made by ADEKA) and the like.

As the oxime ester-based photoinitiator having a carbazole skeleton, it may be used alone or in combination of two or more. Among them, 1-propanone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (such as TR-PBG-304, manufactured by Changzhou Chiang Lidians New Chailao Co., Ltd.), ethanone, 1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (such as Irgacure OXE02, manufactured by BASF) or methanone, (9-ethyl-6- It is preferable to use nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyloxime at the point of high sensitivity.

As the biimidazole-based photoinitiator, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimi Dazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl- 1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromo phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.

As the biimidazole-based photoinitiator, it may be used alone or in combination of two or more, among them 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1; It is preferable to use 2'-biimidazole from the point of making the cross-sectional shape of a micropore favorable.

Examples of the thioxanthone-based photoinitiator include 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2,4-dichlorothioxanthone. can be heard

As the thioxanthone-based photoinitiator, it may be used alone or in combination of two or more types. It is preferable in that it improves.

Benzophenone-based photoinitiators include benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxy Benzophenone, 4,4'-bis (diethylamino) benzophenone, etc. are mentioned.

As a benzophenone-type photoinitiator, it may be used individually or in combination of 2 or more types, Especially, using 4,4'-bis (diethylamino) benzophenone is preferable from the point of making the cross-sectional shape of micropores favorable. Do.

The total content of the photoinitiator used in the photosensitive colored resin composition of the second present invention is not particularly limited as long as the effects of the present invention are not impaired, With respect to the total solid content of the photosensitive colored resin composition, preferably 0.1 mass% or more 12.0 mass % or less, More preferably, it exists in the range of 1.0 mass % or more and 8.0 mass % or less. When this content is more than the said lower limit, photocuring fully advances and it suppresses that an exposed part elutes at the time of image development, On the other hand, if it is below the said upper limit, the luminance fall by yellowing of the colored layer obtained can be suppressed.

Here, solid content is all things other than a solvent, and liquid polyfunctional monomer etc. are contained.

When the photoinitiator contains the oxime ester-based photoinitiator having the diphenyl sulfide skeleton and the other photoinitiators, the content of the oxime ester-based photoinitiator having the diphenyl sulfide skeleton is solvent-resistant with respect to the total amount of the photoinitiator. From the viewpoint of improvement and sensitivity, preferably 10 mass% or more and 98 mass% or less, more preferably 20 mass% or more and 95 mass% or less, still more preferably 30 mass% or more and 95 mass% or less, and improvement of solvent resistance , 50 mass % or more and 90 mass % or less are especially preferable from the point of improvement of the image development residue suppression effect, and the improvement of the cross-sectional shape of a micropore.

<Color material used in the second invention>

In the second aspect of the present invention, the color material is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and may be the same as the color material described in the first aspect of the present invention.

The photosensitive colored resin composition which concerns on 2nd this invention WHEREIN: Content of a color material is not specifically limited. Content of a color material is 3 mass % - 65 mass % with respect to the solid content whole amount of the photosensitive colored resin composition from the point of dispersibility and dispersion stability, More preferably, it is good to mix|blend in the ratio of 4 mass % - 60 mass %. If it is more than the said lower limit, the colored layer at the time of apply|coating the photosensitive colored resin composition with a predetermined|prescribed film thickness (normally 1.0 micrometer - 5.0 micrometers) has sufficient color density. Moreover, while being excellent in storage stability as it is below the said upper limit, the colored layer which has sufficient hardness and adhesiveness with a board|substrate can be obtained. In particular, when forming a colored layer having a high colorant concentration, the total content of the colorant is 15% by mass to 65% by mass, more preferably 25% by mass to 60% by mass relative to the total solid content of the photosensitive colored resin composition. It is better to mix with

<Alkali-soluble resin used in the second invention>

The alkali-soluble resin used in the photosensitive colored resin composition of the second present invention has an acidic group, acts as a binder resin, and can be appropriately selected from among those soluble in an alkali developer used for pattern formation. . Alkali-soluble resin and its content used for 2nd this invention may be the same as alkali-soluble resin and its content demonstrated by 1st this invention.

<Photopolymerizable compound used in the second invention>

The photopolymerizable compound used in the photosensitive colored resin composition of 2nd this invention should just be a thing which can superpose|polymerize with the said photoinitiator. The photopolymerizable compound and its content used in the photosensitive colored resin composition of 2nd this invention may be the same as the photopolymerizable compound and its content demonstrated by 1st this invention.

<Solvent used in the second invention>

It does not react with each component in the photosensitive colored resin composition as a solvent used for 2nd this invention, What is necessary is just an organic solvent which can melt|dissolve or disperse|distribute these, and it will not specifically limit. A solvent can be used individually or in combination of 2 or more types. The solvent and its content used for 2nd this invention may be the same as the solvent and its content demonstrated by 1st this invention.

As another component used for the photosensitive colored resin composition of 2nd this invention, and these content, it may be the same as that of the other component demonstrated by 1st this invention, and these content.

<The manufacturing method of the photosensitive colored resin composition of 2nd this invention>

The second method for producing the photosensitive colored resin composition of the present invention contains a colorant, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additional components used as desired, and the colorant is added to the solvent by the dispersant. A method that can be uniformly dispersed is preferable in terms of improving contrast, and it can be prepared by mixing using a known mixing means.

As a method for preparing the resin composition, for example, (1) first, a color material and a dispersing agent are added to a solvent to prepare a color material dispersion, and in this dispersion, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additional components used as desired How to mix; (2) a method of simultaneously adding and mixing a colorant, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive components used as desired in a solvent; (3) a method of adding a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive components used as desired in a solvent, mixing, and adding a colorant to disperse; (4) In the solvent, a color material, a dispersing agent, and an alkali-soluble resin are added to prepare a color material dispersion, and to this dispersion, an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additive components used as desired are further added. , how to mix; and the like.

Among these methods, the methods (1) and (4) are preferable in that they can effectively prevent aggregation of the color material and uniformly disperse them.

The method for preparing the color material dispersion liquid can be appropriately selected from among conventionally known dispersion methods. For example, (1) a dispersing agent is previously mixed with a solvent and stirred to prepare a dispersant solution, and then, if necessary, an organic acid compound is mixed to form a salt of the amino group of the dispersing agent with the organic acid compound. The method of mixing this with a color material and other components as needed, and dispersing it using a well-known stirrer or a disperser; (2) The dispersant is mixed with a solvent and stirred to prepare a dispersant solution, then, a color material and, if necessary, an organic acid compound, and other components are mixed as necessary, and dispersed using a known stirrer or disperser how to do; (3) The dispersing agent is mixed with a solvent and stirred to prepare a dispersant solution, then, a colorant and other components are mixed as needed, and a known stirrer or disperser is used to form a dispersion, and, if necessary, an organic acid The method of adding a compound, etc. are mentioned.

Examples of the disperser for dispersing treatment include roll mills such as two rolls and three rolls, ball mills such as ball mills and vibrating ball mills, paint conditioners, bead mills such as continuous disk bead mills and continuous annular bead mills. As preferable dispersion conditions for the bead mill, the bead diameter used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

<Preferable aspect of the photosensitive colored resin composition which concerns on 2nd this invention>

In the photosensitive colored resin composition according to the second aspect of the present invention, that the oxime ester-based photoinitiator having a diphenyl sulfide skeleton is an oxime ester compound represented by the general formula (A) is an effect of inhibiting development residues. desirable.

In the photosensitive colored resin composition according to the second aspect of the present invention, the oxime ester-based photoinitiator having a diphenyl sulfide skeleton is an oxime ester compound represented by the formula (A-1). point, solvent resistance is more easily improved, and among the specific dispersants used in the second invention, even in combination with a dispersing agent having a relatively short polyethylene oxide chain, polypropylene oxide chain or ester chain, by a synergistic effect It is preferable in that it is easy to improve the water stain suppression effect.

In the photosensitive colored resin composition according to the second aspect of the present invention, in the dispersing agent, in the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the general formula (III”) It is preferable that the structural unit represented by ) is included at the point that the action|action of the solvent affinity part by an oxygen atom becomes more remarkable.

In the photosensitive colored resin composition according to the second aspect of the present invention, in the dispersing agent, in the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the general formula (III”) ) (provided that m" represents a number of 19 or more and 80 or less) is included from the viewpoint of the water stain suppression effect.

In the photosensitive colored resin composition according to the second aspect of the present invention, the photoinitiator is an α-aminoketone-based photoinitiator, an oxime ester-based photoinitiator having a carbazole skeleton, a biimidazole-based photoinitiator, a thioxanthone-based photoinitiator, and a benzophenone-based photoinitiator It is preferable that at least one selected from the group consisting of

<Use>

Since the photosensitive colored resin composition which concerns on 2nd this invention can satisfy dispersion stability, high contrast, development time shortening, and excellent solvent resistance at the same time, it can use suitably for a color filter use especially.

II-3. Color filter according to the second invention

A second color filter according to the present invention is a color filter comprising at least a substrate and a colored layer formed on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the second present invention. am.

In the color filter according to the second aspect of the present invention, at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the second aspect of the present invention, whereby a color filter with high contrast and excellent productivity can be obtained.

As long as the color filter according to the second invention has a colored layer that is a cured product of the photosensitive colored resin composition according to the second invention, the other configuration may be the same as described for the color filter according to the first invention. Therefore, the description here is omitted.

II-4. Display device according to the second aspect of the present invention

The liquid crystal display device according to the second aspect of the present invention includes the color filter according to the second aspect of the present invention. In the second aspect of the present invention, by using the color filter according to the second aspect of the present invention, a display device with high contrast and excellent productivity can be provided.

If the second display device according to the present invention includes the color filter according to the second present invention, other configurations may be the same as those described in the first display device according to the present invention, so the description here is omitted. do.

Example

Hereinafter, the present invention will be specifically described with reference to Examples. These descriptions do not limit the present invention.

The amine value of the block copolymer before salt formation and the amine value of the salt block copolymer were determined according to the measurement method described in the specification of the present invention.

The weight average molecular weight (Mw) of the block copolymer before salt formation was calculated|required as a standard polystyrene conversion value by GPC (gel permeation chromatography) according to the measuring method described in the specification of this invention mentioned above.

Example I series: first invention

(Synthesis Example 1: Preparation of macromonomer A)

In a reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, 70.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was placed, and the mixture was heated to a temperature of 90° C. while stirring under a nitrogen stream. A monomer having a PEG chain that induces a structural unit represented by the general formula (III) (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R ⁴ in the general formula (III) is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is CH ₃ , m=22) 1.0 parts by mass, methyl methacrylate (MMA) 99.0 parts by mass, mercaptoethanol 4.0 parts by mass, PGMEA 30 parts by mass, α,α'-azobisisobuty The mixed solution of 1.0 mass part of ronitrile (AIBN) was dripped over 1.5 hours, and also reacted for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80°C, and Karenz MOI (manufactured by Showa Denko Co., Ltd.) 8.74 parts by mass, dioctyltin dilaurate 0.125 g, p-methoxyphenol 0.125 parts by mass. And 30 parts by mass of PGMEA was added and stirred for 3 hours to obtain a 50% solution of macromonomer A. The obtained macromonomer A was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol/L lithium bromide addition/polystyrene standard, and a weight average molecular weight (Mw) of 4500, molecular weight distribution ( Mw/Mn) was 1.6.

(Synthesis Examples 2 to 10: Preparation of macromonomers B to K)

In the preparation of the macromonomer A of Synthesis Example 1, instead of using 1.0 parts by mass of a monomer and 99.0 parts by mass of MMA for deriving the structural unit represented by the general formula (III) as a monomer, as shown in Table 1, the type of monomer and Macromonomers B to K were prepared in the same manner as in Synthesis Example 1, except that at least one of the mass ratios was changed and used. Table 1 shows the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained macromonomer.

(Comparative Synthesis Examples 1-3: Preparation of macromonomers L to N)

In the preparation of the macromonomer A of Synthesis Example 1, instead of using 1.0 parts by mass of a monomer and 99.0 parts by mass of MMA for deriving the structural unit represented by the general formula (III) as a monomer, as shown in Table 1, the type of monomer and Macromonomers L to N were produced in the same manner as in Synthesis Example 1 except that at least one of the mass ratios was changed and used. Table 1 shows the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained macromonomer.

In addition, the abbreviation in a table|surface is as follows.

a monomer having a PEG chain (m=30); Nichiyu Co., Ltd., trade name: Blemma PSE-1300, in the general formula (III), R ⁴ is CH ₃ , A ³ is COO, R ⁵ is ethylene group, R ⁶ is C ₁₈ H ₃₇ , m=30

a monomer having a PEG chain (m=45); Evonik make, trade name: VISIOMER MPEG 2005 MA W, in general formula (III), R ⁴ is CH ₃ , A ³ is COO, R ⁵ is ethylene group, R ⁶ is CH ₃ , m=45

a monomer having a PEG chain (m=90); Nichiyu Co., Ltd., trade name: Blemma PME-4000, PEG chain repeat number m = 90

a monomer having a PEG chain (m=17); Evonik manufacture, trade name: VISIOMER MPEG 750 MA W, PEG chain repetition number m=17

a monomer having a PEG chain (m=9); Nichiyu Co., Ltd., trade name: Blemma PME-400, PEG chain repeat number m = 9

a monomer having a PEG chain (m=3); Tokyo Kasei Kogyo Co., Ltd., trade name: triethylene glycol monoethyl ether methacrylate, repeating number of PEG chains m = 3

BMA; n-Butyl methacrylate

2-EHMA; 2-ethylhexyl methacrylate

BzMA; benzyl methacrylate

(Preparation Example 1: Preparation of graft copolymer A)

In a reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, 63.1 parts by mass of PGMEA was placed and heated to a temperature of 85° C. while stirring under a nitrogen stream. 141 parts by mass of macromonomer A solution of Synthesis Example 1 (effective solid content 70.5 parts by mass), 29.5 parts by mass of methacrylic acid 2-(dimethylamino)ethyl (DMMA), 1.24 parts by mass of n-dodecylmercaptan, 49.4 parts by mass of PGMEA , The mixed solution of 1.0 mass part of AIBN is dripped over 1.5 hours, and after heating and stirring for 3 hours, the mixed liquid of AIBN 0.10 mass part and PGMEA 6.0 mass parts is dripped over 10 minutes, and also by aging at the same temperature for 1 hour, graft air A 35.0 mass % solution of Coalescing A was obtained. The obtained graft copolymer A had a weight average molecular weight (Mw) of 10000 as a result of GPC measurement. In addition, the amine titer was 105 mgKOH/g.

(Preparation Examples 2 to 9: Preparation of graft copolymers B to K)

In Production Example 1, instead of using 70.5 parts by mass of effective solid content of macromonomer A and 29.5 parts by mass of DMMA, as shown in Table 2, except that the type of macromonomer and the mass ratio of the macromonomer and DMMA were changed, Production Example 1 Graft copolymers B to K were prepared in the same manner as described above. Table 2 shows the weight average molecular weight (Mw) and the amine number before modification of the obtained graft copolymers B to K.

(Comparative Preparation Examples 1-4: Preparation of graft copolymer L to O)

In Production Example 1, instead of using 70.5 parts by mass of effective solid content of macromonomer A and 29.5 parts by mass of DMMA, as shown in Table 2, except that the type of macromonomer and the mass ratio of the macromonomer and DMMA were changed, Production Example 1 In the same manner as described above, graft copolymers L to O were prepared. Table 2 shows the weight average molecular weight (Mw) and the amine number before modification of the obtained graft copolymers L to O.

In addition, in manufacture of the graft copolymer O of Comparative Production Example 4, a monomer having a PEG chain (m=90) was used instead of the macromonomer A. The monomer having a PEG chain (m = 90) was manufactured by Nichiyu, trade name: Blemma PME-4000, the number of repetitions of the PEG chain m = 90.

(Preparation Example 3': Preparation of salt-type graft copolymer C)

To 4.22 parts by mass of the graft copolymer C solution, 0.15 parts by mass of phenylphosphonic acid (manufactured by Nissan Chemical Industry Co., Ltd., “PPA”) as a salt-forming component (0.5 equivalents based on the DMMA unit of the graft copolymer C) ) and stirred at room temperature for 1 hour to prepare a salt-type graft copolymer C solution. The obtained salt-type graft copolymer C solution was adjusted so that it might become 35% of solid content by PGMEA.

(Preparation Examples 6', 7', 8', 9', 10' and 11', Comparative Preparation Examples 2' and 3': salt-type graft copolymers F, G, H, I, J, K, M and N manufacturing)

In Preparation Example 3', instead of the graft copolymer C solution, a graft copolymer F, G, H, I, J, K, M or N solution was used, and the type and amount of the salt forming agent (graft Salt-type graft copolymers F, G, H, I, J, K, M and N solutions were prepared respectively. Table 2 shows the amine number after salt formation of the salt-type graft copolymer.

(Comparative Preparation Example 5: Preparation of block copolymer P)

250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round bottom four-necked separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 degreeC, 4.9 mass parts of butyllithium (15 mass % hexane solution), 1.1 mass parts of diisopropylamine, and 1.0 mass parts of methyl isobutyrate were injected using a syringe. A monomer having a PEG chain that induces a structural unit represented by the general formula (III) of the monomer for the B block (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R ⁴ in the general formula (III) is CH ₃ , A ³ Silver COO, R5 is ethylene group, R6 is CH3, _m = ²² ) 23.0 mass parts, MMA 30.0 mass parts, and BMA 22.0 mass parts were dripped over ⁶⁰ minutes using the funnel for addition. After 30 minutes, 25.0 mass parts of DMMA which is a monomer for A blocks was dripped over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a 35 mass% solid solution solution to obtain a block copolymer P solution. Thus, when the obtained block copolymer P was confirmed by GPC, the weight average molecular weight (Mw) was 15800. In addition, the amine titer was 89 mgKOH/g.

Table 1 shows the composition, weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the monomers of the block copolymer P. Table 2 shows the amine value of the block copolymer P.

(Comparative Preparation Example 6: Preparation of salt-type block copolymer Q)

250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round bottom four-necked separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 degreeC, 4.9 mass parts of butyllithium (15 mass % hexane solution), 1.1 mass parts of diisopropylamine, and 1.0 mass parts of methyl isobutyrate were injected using a syringe. A monomer having a PEG chain that induces a structural unit represented by the general formula (IIIa) of the monomer for block B (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: triethylene glycol monoethyl ether methacrylate, R in the general formula (IIIa) ⁴ is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is CH ₃ , m=3) 8.3 parts by mass, MMA 18.8 parts by mass, BMA 20.1 parts by mass, 2-EHMA 14.1 parts by mass, BzMA 11.8 parts by mass The part was dripped over 60 minutes using the funnel for addition. After 30 minutes, 26.9 mass parts of DMMA which is a monomer for A blocks were dripped over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane and purified by filtration and vacuum drying. Thus, when the obtained block copolymer was confirmed by GPC, the weight average molecular weight (Mw) was 4900. In addition, the amine titer was 81 mgKOH/g. Then, 8.0 parts by mass of the obtained block copolymer is diluted with 10.0 parts by mass of PGMEA, 1.2 parts by mass of benzyl chloride (0.83 equivalents relative to the DMMA unit of the block copolymer) is added, and stirred at 80° C. for 4 hours to obtain a salt-type block copolymer Q solution prepared The obtained salt block copolymer Q solution was adjusted so that it might become 35% of solid content by PGMEA.

Table 1 shows the composition, weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the monomers of the block copolymer Q. Table 2 shows the amine number of the block copolymer Q before salt formation and the amine number of the salt block copolymer Q after salt formation.

(Preparation Example 1: Preparation of alkali-soluble resin A)

In a polymerization tank, 300 parts by mass of PGMEA was put, and after heating up to 100° C. under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, and methacrylic acid (MAA) ) 36 parts by mass, 6 parts by mass of perbutyl O (manufactured by Nichi Oil Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dripped over 1.5 hours. Thereafter, the reaction was continued while the temperature was maintained at 100°C, and after 2 hours from the end of the dropwise addition of the mixture for forming the main chain, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor was added to stop the polymerization.

Then, 20 parts by mass of glycidyl methacrylate (GMA) is added as an epoxy group-containing compound while blowing air, and the temperature is raised to 110 ° C., 0.8 parts by mass of triethylamine is added and reaction is carried out at 110 ° C. for 15 hours, Alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40 mass %) was obtained.

In addition, as for the measuring method of the said weight average molecular weight, the weight average molecular weight was measured by the Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. In addition, the measuring method of an acid value was measured based on JISK0070.

(Example 1)

(1) Preparation of color material dispersion G-1

9.29 parts by mass of the graft copolymer A of Synthesis Example 1 as a dispersant, and C.I. Pigment Green 58 (PG58) in 9.10 parts by mass, C.I. Pigment Yellow 138 (PY138) in 3.90 parts by mass, 14.63 parts by mass of the alkali-soluble resin A solution obtained in Preparation Example 1, 63.09 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0 mm in a mayonnaise bottle, and preliminary crushing.碎) as a paint shaker (manufactured by Asada Tech Co., Ltd.), shaken for 1 hour, then zirconia beads with a particle size of 2.0 mm are taken out, 200 parts by mass of zirconia beads with a particle size of 0.1 mm are added, and as a full-scale disintegration, dispersion for 4 hours with a paint shaker It carried out and obtained the color material dispersion liquid G-1.

(2) Preparation of photosensitive colored resin composition G-1

9.77 parts by mass of the color material dispersion G-1 obtained in (1) above, 0.28 parts by mass of the alkali-soluble resin A solution obtained in Preparation Example 1, and a polyfunctional monomer (trade name: Aronix M-403, manufactured by Toagosei Co., Ltd.) 0.99 parts by mass of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Co., Ltd.) 0.05 parts by mass; 0.05 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan), 1,2-octanedione, 1 0.02 parts by mass of -[4-(phenylthio)-, 2-(O-benzoyloxime)] (photoinitiator: trade name Irgacure OXE01, manufactured by BASF Japan Co., Ltd.), a fluorine-based surfactant (trade name Megapark R-08MH) 0.07 mass parts and 8.73 mass parts of PGMEA were added for DIC (Co., Ltd. product), and the photosensitive colored resin composition G-1 was obtained.

(Examples 2 to 11)

(1) Preparation of color material dispersions G-2 to G-11

In Example 1 (1), instead of the graft copolymer A, as shown in Table 3, (salt type) graft copolymers B, C, D, E, F, G, H, I, J and Color material dispersion liquids G-2 to G-11 were prepared in the same manner as in Example 1 except that K was used respectively.

(2) Preparation of photosensitive colored resin compositions G-2 to G-11

In Example 1 (2), the photosensitive colored resin composition was carried out in the same manner as in Example 1 (2), except that the color material dispersion liquids G-2 to G-11 were used instead of the color material dispersion liquid G-1. G-2 to G-11 were obtained.

(Comparative Examples 1 to 6)

(1) Preparation of comparative colorant dispersions G-1 to G-6

In Example 1 (1), instead of the graft copolymer A, as shown in Table 3, (salt type) graft copolymers L, M, N and O, and block copolymers P and Q were respectively used. Except that, it was carried out in the same manner as in Example 1 to obtain comparative colorant dispersions G-1 to G-6.

(2) Preparation of photosensitive colored resin compositions G-1 to G-6 for comparison

Comparative photosensitive coloring was carried out in the same manner as in Example 1 (2), except that in Example 1 (2), the comparative color material dispersions G-1 to G-6 were respectively used instead of the color material dispersion G-1. Resin compositions G-1 to G-6 were obtained.

(Example 12)

(1) Preparation of color material dispersion G-12

In Example 1 (1), as the color material, C.I. Pigment Green 58 (PG58) in 9.10 parts by mass, C.I. Instead of using 3.90 parts by mass of Pigment Yellow 138 (PY138), C.I. Pigment Green 59 (PG59) in 9.10 parts by mass, C.I. Except having used 3.90 mass parts of Pigment Yellow 150 (PY150), it carried out similarly to Example 1, and manufactured the color material dispersion liquid G-12.

(2) Preparation of photosensitive colored resin composition G-12

In Example 1 (2), the photosensitive colored resin composition G-12 was obtained in the same manner as in Example 1 (2) except that the color material dispersion G-12 was used instead of the color material dispersion G-1. .

(Examples 13 to 22)

(1) Preparation of color material dispersions G-13 to G-22

In Example 12 (1), instead of the graft copolymer A, as shown in Table 4, (salt type) graft copolymers B, C, D, E, F, G, H, I, J and Colorant dispersions G-13 to G-22 were prepared in the same manner as in Example 1 except that K was used respectively.

(2) Preparation of photosensitive colored resin compositions G-13 to G-22

In Example 1 (2), the photosensitive colored resin composition was carried out in the same manner as in Example 1 (2), except that the color material dispersions G-13 to G-22 were respectively used instead of the color material dispersion G-1. G-13 to G-22 were obtained.

(Comparative Examples 7 to 12)

(1) Preparation of comparative colorant dispersions G-7 to G-12

In Example 12 (1), instead of the graft copolymer A, as shown in Table 4, (salt type) graft copolymers L, M, N and O, and block copolymers P and Q were respectively used. Except that, it was carried out in the same manner as in Example 1 to obtain comparative colorant dispersions G-7 to G-12.

(2) Preparation of photosensitive colored resin compositions G-7 to G-12 for comparison

Comparative photosensitive coloring was carried out in the same manner as in Example 1 (2), except that in Example 1 (2), the comparative color material dispersions G-7 to G-12 were respectively used instead of the color material dispersion G-1. Resin compositions G-7 to G-12 were obtained.

(Example 23)

(1) Preparation of color material dispersion R-1

In Example 1 (1), 9.10 parts by mass of C.I. Pigment Green 58 (PG58), C.I. Instead of using 3.90 parts by mass of Pigment Yellow 138 (PY138), C.I. Pigment Red 177 (PR177) was added to 3.90 parts by mass, C.I. Except having used 9.10 mass parts of Pigment Red 291 (PR291), it carried out similarly to Example 1, and manufactured the color material dispersion liquid R-1.

(2) Preparation of photosensitive colored resin composition R-1

In Example 1 (2), in place of the color material dispersion liquid G-1, except having used the said color material dispersion liquid R-1, it carried out similarly to Example 1 (2), and obtained the photosensitive colored resin composition R-1. .

(Examples 24-33)

(1) Preparation of color material dispersion R-2 to R-11

In Example 23 (1), instead of the graft copolymer A, as shown in Table 5, (salt type) graft copolymers B, C, D, E, F, G, H, I, J and Colorant dispersions R-2 to R-11 were prepared in the same manner as in Example 23, except that K was used respectively.

(2) Preparation of photosensitive colored resin compositions R-2 to R-11

In Example 1 (2), the photosensitive colored resin composition was carried out in the same manner as in Example 1 (2), except that the color material dispersion R-2 to R-11 were respectively used instead of the color material dispersion G-1. R-2 to R-11 were obtained.

(Comparative Examples 13 to 18)

(1) Preparation of comparative colorant dispersions R-1 to R-6

In Example 23 (1), instead of the graft copolymer A, as shown in Table 5, (salt type) graft copolymers L, M, N, and O, and block copolymers P and Q, respectively Comparative color material dispersions R-1 to R-6 were obtained in the same manner as in Example 23, except that they were used.

(2) Preparation of photosensitive colored resin compositions R-1 to R-6 for comparison

Comparative photosensitive coloring was carried out in the same manner as in Example 1 (2), except that in Example 1 (2), the comparative color material dispersions R-1 to R-6 were respectively used instead of the color material dispersion G-1. Resin compositions R-1 to R-6 were obtained.

(Example 34)

(1) Preparation of color material dispersion B-1

In Example 1 (1), as the color material, C.I. Pigment Green 58 (PG58) in 9.10 parts by mass, C.I. Instead of using 3.90 parts by mass of Pigment Yellow 138 (PY138), C.I. Pigment Blue 15:6 (PB15:6) was added to 11.70 parts by mass, C.I. Except having used 1.30 mass parts of pigment violet 23 (PV23), it carried out similarly to Example 1, and manufactured the color material dispersion liquid B-1.

(2) Preparation of photosensitive colored resin composition B-1

6.78 parts by mass of the color material dispersion B-1 obtained in (1) above, 1.28 parts by mass of the alkali-soluble resin A solution obtained in Preparation Example 1, and a polyfunctional monomer (trade name: Aronix M-403, manufactured by Toagosei Co., Ltd.) 1.20 parts by mass of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan) 0.08 parts by mass; 0.08 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan), 1,2-octanedione, 1 -[4-(phenylthio)-, 2-(O-benzoyloxime)] (photoinitiator: trade name Irgacure OXE01, manufactured by BASF Japan Co., Ltd.) 0.04 parts by mass, fluorine-based surfactant (trade name Megapark R-08MH) 0.07 mass parts and 10.48 mass parts of PGMEA were added for DIC (Co., Ltd. product), and the photosensitive colored resin composition B-1 was obtained.

(Examples 35-44)

(1) Preparation of colorant dispersions B-2 to B-11

In Example 34 (1), instead of the graft copolymer A, as shown in Table 6, (salt type) graft copolymers B, C, D, E, F, G, H, I, J and Colorant dispersions B-2 to B-11 were prepared in the same manner as in Example 34 except that K was used respectively.

(2) Preparation of photosensitive colored resin compositions B-2 to B-11

In Example 34 (2), the photosensitive colored resin composition was carried out in the same manner as in Example 34 (2), except that the color material dispersion liquids B-2 to B-11 were respectively used instead of the color material dispersion liquid B-1. B-2 to B-11 were obtained.

(Comparative Examples 19 to 24)

(1) Preparation of Comparative Color Material Dispersion Liquids B-1 to B-6

In Example 34 (1), instead of the graft copolymer A, as shown in Table 6, (salt type) graft copolymers L, M, N and O, and block copolymers P and Q were respectively used. Except that, it was carried out in the same manner as in Example 34 to obtain comparative colorant dispersions B-1 to B-6.

(2) Preparation of photosensitive colored resin compositions B-1 to B-6 for comparison

Comparative photosensitive coloring was carried out in the same manner as in Example 34 (2), except that in Example 34 (2), the comparative color material dispersions B-1 to B-6 were respectively used instead of the color material dispersion B-1. Resin compositions B-1 to B-6 were obtained.

[Assessment Methods]

<Water stain suppression evaluation>

Post-baking the photosensitive colored resin compositions obtained in Examples and Comparative Examples on a glass substrate (NH Techno Glass Co., Ltd., "NA35", 0.7 mm thick, 100 mm x 100 mm) using a spin coater, respectively. After drying, it was applied to a film thickness to form a colored layer with a thickness of 2.0 μm, dried at 60° C. for 3 minutes using a hot plate, and irradiated with UV light of 30 mJ/cm 2 using an ultra-high pressure mercury lamp without passing through a photomask. By doing so, the colored layer was formed on the glass substrate. Then, using 0.05 wt% potassium (KOH) as a developer, shower development for 60 seconds, and then washing with pure water for development treatment, and rotating the cleaned substrate for 10 seconds to centrifuge the water immediately after removing the water, the contact angle of the pure water is measured as follows to evaluate the water stain.

For measurement of the contact angle of pure water, 1.0 µL of pure water was dropped onto the surface of the colored layer immediately after centrifugation of the water, and the static contact angle after 10 seconds at which the water droplet adhered was measured according to the θ/2 method. The measuring apparatus was measured using the contact angle measuring instrument DM500 by Kyowa Gaimen Chemicals.

(Evaluation standard)

A: Contact angle of 70 degrees or more

B: Contact angle of 50 degrees or more and less than 70 degrees

C: contact angle of 30 degrees or more and less than 50 degrees

D: contact angle less than 30 degrees

If the water stain evaluation criterion is A or B, it can be practically used, but if the evaluation result is A, the effect is more excellent.

<Evaluation of development residue>

After post-baking the photosensitive colored resin compositions obtained in Examples and Comparative Examples on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater, a colored layer having a thickness of 2.0 μm is formed. After apply|coating to the film thickness to say, it dried at 80 degreeC for 3 minutes using a hotplate, and formed the colored layer on the glass substrate. The glass plate on which the colored layer was formed was developed by washing with pure water after shower development for 60 seconds using a 0.05 mass% aqueous potassium hydroxide solution as an alkali developer. The colored layer forming part after development was observed by visually confirming it, and then thoroughly wiped with a lens cleaner containing ethanol (manufactured by Toray Corporation, trade name: Toreshi MK Clean Cloth), and the degree of coloration of the lens cleaner was visually checked and observed. did.

(Based on evaluation of developing residues)

A: The development residue was not confirmed by visual confirmation, and the lens cleaner was not colored at all.

B: The development residue was not confirmed by visual confirmation, but coloration of the lens cleaner was confirmed slightly.

C: Visually, some development residue was confirmed, and coloration of the lens cleaner was confirmed.

D: The development residue was confirmed by visual confirmation, and coloring of the lens cleaner was confirmed.

If the development residue evaluation criterion is A or B, it is evaluated that the development residue is sufficiently suppressed, and it can be used practically without any problem.

<Evaluation of developing time>

After post-baking the photosensitive colored resin compositions obtained in Examples and Comparative Examples on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater, a colored layer having a thickness of 2.0 μm is formed. After apply|coating with the film thickness to say, the colored layer was formed on the glass substrate by drying at 80 degreeC for 3 minute(s) using a hotplate. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 through a photomask using an ultra-high pressure mercury lamp. After that, the glass substrate on which the colored layer is formed is shower-developed using 0.05 mass % potassium hydroxide aqueous solution as an alkali developer, and the time until the colored layer is completely dissolved and the glass surface where the colored layer is formed appears was measured as the development time.

<Evaluation of solvent resistance (NMP resistance)>

After post-baking the photosensitive colored resin compositions obtained in Examples and Comparative Examples on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater, a colored layer having a thickness of 2.0 μm is formed. After apply|coating with the film thickness to say, the colored layer was formed on the glass substrate by drying at 80 degreeC for 3 minute(s) using a hotplate. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 using an ultra-high pressure mercury lamp.

Next, the said colored board|substrate was post-baked for 30 minutes in a 230 degreeC clean oven, and the colored board|substrate was created. After measuring the film thickness of the obtained colored substrate, after being immersed in NMP for 30 minutes, it air-dried and the film thickness was measured again. In addition, for the measurement of the film thickness, a stylus type step difference film thickness meter "P-15 Tencor" (manufactured by Instruments) was used.

(NMP resistance evaluation criteria)

A: The rate of change of the film thickness before and after NMP immersion is less than 2%

B: The rate of change of the film thickness before and after NMP immersion is 2% or more and less than 5%

C: The rate of change of the film thickness before and after NMP immersion is 5% or more and less than 8%

D: The rate of change of the film thickness before and after NMP immersion is 8% or more

<Evaluation of dispersibility stability of color material dispersion>

Regarding the color material dispersions obtained in Examples and Comparative Examples, the viscosity was measured immediately after preparation and after storage at 25° C. for 30 days, respectively, the viscosity change rate was calculated from the viscosity before and after storage, and viscosity stability was evaluated. For the viscosity measurement, the viscosity at 25.0±0.5° C. was measured using a vibratory viscometer.

(Based on dispersion stability evaluation)

A: The rate of change of viscosity before and after storage is less than 20%

B: The rate of change of viscosity before and after storage is 20% or more and less than 40%

C: The rate of change of viscosity before and after storage is 40% or more and less than 60%

D: The rate of change of viscosity before and after storage is 60% or more

However, it is a value when the color material is 13 mass % with respect to the total mass including the solvent of a color material dispersion liquid.

When the evaluation result is B, the color material dispersion is good, and when the evaluation result is A, the color material dispersion is excellent in dispersion stability.

<Evaluation of optical performance, evaluation of contrast>

The photosensitive colored resin composition for color filters obtained in Examples and Comparative Examples was applied on a glass substrate (NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm and 100 mm x 100 mm, respectively, using a spin coater. and apply|coating, the colored layer was formed by drying at 80 degreeC for 3 minute(s) using a hotplate. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 using an ultra-high pressure mercury lamp.

Next, the colored substrate was post-baked in a clean oven at 230° C. for 30 minutes, and the contrast, chromaticity (x, y), and luminance (Y) of the obtained colored substrate were measured with a Tsubosaka Denki contrast measuring device CT-1B and Olympus brown rice. It measured using the spectroscopy apparatus OSP-SP200.

(based on contrast evaluation)

A: Green is over 7000, Red is over 5000, Blue is over 6000

B: Green is more than 5600 and less than 7000, Red is more than 4000 and less than 5000, Blue is more than 4800 and less than 6000

C: Green is 4200 or more and 5600 or less, Red is 3000 or more and 4000 or less, Blue is 3600 or more and 4800 or less

D: Green is less than 4200, Red is less than 3000, Blue is less than 3600

However, y = 0.570 for the green of Examples 1-22 and Comparative Examples 1-12, x = 0.650 for the red of Examples 23-33 and Comparative Examples 13-18, and Examples 34-44 and Comparative Examples with C light source, respectively. Blue in 19 to 24 is a value when y = 0.107.

[Summary of results]

By comparing the Examples and Comparative Examples of the first invention, in Examples 1-44 using the specific graft copolymer or salt-type graft copolymer in the first invention, suppression of occurrence of development residue, shortening of development time, It became clear that the photosensitive colored resin composition which simultaneously satisfies suppression of occurrence of water stains and excellent solvent resistance can be obtained.

On the other hand, in Comparative Examples 1, 7, 13, and 19 using the graft copolymer L having an excessively long branched chain in which the number of repeating units of the ethylene oxide chain is 90 in the graft chain (polymer chain) of the graft copolymer. In the comparative photosensitive colored resin composition, the effect of suppressing the occurrence of development residues was insufficient, and furthermore, dispersion stability and contrast were poor.

Comparative photosensitive coloring of Comparative Examples 2, 8, 14 and 20 using the graft copolymer M having a relatively short branched chain in which the number of repeating units of the ethylene oxide chain is 17 in the graft chain (polymer chain) of the graft copolymer The resin composition was insufficient in the effect of suppressing the occurrence of water stains.

Comparative Examples 3, 9, 15, and 21 using the graft copolymer N in which the graft chain (polymer chain) of the graft copolymer is composed of structural units derived from MMA and BMA as disclosed in Patent Document 2, which is a prior art In the comparative photosensitive colored resin composition, it was easy to generate|occur|produce water unevenness, and it was easy to generate|occur|produce the image development residue also.

Comparative photosensitive colored resin compositions of Comparative Examples 4, 10, 16 and 22 using the graft copolymer O in which the number of repeating units of the ethylene oxide chain was 90 as the graft chain (polymer chain) of the graft copolymer. , the effect of inhibiting the occurrence of water stains and the effect of inhibiting the occurrence of development residues were insufficient, and furthermore, the dispersion stability and contrast were deteriorated.

Comparative photosensitive colored resin compositions of Comparative Examples 5, 11, 17 and 23 using block copolymer P having a polymer chain in which the number of repeating units of ethylene oxide chain is 22 as a structural unit of the block copolymer, the effect of inhibiting the occurrence of water stains was insufficient, and furthermore, the effect of solvent resistance could not be obtained.

As disclosed in Patent Document 1, which is a prior art, as a structural unit of the block copolymer, a block copolymer Q containing a structural unit derived from triethylene glycol ethyl ether methacrylate in which the number of repeating units of an ethylene oxide chain is 3 was used. The comparative photosensitive colored resin compositions of Comparative Examples 6, 12, 18, and 24 were insufficient in the water stain generation inhibitory effect and the development residue generation inhibitory effect, and furthermore, the solvent resistance effect was not obtained.

Example II Series: Second Invention

(Synthesis Example II-1: Preparation of macromonomer II-A)

In a reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, 70.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was placed, and the mixture was heated to a temperature of 90° C. while stirring under a nitrogen stream. A monomer having a PEG chain deriving a structural unit represented by the general formula (III") (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R ⁴ in the general formula (III") is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is CH ₃ , m"=22) 1.0 parts by mass, methyl methacrylate (MMA) 99.0 parts by mass, mercaptoethanol 4.0 parts by mass, PGMEA 30 parts by mass, α,α'-azo The mixed solution of 1.0 mass part of bisisobutyronitrile (AIBN) was dripped over 1.5 hours, and reacted for 3 hours.Then, stop nitrogen flow, and cool this reaction solution to 80 degreeC, Karenz MOI (Showa Denko) Co., Ltd.) 8.74 parts by mass, 0.125 g of dioctyltin dilaurate, 0.125 parts by mass of p-methoxyphenol and 30 parts by mass of PGMEA were added and stirred for 3 hours to obtain a 50% solution of macromonomer A. Obtained macromonomer A was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol/L lithium bromide addition/polystyrene standard, weight average molecular weight (Mw) 4500, molecular weight distribution (Mw/Mn) It was 1.6.

(Synthesis Examples II-2 to II-10: Preparation of macromonomers II-B to II-M)

In the preparation of the macromonomer II-A of Synthesis Example II-1, instead of using 1.0 parts by mass of a monomer and 99.0 parts by mass of MMA for deriving a structural unit represented by the general formula (III") as a monomer, the ones shown in Table 7 In the same manner as in Synthesis Example II-1, except that at least one of the monomer types and mass ratio was changed and used, macromonomers II-B to II-M were prepared. The molecular weight distribution (Mw/Mn) is shown in Table 7.

(Synthesis Example II-11: Preparation of macromonomer II-N)

Into a reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, 30.0 parts by mass of PGMEA was placed, and the mixture was heated to a temperature of 90° C. while stirring under a nitrogen stream. MMA 25.0 parts by mass, caprolactone-modified hydroxyethyl methacrylate (trade name; Fraxel FM5, manufactured by Daicel Corporation, caprolactone chain repetition number n=5) (PCL-FM5) 75.0 parts by mass, mercaptopropionic acid 7.0 mass Part and the mixed solution of 1.0 mass part of AIBN were dripped over 1.5 hours, and also reacted for 3 hours. After cooling, the reaction solution was diluted with 200 parts by mass of tetrahydrofuran (THF) and reprecipitated with 3000 parts by mass of hexane to obtain 106.0 parts by mass of a white powder. Next, 50.0 parts by mass of PGMEA, 3.7 parts by mass of glycidyl methacrylate (GMA), 0.15 parts by mass of N,N-dimethyldodecylamine and 0.1 parts by mass of p-methoxyphenol are added to 50.0 parts by mass of this white powder, It stirred at 110 degreeC for 24 hours, performing air bubbling. After cooling, 52.0 parts by mass of macromonomer II-N was obtained by reprecipitating this reaction solution with 3000 parts by mass of hexane.

Table 7 shows the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained macromonomer.

(Comparative Synthesis Examples II-1 to II-2: Preparation of macromonomers II-O to II-P)

In the preparation of the macromonomer II-A of Synthesis Example II-1, instead of using 1.0 parts by mass of a monomer and 99.0 parts by mass of MMA for deriving a structural unit represented by the general formula (III") as a monomer, the ones shown in Table 7 In the same manner as in Synthesis Example II-1, except that at least one of the monomer types and mass ratio was changed and used, macromonomers II-O to II-P were prepared.The weight average molecular weight (Mw) of the obtained macromonomer and The molecular weight distribution (Mw/Mn) is shown in Table 7.

In addition, the abbreviation in a table|surface is as follows.

Monomer having a PEG chain (m"=30); Nichiyu Co., Ltd. trade name: Blemma PSE-1300, in the general formula (III"), R ⁴ is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is C ₁₈ H ₃₇ , m"=30

A monomer having a PEG chain (m"=45); manufactured by Evonik, trade name: VISIOMER MPEG 2005 MA W, in the general formula (III"), R ⁴ is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is CH ₃ , m"=45

Monomer having PEG chain (m"=17); manufactured by Evonik, trade name: VISIOMER MPEG 750 MA W, number of repeats of PEG chain m"=17

Monomer having PEG chain (m"=9); Nichiyu Co., Ltd. trade name: Blemma PME-400, PEG chain repeat number m"=9

Monomer having a PEG chain (m" = 3); manufactured by Tokyo Chemical Industry Co., Ltd., trade name: triethylene glycol monoethyl ether methacrylate, repeating number of PEG chains m" = 3

Monomer having PEG chain (m"=90); Nichiyu Co., Ltd. trade name: Blemma PME-4000, PEG chain repeat number m"=90

BMA; n-Butyl methacrylate

2-EHMA; 2-ethylhexyl methacrylate

BzMA; benzyl methacrylate

(Preparation Example II-1: Preparation of graft copolymer II-A)

In a reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, 63.1 parts by mass of PGMEA was placed and heated to a temperature of 85° C. while stirring under a nitrogen stream. 141 parts by mass of macromonomer II-A solution of Synthesis Example II-1 (70.5 parts by mass of effective solid content), 29.5 parts by mass of methacrylic acid 2-(dimethylamino)ethyl (DMMA), 1.24 parts by mass of n-dodecyl mercaptan; A mixed solution of 49.4 parts by mass of PGMEA and 1.0 parts by mass of AIBN is added dropwise over 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA is added dropwise over 10 minutes, and aging at the same temperature for 1 hour , to obtain a 35.0 mass% solution of the graft copolymer II-A. As a result of GPC measurement, the obtained graft copolymer II-A had a weight average molecular weight (Mw) of 10000. In addition, the amine titer was 105 mgKOH/g.

(Preparation Examples II-2 to II-9: Preparation of graft copolymers II-B to II-N)

In Production Example 1, instead of using 70.5 parts by mass of effective solid content of macromonomer II-A and 29.5 parts by mass of DMMA, as shown in Table 8, the type of macromonomer and the mass ratio of the macromonomer and DMMA were changed, except that In the same manner as in Example II-1, graft copolymers II-B to II-N were prepared. Table 8 shows the weight average molecular weight (Mw) and the amine value before modification of the obtained graft copolymers II-B to II-N.

(Comparative Preparation Examples II-1 to II-3: Preparation of graft copolymers II-O to II-Q)

In Production Example II-1, instead of using 70.5 parts by mass of effective solid content of macromonomer II-A and 29.5 parts by mass of DMMA, as shown in Table 8, the type of macromonomer and the mass ratio of the macromonomer and DMMA were changed. , to prepare graft copolymers II-O to II-P in the same manner as in Preparation Example II-1. Table 8 shows the weight average molecular weight (Mw) and the amine value before modification of the obtained graft copolymers II-O to II-P.

In addition, in the preparation of the graft copolymer II-Q of Comparative Production Example II-3, a monomer having a PEG chain (m" = 90) was used instead of the macromonomer II-A. The monomer having this PEG chain ( m" = 90), manufactured by Nichiyu Oil, trade name: Blemma PME-4000, PEG chain repeat number m" = 90.

(Preparation Example II-3': Preparation of salt-type graft copolymer II-C)

To 4.22 parts by mass of the graft copolymer II-C solution, 0.15 parts by mass of phenylphosphonic acid (manufactured by Nissan Chemical Industry Co., Ltd., “PPA”) as a salt-forming component (DMMA unit of graft copolymer II-C) 0.5 equivalent) was added and stirred at room temperature for 1 hour to prepare a salt-type graft copolymer II-C solution. The obtained salt-type graft copolymer II-C solution was adjusted so that it might become 35% of solid content by PGMEA.

(Preparation Example II-6', II-7', II-8', II-9', II-10', II-11', II-12', Comparative Preparation II-2': salt-type graft aerial Preparation of Copolymers II-F, II-G, II-H, II-I, II-J, II-K, II-L and II-P)

In Preparation Example II-3', instead of the graft copolymer II-C solution, the graft copolymer II-F, II-G, II-H, II-I, II-J, II-K, II- Preparation Example II-3' using L or II-P solution, except that the type and amount of the salt forming agent (equivalent to the DMMA unit of the graft copolymer II-C) was changed as shown in Table 8 Salt-type graft copolymers II-F, II-G, II-H, II-I, II-J, II-K, II-L and II-P solutions were prepared in the same manner as described above, respectively. Table 8 shows the amine number after salt formation of the salt-type graft copolymer.

(Comparative Preparation Example II-4: Preparation of block copolymer II-R)

250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round bottom four-necked separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 degreeC, 4.9 mass parts of butyllithium (15 mass % hexane solution), 1.1 mass parts of diisopropylamine, and 1.0 mass parts of methyl isobutyrate were injected using a syringe. A monomer having a PEG chain, which induces a structural unit represented by the general formula (III") of the monomer for the B block (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R ⁴ in the general formula (III") is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is CH ₃ , m"=22) 23.0 mass parts, MMA 30.0 mass parts, and BMA 22.0 mass parts were dripped over 60 minutes using the funnel for addition. 30 minutes Then, 25.0 parts by mass of DMMA, which is a monomer for block A, was added dropwise over 20 minutes.After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction.The resulting block copolymer THF solution was reprecipitated in hexane, filtered and vacuum Purified by drying, diluted with PGMEA to obtain a solution of 35 mass% solid content to obtain a block copolymer II-R solution.The block copolymer II-R thus obtained was confirmed by GPC, and the weight average molecular weight (Mw) was 15800. In addition, the amine titer was 89 mgKOH/g.

Table 7 shows the monomer composition, weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of block copolymer II-R. Table 8 shows the amine values of block copolymers II-R.

(Comparative Preparation Example II-5: Preparation of salt-type block copolymer II-S)

250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round bottom four-necked separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 degreeC, 4.9 mass parts of butyllithium (15 mass % hexane solution), 1.1 mass parts of diisopropylamine, and 1.0 mass parts of methyl isobutyrate were injected using a syringe. A monomer having a PEG chain (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: triethylene glycol monoethyl ether methacrylate, in the general formula (III"), R ⁴ is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ Silver CH ₃ , m"=3) 8.3 mass parts, MMA 18.8 mass parts, BMA 20.1 mass parts, 2-EHMA 14.1 mass parts, and BzMA 11.8 mass parts were dripped over 60 minutes using the funnel for addition. After 30 minutes, 26.9 mass parts of DMMA which is a monomer for A blocks were dripped over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane and purified by filtration and vacuum drying. Thus, when the obtained block copolymer was confirmed by GPC, the weight average molecular weight (Mw) was 4900. In addition, the amine titer was 81 mgKOH/g. Then, 8.0 parts by mass of the obtained block copolymer is diluted with 10.0 parts by mass of PGMEA, 1.2 parts by mass of benzyl chloride (0.83 equivalents with respect to the DMMA unit of the block copolymer) is added, and stirred at 80° C. for 4 hours, salt type block copolymer II-S A solution was prepared. The obtained salt type block copolymer II-S solution was adjusted so that it might become 35% of solid content by PGMEA.

Table 7 shows the composition, weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the monomers of the block copolymer II-S. Table 8 shows the amine number of the block copolymer II-S before salt formation and the amine number of the salt block copolymer II-S after salt formation.

(Preparation Example II-1: Preparation of alkali-soluble resin II-A)

Put 300 parts by mass of PGMEA in a polymerization tank, and after raising the temperature to 100° C. under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA) and 6 parts by mass of perbutyl O (manufactured by Nichi Oil Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dripped over 1.5 hours. Thereafter, the reaction was continued while maintaining 100°C, and after 2 hours from the end of the dropwise addition of the mixture for forming the main chain, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor was added to stop polymerization.

Then, 20 parts by mass of glycidyl methacrylate (GMA) is added as an epoxy group-containing compound while blowing air, and the temperature is raised to 110 ° C., 0.8 parts by mass of triethylamine is added and reaction is carried out at 110 ° C. for 15 hours, Alkali-soluble resin II-A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40 mass %) was obtained.

In addition, as for the measuring method of the said weight average molecular weight, the weight average molecular weight was measured by the Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. In addition, the measuring method of an acid value was measured based on JISK0070.

(Example II-1)

(1) Preparation of colorant dispersion II-G1

9.29 parts by mass of the graft copolymer II-A of Preparation Example II-1 as a dispersant, and C.I. Pigment Green 58 (PG58) in 9.10 parts by mass, C.I. 3.90 parts by mass of Pigment Yellow 138 (PY138), 14.63 parts by mass of the alkali-soluble resin II-A solution obtained in Preparation Example II-1, 63.09 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0 mm in a mayonnaise bottle, Shake for 1 hour with a paint shaker (manufactured by Asada Tech Co., Ltd.) as preliminary disintegration, then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly disperse for 4 hours with a paint shaker as full-scale disintegration It carried out and obtained the color material dispersion liquid II-G1.

(2) Preparation of photosensitive colored resin composition II-G1

9.77 parts by mass of the color material dispersion G-1 obtained in (1) above, 0.28 parts by mass of the alkali-soluble resin II-A solution obtained in Preparation Example II-1, and 0.28 parts by mass of a polyfunctional monomer (trade name: Aronix M-403, Toagosei Co., Ltd.) ) of 0.99 parts by mass (manufactured by ), 0.12 parts by mass of an oxime ester compound represented by the formula (A-1) (oxime ester photoinitiator having a diphenyl sulfide skeleton: Compound E described in WO2018/062105), a fluorine-based surfactant 0.07 mass parts and 8.73 mass parts of PGMEA were added to (brand name Megapark R-08MH, DIC Corporation make), and photosensitive colored resin composition II-G1 was obtained.

(Examples II-2 to II-8)

(1) Preparation of colorant dispersions II-G2 to II-G8

In (1) of Example II-1, instead of the graft copolymer II-A, as shown in Table 9, (salt type) graft copolymers II-B, II-C, II-D, II- Colorant dispersions II-G2 to II-G8 were prepared in the same manner as in Example II-1 except that E, II-F, II-G and II-H were used, respectively.

(2) Preparation of photosensitive colored resin compositions II-G2 to II-G8

In Example II-1 (2), in the same manner as in Example II-1 (2), except that the color material dispersions II-G2 to II-G8 were respectively used instead of the color material dispersion II-G1. Photosensitive colored resin compositions II-G2 to II-G8 were obtained.

(Examples II-9 to II-10)

(1) Preparation of colorant dispersions II-G9 to II-G10

Colorant dispersions II-G9 to II-G10 were prepared in the same manner as in Example II-8.

(2) Preparation of photosensitive colored resin compositions II-G9 to II-G10

In (2) of Example II-1, instead of the color material dispersion II-G1, the color material dispersions II-G9 to II-G10 were used, respectively, and as the photoinitiator, the oxime ester compound represented by the formula (A-1) Instead, the photosensitive colored resin compositions II-G9 to II-G10 were obtained in the same manner as in (2) of Example II-1 except that the initiators shown in Table 9 were used in the same amount respectively.

(Comparative Examples II-1 to II-8)

(1) Preparation of comparative colorant dispersions II-G1 to II-G8

Comparative color material dispersions II-G1 to II-G8 were obtained in the same manner as in Example II-1.

(2) Preparation of comparative photosensitive colored resin compositions II-G1 to II-G8

In Example II-1 (2), instead of the color material dispersion II-G1, the comparative color material dispersions II-G1 to II-G8 were respectively used, and as the photoinitiator, the oxime ester represented by the formula (A-1) Comparative photosensitive colored resin compositions II-G1 to II-G8 were obtained in the same manner as in (2) of Example II-1 except that the initiator shown in Table 9 was used instead of the compound in the same amount.

(Examples II-11 to II-20)

(1) Preparation of colorant dispersions II-G11 to II-G20

Colorant dispersions II-G11 to II-G20 were prepared in the same manner as in Example II-8.

(2) Preparation of photosensitive colored resin compositions II-G11 to II-G20

In (2) of Example II-1, instead of the color material dispersion II-G1, the color material dispersions II-G11 to II-G20 were respectively used, and as the photoinitiator, the oxime ester compound represented by the formula (A-1) Photosensitive colored resin compositions II-G11 to II-G20 were obtained in the same manner as in Example II-1 (2) except that the initiators shown in Table 10 were used in the amounts shown in Table 10 instead of 0.12 parts by mass. .

(Examples II-21 to II-26)

(1) Preparation of colorant dispersions II-G21 to II-G26

In (1) of Example II-1, instead of the graft copolymer II-A, as shown in Table 10, (salt type) graft copolymers II-I, II-J, II-K, II- Colorant dispersions II-G21 to II-G26 were prepared in the same manner as in Example II-1 except that L, II-M and II-N were used respectively.

(2) Preparation of photosensitive colored resin compositions II-G21 to II-G26

In Example II-1 (2), in the same manner as in Example II-1 (2), except that the color material dispersions II-G21 to II-G26 were respectively used instead of the color material dispersion II-G1. Photosensitive colored resin compositions II-G21 to II-G26 were obtained.

(Comparative Examples II-9 to II-13)

(1) Preparation of comparative colorant dispersions II-G9 to II-G13

In (1) of Example II-1, instead of graft copolymer II-A, as shown in Table 10, (salt type) graft copolymers II-O, II-P and II-Q, and block Comparative color material dispersions II-G9 to II-G13 were obtained in the same manner as in Example II-1 except that copolymers II-R and II-S were used, respectively.

(2) Preparation of comparative photosensitive colored resin compositions II-G9 to II-G13

In Example II-1 (2), in the same manner as in Example II-1 (2), except that the comparative color material dispersions II-G9 to II-G13 were used instead of the color material dispersion II-G1, respectively. Thus, comparative photosensitive colored resin compositions II-G9 to II-G13 were obtained.

(Example II-27)

(1) Preparation of color material dispersion II-G27

In (1) of Example II-1, as the color material, C.I. Pigment Green 58 (PG58) in 9.10 parts by mass, C.I. Instead of using 3.90 parts by mass of Pigment Yellow 138 (PY138), C.I. Pigment Green 59 (PG59) in 9.10 parts by mass, C.I. Except having used 3.90 mass parts of Pigment Yellow 150 (PY150), it carried out similarly to Example II-1, and manufactured the color material dispersion liquid II-G27.

(2) Preparation of photosensitive colored resin composition II-G27

In Example II-1 (2), in the same manner as in Example II-1 (2), except that the color material dispersion II-G27 was used instead of the color material dispersion II-G1, and the photosensitive colored resin composition II -G27 was obtained.

(Examples II-28 to II-34)

(1) Preparation of colorant dispersions II-G28 to II-G34

In Example II-27 (1), instead of the graft copolymer II-A, as shown in Table 11, (salt type) graft copolymers II-B, II-C, II-D, II- Colorant dispersions II-G28 to II-G34 were prepared in the same manner as in Example II-27 except that E, II-F, II-G and II-H were used, respectively.

(2) Preparation of photosensitive colored resin compositions II-G28 to II-G34

In Example II-27 (2), in the same manner as in Example II-1 (2), except that the color material dispersions II-G28 to II-G34 were respectively used instead of the color material dispersion II-G27. Photosensitive colored resin compositions II-G28 to II-G34 were obtained.

(Examples II-35 to II-36)

(1) Preparation of colorant dispersions II-G35 to II-G36

Colorant dispersions II-G35 to II-G36 were prepared in the same manner as in Example II-34.

(2) Preparation of photosensitive colored resin compositions II-G35 to II-G36

In Example II-27 (2), instead of the color material dispersion II-G27, the color material dispersions II-G35 to II-G36 were used, respectively, and as the photoinitiator, the oxime ester compound represented by the formula (A-1) Instead, photosensitive colored resin compositions II-G35 to II-G36 were obtained in the same manner as in (2) of Example II-27 except that the initiators shown in Table 11 were used in the same amount respectively.

(Comparative Examples II-14 to II-21)

(1) Preparation of comparative colorant dispersions II-G14 to II-G21

Comparative color material dispersions II-G14 to II-G21 were obtained in the same manner as in Example II-27.

(2) Preparation of comparative photosensitive colored resin compositions II-G14 to II-G21

In Example II-27 (2), instead of the color material dispersion II-G27, the comparative color material dispersions II-G14 to II-G21 were respectively used, and as the photoinitiator, the oxime ester represented by the formula (A-1) Comparative photosensitive colored resin compositions II-G14 to II-G21 were obtained in the same manner as in Example II-27 (2) except that the initiator shown in Table 11 was used instead of the compound in the same amount.

(Examples II-37 to II-46)

(1) Preparation of colorant dispersions II-G37 to II-G46

Colorant dispersions II-G37 to II-G46 were prepared in the same manner as in Example II-34.

(2) Preparation of photosensitive colored resin compositions II-G37 to II-G46

In Example II-27 (2), instead of the color material dispersion II-G27, the color material dispersions II-G37 to II-G46 were used, respectively, and as the photoinitiator, the oxime ester compound represented by the formula (A-1) In the same manner as in Example II-27 (2), except that the initiators shown in Table 12 were used in the amounts shown in Table 12 instead of 0.12 parts by mass, photosensitive colored resin compositions II-G37 to II-G46 were obtained. .

(Examples II-47 to II-52)

(1) Preparation of colorant dispersions II-G47 to II-G52

In Example II-27 (1), instead of the graft copolymer A, as shown in Table 12, (salt type) graft copolymers II-I, II-J, II-K, II-L, Colorant dispersions II-G47 to II-G52 were prepared in the same manner as in Example II-27 except that II-M and II-N were used, respectively.

(2) Preparation of photosensitive colored resin compositions II-G47 to II-G52

In Example II-27 (2), in the same manner as in Example II-1 (2), except that the color material dispersions II-G47 to II-G52 were respectively used instead of the color material dispersion II-G27. Photosensitive colored resin compositions II-G47 to II-G52 were obtained.

(Comparative Examples II-22 to II-26)

(1) Preparation of comparative colorant dispersions II-G22 to II-G26

In (1) of Example II-27, instead of graft copolymer II-A, as shown in Table 12, (salt type) graft copolymers II-O, II-P and II-Q, and block Comparative colorant dispersions II-G22 to II-G26 were obtained in the same manner as in Example II-27 except that copolymers II-R and II-S were used, respectively.

(2) Preparation of comparative photosensitive colored resin compositions II-G22 to II-G26

In Example II-27 (2), in the same manner as in Example II-27 (2), except that the comparative color material dispersions II-G22 to II-G26 were respectively used instead of the color material dispersion II-G27. Thus, comparative photosensitive colored resin compositions II-G22 to II-G26 were obtained.

(Example II-53)

(1) Preparation of color material dispersion II-R1

In (1) of Example II-1, as the color material, C.I. Pigment Green 58 (PG58) in 9.10 parts by mass, C.I. Instead of using 3.90 parts by mass of Pigment Yellow 138 (PY138), C.I. Pigment Red 177 (PR177) was added to 3.90 parts by mass, C.I. Except having used 9.10 mass parts of Pigment Red 291 (PR291), it carried out similarly to Example II-1, and produced colorant dispersion liquid II-R1.

(2) Preparation of photosensitive colored resin composition II-R1

Photosensitive colored resin composition II in the same manner as in Example II-1 (2) except that the color material dispersion II-R1 was used instead of the color material dispersion liquid II-G1 in (2) of Example II-1. -R1 was obtained.

(Examples II-54 to II-60)

(1) Preparation of colorant dispersions II-R2 to II-R8

In (1) of Example II-53, instead of the graft copolymer II-A, as shown in Table 13, (salt type) graft copolymers II-B, II-C, II-D, II- Colorant dispersions II-R2 to II-R8 were prepared in the same manner as in Example II-53 except that E, II-F, II-G and II-H were used respectively.

(2) Preparation of photosensitive colored resin compositions II-R2 to II-R8

In Example II-53 (2), in the same manner as in Example II-53 (2), except that the color material dispersions II-R2 to II-R8 were respectively used instead of the color material dispersion II-R1. Photosensitive colored resin compositions II-R2 to II-R8 were obtained.

(Examples II-61 to II-62)

(1) Preparation of colorant dispersions II-R9 to II-R10

Colorant dispersions II-R9 to II-R10 were prepared in the same manner as in Example II-60.

(2) Preparation of photosensitive colored resin compositions II-R9 to II-R10

In Example II-53 (2), instead of the color material dispersion II-R1, the color material dispersions II-R9 to II-R10 were respectively used, and as the photoinitiator, the oxime ester compound represented by the formula (A-1) Instead, photosensitive colored resin compositions II-R9 to II-R10 were obtained in the same manner as in Example II-60 (2) except that the initiators shown in Table 13 were used in the same amount respectively.

(Comparative Examples II-27 to II-34)

(1) Preparation of comparative colorant dispersions II-R1 to II-R8

Comparative color material dispersions II-R1 to II-R8 were obtained in the same manner as in Example II-53.

(2) Preparation of comparative photosensitive colored resin compositions II-R1 to II-R8

In Example II-53 (2), instead of the color material dispersion II-R1, the comparative color material dispersions II-R1 to II-R8 were respectively used, and as the photoinitiator, the oxime ester represented by the formula (A-1) Comparative photosensitive colored resin compositions II-R1 to II-R8 were obtained in the same manner as in (2) of Example II-53 except that the initiator shown in Table 13 was used instead of the compound in the same amount.

(Examples II-63 to II-72)

(1) Preparation of colorant dispersions II-R11 to II-R20

Colorant dispersions II-R11 to II-R20 were prepared in the same manner as in Example II-60.

(2) Preparation of photosensitive colored resin compositions II-R11 to II-R20

In Example II-53 (2), instead of the color material dispersion II-R1, the color material dispersions II-R11 to II-R20 were respectively used, and as the photoinitiator, the oxime ester compound represented by the formula (A-1) Instead of 0.12 mass part, except having used the initiator shown in Table 14 in the compounding quantity shown in Table 14, respectively, it carried out similarly to (2) of Example II-53, and obtained photosensitive colored resin composition II-R11-II-R20. .

(Examples II-73 to II-78)

(1) Preparation of colorant dispersions II-R21 to II-R26

In (1) of Example II-53, instead of the graft copolymer II-A, as shown in Table 14, (salt type) graft copolymers II-I, II-J, II-K, II- Colorant dispersions II-R21 to II-R26 were prepared in the same manner as in Example II-53 except that L, II-M and II-N were used respectively.

(2) Preparation of photosensitive colored resin compositions II-R21 to II-R26

In Example II-53 (2), in the same manner as in Example II-53 (2), except that the color material dispersions II-R21 to II-R26 were respectively used instead of the color material dispersion II-R1. Photosensitive colored resin compositions II-R21 to II-R26 were obtained.

(Comparative Examples II-35 to II-39)

(1) Preparation of comparative colorant dispersions II-R9 to II-R13

In (1) of Example II-53, instead of graft copolymer II-A, as shown in Table 14, (salt type) graft copolymers II-O, II-P and II-Q, and block Comparative colorant dispersions II-R9 to II-R13 were obtained in the same manner as in Example II-53 except that copolymers II-R and II-S were used, respectively.

(2) Preparation of comparative photosensitive colored resin compositions II-R9 to II-R13

In Example II-53 (2), in the same manner as in Example II-53 (2), except that the comparative color material dispersions II-R9 to II-R13 were respectively used instead of the color material dispersion II-R1 Thus, comparative photosensitive colored resin compositions II-R9 to II-R13 were obtained.

(Example II-79)

(1) Preparation of color material dispersion II-B1

In (1) of Example II-1, as the color material, C.I. Pigment Green 58 (PG58) in 9.10 parts by mass, C.I. Instead of using 3.90 parts by mass of Pigment Yellow 138 (PY138), C.I. Pigment Blue 15:6 (PB15:6) was added to 11.70 parts by mass, C.I. Except having used 1.30 mass parts of pigment violet 23 (PV23), it carried out similarly to Example II-1, and manufactured the color material dispersion liquid II-B1.

(2) Preparation of photosensitive colored resin composition II-B1

Photosensitive colored resin composition II in the same manner as in Example II-1 (2) except that the color material dispersion II-B1 was used instead of the color material dispersion liquid II-G1 in (2) of Example II-1. -B1 was obtained.

(Examples II-80 to II-86)

(1) Preparation of colorant dispersions II-B2 to II-B8

In (1) of Example II-79, instead of the graft copolymer II-A, as shown in Table 15, (salt type) graft copolymers II-B, II-C, II-D, II- Colorant dispersions II-B2 to II-B8 were prepared in the same manner as in Example II-79 except that E, II-F, II-G and II-H were used respectively.

(2) Preparation of photosensitive colored resin compositions II-B2 to II-B8

In Example II-79 (2), in the same manner as in Example II-79 (2), except that the color material dispersion liquids II-B2 to II-B8 were respectively used instead of the color material dispersion liquid II-B1. Photosensitive colored resin compositions II-B2 to II-B8 were obtained.

(Examples II-87 to II-88)

(1) Preparation of colorant dispersions II-B9 to II-B10

Colorant dispersions II-B9 to II-B10 were prepared in the same manner as in Example II-86.

(2) Preparation of photosensitive colored resin compositions II-B9 to II-B10

In Example II-79 (2), instead of the color material dispersion II-B1, the color material dispersions II-B9 to II-B10 were used, respectively, and as the photoinitiator, the oxime ester compound represented by the formula (A-1) Instead, the photosensitive colored resin compositions II-B9 to II-B10 were obtained in the same manner as in (2) of Example II-79 except that the initiators shown in Table 15 were used in the same amount respectively.

(Comparative Examples II-40 to II-47)

(1) Preparation of comparative colorant dispersions II-B1 to II-B8

Comparative color material dispersions II-B1 to II-B8 were obtained in the same manner as in Example II-79.

(2) Preparation of comparative photosensitive colored resin compositions II-B1 to II-B8

In Example II-79 (2), instead of the color material dispersion II-B1, the comparative color material dispersions II-B1 to II-B8 were respectively used, and as the photoinitiator, the oxime ester represented by the formula (A-1) Comparative photosensitive colored resin compositions II-B1 to II-B8 were obtained in the same manner as in (2) of Example II-79 except that the initiator shown in Table 15 was used instead of the compound in the same amount.

(Examples II-89 to II-98)

(1) Preparation of colorant dispersions II-B11 to II-B20

Colorant dispersions II-B11 to II-B20 were prepared in the same manner as in Example II-86.

(2) Preparation of photosensitive colored resin compositions II-B11 to II-B20

In Example II-79 (2), instead of the color material dispersion II-B1, the color material dispersions II-B11 to II-B20 were respectively used, and as the photoinitiator, the oxime ester compound represented by the formula (A-1) In place of 0.12 mass part, except having used the initiator shown in Table 16 in the compounding quantity shown in Table 16, it carried out similarly to Example II-79 (2), and obtained photosensitive colored resin composition II-B11 - II-B20. .

(Examples II-99 to II-104)

(1) Preparation of colorant dispersions II-B21 to II-B26

In (1) of Example II-79, instead of the graft copolymer II-A, as shown in Table 16, (salt type) graft copolymers II-I, II-J, II-K, II- Colorant dispersions II-B21 to II-B26 were prepared in the same manner as in Example II-79 except that L, II-M and II-N were used respectively.

(2) Preparation of photosensitive colored resin compositions II-B21 to II-B26

In Example II-79 (2), in the same manner as in Example II-79 (2), except that the color material dispersion liquids II-B21 to II-B26 were respectively used instead of the color material dispersion liquid II-B1. Photosensitive colored resin compositions II-B21 to II-B26 were obtained.

(Comparative Examples II-48 to II-52)

(1) Preparation of comparative colorant dispersions II-B9 to II-B13

In (1) of Example II-79, instead of graft copolymer II-A, as shown in Table 16, (salt type) graft copolymers II-O, II-P and II-Q, and block Comparative colorant dispersions II-B9 to II-B13 were obtained in the same manner as in Example II-79 except that copolymers II-R and II-S were used, respectively.

(2) Preparation of comparative photosensitive colored resin compositions II-B9 to II-B13

In Example II-79 (2), in the same manner as in Example II-79 (2), except that the comparative color material dispersions II-B9 to II-B13 were used instead of the color material dispersion II-B1, respectively. Thus, comparative photosensitive colored resin compositions II-B9 to II-B13 were obtained.

[Assessment Methods]

<Evaluation of developing time>

After post-baking the photosensitive colored resin compositions obtained in Examples and Comparative Examples on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater, a colored layer having a thickness of 2.0 μm is formed. After apply|coating to the film thickness to say, the colored layer was formed on the glass substrate by drying at 80 degreeC for 3 minutes using a hotplate. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 through a photomask using an ultra-high pressure mercury lamp. Thereafter, the glass substrate on which the colored layer is formed is shower-developed using 0.05 mass % aqueous potassium hydroxide solution as an alkali developer, and the time until the colored layer is completely dissolved and the glass surface where the colored layer is formed appears was measured as the development time.

<Evaluation of solvent resistance (NMP resistance)>

After post-baking the photosensitive colored resin compositions obtained in Examples and Comparative Examples on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater, a colored layer having a thickness of 2.0 μm is formed. After apply|coating with the film thickness to say, the colored layer was formed on the glass substrate by drying at 80 degreeC for 3 minute(s) using a hotplate. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 using an ultra-high pressure mercury lamp.

Next, the said colored board|substrate was post-baked for 30 minutes in a 230 degreeC clean oven, and the colored board|substrate was created. After measuring the film thickness of the obtained colored substrate, after being immersed in NMP for 30 minutes, it air-dried and the film thickness was measured again. In addition, for the film thickness measurement, the stylus-type step difference film thickness meter "P-15 Tencor" (manufactured by Instruments) was used.

(NMP resistance evaluation criteria)

AA: When it is set as the conditions of NMP immersion time 60 minutes, the rate of change of the film thickness before and behind NMP immersion is less than 2 %

A: The rate of change of the film thickness before and after NMP immersion is less than 2%

B: The rate of change of the film thickness before and after NMP immersion is 2% or more and less than 5%

C: The rate of change of the film thickness before and after NMP immersion is 5% or more and less than 8%

D: The rate of change of the film thickness before and after NMP immersion is 8% or more

If an evaluation result is B, NMP resistance is favorable, and if an evaluation result is A and further AA, it is excellent in NMP resistance.

<Evaluation of dispersibility stability of color material dispersion>

Regarding the color material dispersions obtained in Examples and Comparative Examples, the viscosity was measured immediately after preparation and after storage at 25° C. for 30 days, respectively, the viscosity change rate was calculated from the viscosity before and after storage, and viscosity stability was evaluated. For the viscosity measurement, the viscosity at 25.0±0.5°C was measured using a vibratory viscometer.

(Based on dispersion stability evaluation)

A: The rate of change of viscosity before and after storage is less than 20%

B: The rate of change of viscosity before and after storage is 20% or more and less than 40%

C: The rate of change of viscosity before and after storage is 40% or more and less than 60%

D: The rate of change of viscosity before and after storage is 60% or more

However, it is a value when the color material is 13 mass % with respect to the total mass including the solvent of a color material dispersion liquid.

When the evaluation result is B, the color material dispersion is good, and when the evaluation result is A, the color material dispersion is excellent in dispersion stability.

<Evaluation of optical performance, evaluation of contrast>

The photosensitive colored resin composition obtained in Examples and Comparative Examples was coated on a glass substrate (NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm and 100 mm × 100 mm, respectively, using a spin coater. Then, the colored layer was formed by drying at 80 degreeC for 3 minutes using a hotplate. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 using an ultra-high pressure mercury lamp.

Next, the colored substrate was post-baked in a clean oven at 230°C for 30 minutes, and the contrast, chromaticity (x, y), and luminance (Y) of the obtained colored substrate were measured with a Tsubosaka Denki contrast measuring device CT-1B and Olympus brown rice. It measured using the spectroscopy apparatus OSP-SP200.

(based on contrast evaluation)

A: Green is over 7000, Red is over 5000, Blue is over 6000

B: Green is more than 5600 and less than 7000, Red is more than 4000 and less than 5000, Blue is more than 4800 and less than 6000

C: Green is 4200 or more and 5600 or less, Red is 3000 or more and 4000 or less, Blue is 3600 or more and 4800 or less

D: Green is less than 4200, Red is less than 3000, Blue is less than 3600

However, the greens of Examples II-1 to II-52 and Comparative Examples II-1 to II-26 were y = 0.570, Examples II-53 to II-78 and Comparative Examples II-27 to II- Red in 39 is a value when x = 0.650, and blue in Examples II-79 to II-104 and Comparative Examples II-40 to II-52 is a value when y = 0.107.

<Water stain suppression evaluation>

Post-baking the photosensitive colored resin compositions obtained in Examples and Comparative Examples on a glass substrate (NH Techno Glass Co., Ltd., "NA35", 0.7 mm thick, 100 mm x 100 mm) using a spin coater, respectively. After drying, it was applied to a film thickness to form a colored layer with a thickness of 2.0 μm, dried at 60° C. for 3 minutes using a hot plate, and irradiated with UV light of 30 mJ/cm 2 using an ultra-high pressure mercury lamp without passing through a photomask. By doing so, the colored layer was formed on the glass substrate. Then, using 0.05 wt% potassium (KOH) as a developer, shower development for 60 seconds, and then washing with pure water for development treatment, and rotating the cleaned substrate for 10 seconds to centrifuge the water immediately after removing the water, the contact angle of the pure water is measured as follows to evaluate the water stain.

For measurement of the contact angle of pure water, 1.0 µL of pure water was dropped onto the surface of the colored layer immediately after centrifugation of the water, and the static contact angle after 10 seconds at which the water droplet adhered was measured according to the θ/2 method. The measuring apparatus was measured using the contact angle measuring instrument DM500 by Kyowa Gaimen Chemicals.

(Evaluation standard)

A: Contact angle of 70 degrees or more

B: Contact angle of 50 degrees or more and less than 70 degrees

C: contact angle of 30 degrees or more and less than 50 degrees

D: contact angle less than 30 degrees

If the water stain evaluation criterion is A or B, it can be practically used, but if the evaluation result is A, the effect is more excellent.

<Evaluation of development residue>

After post-baking the photosensitive colored resin compositions obtained in Examples and Comparative Examples on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater, a colored layer having a thickness of 2.0 μm is formed. After apply|coating to the film thickness to say, it dried at 80 degreeC for 3 minutes using a hotplate, and formed the colored layer on the glass substrate. The glass plate on which the colored layer was formed was developed by washing with pure water after shower development for 60 seconds using a 0.05 mass% aqueous potassium hydroxide solution as an alkali developer. The colored layer forming part after development was observed by visually confirming it, and then thoroughly wiped with a lens cleaner containing ethanol (manufactured by Toray Corporation, trade name: Toreshi MK Clean Cloth), and the degree of coloration of the lens cleaner was visually checked and observed. did.

(Based on evaluation of developing residues)

AA: When the drying temperature on a hot plate was 90 degreeC and forced evaluation of the developing residue was performed, the developing residue was not confirmed by visual confirmation, and the lens cleaner was not colored at all.

A: The development residue was not confirmed by visual confirmation, and the lens cleaner was not colored at all.

B: The development residue was not confirmed by visual confirmation, but coloration of the lens cleaner was confirmed slightly.

C: Visually, some development residue was confirmed, and coloration of the lens cleaner was confirmed.

D: The development residue was confirmed by visual confirmation, and coloring of the lens cleaner was confirmed.

If the evaluation result is B, the image development residue suppression effect is favorable, and if the evaluation result is A and further AA, the image development residue suppression effect is excellent.

<Cross-sectional shape of micropores>

The photosensitive colored resin composition obtained in each Example and each comparative example was applied on a glass substrate (NH Techno Glass Co., Ltd., "NA35") using a spin coater so that the cured coating film had a thickness of 3.0 μm. It dried at 80 degreeC for 3 minutes using a hotplate, and formed the coating film on the glass substrate. In this coating film, through a pattern photomask (chrome mask) in which a 20 μm×20 μm chromium mask is disposed in the center of an independent thin wire having an opening size of 90 μm×300 μm, using an ultra-high pressure mercury lamp, ultraviolet light of 40 mJ/cm 2 By exposing, the coating film after exposure was formed on the glass substrate. Then, it spin-developed using 0.05 wt% potassium hydroxide aqueous solution as a developing solution, and after making it wet for 60 seconds in a developing solution, it developed by washing|cleaning with pure water, and obtained the coating film of an independent thin wire|line pattern type with micropores. Thereafter, by post-baking in a clean oven at 230°C for 25 minutes, a colored layer of an independent fine wire pattern having micropores was formed. The following evaluation was performed about the obtained colored layer.

The cross-sectional shape in the thickness direction of the colored layer of the micropores was observed with a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification 10000 times), and according to the following evaluation criteria, It evaluated about the taper angle (theta) (refer FIG. 5) of a cross-sectional shape.

[Cross-sectional shape of micropores]

A: The taper angle (θ) is 15 degrees or more and 60 degrees or less

B: The taper angle (θ) is greater than 60 degrees and less than or equal to 90 degrees

C: The taper angle θ is greater than 90 degrees

In addition, in Tables 9 to 16, initiators 1 to 3 are oxime ester photoinitiators having a diphenyl sulfide skeleton, and other initiators 1 to 8 are initiators different from oxime ester photo initiators having a diphenyl sulfide skeleton. , respectively, as follows.

Initiator 1: Oxime ester compound represented by formula (A-1) (Compound E described in WO2018/062105)

Initiator 2: 3-cyclopentyl-1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime] (trade name TR-PBG-305, manufactured by Changzhou Qiangli Diens New Chailao Co., Ltd.)

Initiator 3: 1,2-octadione, 1- [4- (phenylthio) phenyl] -, 2- (o-benzoyloxime] (trade name Irgacure OXE01, manufactured by BASF)

Other initiator 1: α-aminoketone-based photoinitiator, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF)

Other initiator 2: α-aminoketone-based photoinitiator, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (trade name: Irgacure 369, manufactured by BASF)

Other initiator 3: oxime ester-based photoinitiator having a carbazole skeleton, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyl oxime) (trade name Irgacure OXE02, manufactured by BASF)

Other Initiator 4: Oxime ester photoinitiator having a carbazole skeleton, 1-propanone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]- , 1-(o-acetyloxime) (trade name TR-PBG-304, manufactured by Changzhou Chiang Lidians New Chailao Co., Ltd.)

Other initiator 5: Oxime ester-based photoinitiator having a carbazole skeleton, trade name ADEKA ACLES NCI-831, manufactured by ADEKA

Other Initiator 6: Biimidazole-based photoinitiator, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Kurogane Gassei Co., Ltd.) )

Other initiator 7: thioxanthone-based photoinitiator, 2,4-diethylthioxanthone (trade name: DOUBLECURE DETX, manufactured by Double Bond Chemical)

Other initiator 8: benzophenone-based photoinitiator, 4,4'-bis(diethylamino)benzophenone (trade name: HiCure ABP, manufactured by Kawaguchi Yakuhin Co., Ltd.)

[Summary of results]

By comparison of the Examples and Comparative Examples of the Example II series, Example II using a specific graft copolymer or salt-type graft copolymer and an oxime ester-based photoinitiator having a diphenyl sulfide backbone in the second present invention in combination In -1 to II-104, it became clear that the photosensitive colored resin composition satisfying dispersion stability, high contrast, shortening of development time, and excellent solvent resistance at the same time could be obtained.

In contrast, Comparative Examples II-1 to II-8 using a specific graft copolymer or salt-type graft copolymer in the second invention in combination with an oxime ester-based photoinitiator having a diphenylsulfide backbone and a different photoinitiator , II-14 to II-21, II-27 to II-34, and II-40 to II-47, it became clear that solvent resistance was inferior.

In addition, in the graft chain (polymer chain) of the graft copolymer, Comparative Examples II-9, II- using the graft copolymer II-O containing an excessively long branched chain in which the number of repeating units of the ethylene oxide chain is 90 22, II-35, and the comparative photosensitive colored resin composition of II-48 were a thing from which dispersion stability and contrast worsen.

Comparative Examples II-10, II- using the graft copolymer II-P in which the graft chain (polymer chain) of the graft copolymer is composed of structural units derived from MMA and BMA as disclosed in Patent Document 2, which is a prior art 23, II-36, and the comparative photosensitive colored resin composition of II-49 were inferior in solvent resistance, and image development time also became long.

Comparative Examples II-11, II-24, II-37, using graft copolymer II-Q in which the number of repeating units of ethylene oxide chain is 90 as the graft chain (polymer chain) of the graft copolymer. As for the comparative photosensitive colored resin composition of II-50, dispersion stability and contrast worsened.

Comparative photosensitivity of Comparative Examples II-12, II-25, II-38, II-51 using block copolymer II-R having a polymer chain in which the number of repeating units of ethylene oxide chain is 22 as a structural unit of the block copolymer The colored resin composition was not able to acquire the solvent resistance effect.

As disclosed in Patent Document 1, which is a prior art, block copolymer II-S comprising, as a structural unit of a block copolymer, a structural unit derived from triethylene glycol ethyl ether methacrylate in which the number of repeating units of an ethylene oxide chain is 3 The comparative photosensitive colored resin compositions of Comparative Examples II-13, II-26, II-39, and II-52 using were not able to obtain a solvent-resistance effect, developing time was long, and furthermore, the dispersion stability was inferior.

In the second embodiment of the present invention, in the graft chain (polymer chain) of the graft copolymer, when the number of repeating units of the ethylene oxide chain becomes greater than a certain level, such as m" = 19 or more, the effect of suppressing the occurrence of water stains is improved became

Further, in the second embodiment of the present invention, in the graft chain (polymer chain) of the graft copolymer, the number of repeating units in the ethylene oxide chain is m" = 19 or more, a structural unit larger than a certain amount, and m" When structural units smaller than a certain amount, such as 3 or more and 10 or less, were contained in combination, the solvent resistance was improved and the effect of suppressing the development residue was improved.

Further, among the examples of the second invention, as a photoinitiator, a diphenylsulfide-based oxime ester initiator, an α-aminoketone-based photoinitiator, an oxime ester-based photoinitiator having a carbazole skeleton, a biimidazole-based photoinitiator, and thiok When at least one selected from the group consisting of a santhone-based photoinitiator and a benzophenone-based photoinitiator is further contained in combination, the effect of suppressing development residues is improved and the cross-sectional shape of the micropores is improved.

1: Substrate
2: shading part
3: colored layer
10: color filter
20: counter substrate
30: liquid crystal layer
40: liquid crystal display device
50: organic protective layer
60: inorganic oxide film
71: transparent anode
72: hole injection layer
73: hole transport layer
74: light emitting layer
75: electron injection layer
76: cathode
80: organic light emitting material
100: organic light emitting display device
110: graft copolymer
112: main chain part
121: structural unit represented by general formula (I)
122: structural unit represented by general formula (II)
123: at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons
124: grafted polymer chain
125: structural unit represented by the general formula (III)
126: polyethylene oxide chain or polypropylene oxide chain having a specific repeating number
201: substrate
203: colored layer
205: smile hole

Claims (10)

A colorant dispersion comprising a colorant, a dispersant, and a solvent, the colorant dispersion comprising:
The dispersant is a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the graft copolymer represented by the general formula (I) A colorant dispersion comprising at least one kind of a salt-type graft copolymer in which at least a part of the nitrogen moiety of the structural unit and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon form a salt.

(in general formula (I), R ¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, R ² and R ³ may combine with each other to form a ring structure.
In the general formula (II), R ^1' is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer is a polymer chain, and the structural unit of the polymer chain is a structure represented by the following general formula (III) units are included.)

(in general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m is a number from 19 to 80 indicates.) The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer according to claim 1, wherein the structural unit represented by the general formula (III) and the general formula (III) A structural unit represented by the following general formula (IV) different from the structural unit represented by A color material dispersion liquid having a total ratio of 1% by mass or more and 75% by mass or less.

(In the general formula (IV), R ^4″ is a hydrogen atom or a methyl group, A ⁴ is a divalent linking group, R ¹⁰ is a hydrogen atom, or a hydrocarbon group which may have a substituent or include a hetero atom.) The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer according to claim 1 or 2, further comprising a structural unit represented by the following general formula (IIIa). colorant dispersion.

(in general formula (IIIa), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m' is a number of 10 or less indicate.) A graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and a structural unit represented by the general formula (I) of the graft copolymer A dispersant, which is at least one kind of a salt-type graft copolymer in which at least a part of a nitrogen moiety and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon form a salt.

(in general formula (I), R ¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, R ² and R ³ may combine with each other to form a ring structure.
In the general formula (II), R ^1' is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer is a polymer chain, and the structural unit of the polymer chain is a structure represented by the following general formula (III) units are included.)

(in general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m is a number from 19 to 80 indicates.) The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer according to claim 4, wherein the structural unit represented by the general formula (III) and the general formula (III) A structural unit represented by the following general formula (IV) different from the structural unit represented by The dispersing agent whose total ratio is 1 mass % or more and 75 mass % or less.

(In the general formula (IV), R ^4″ is a hydrogen atom or a methyl group, A ⁴ is a divalent linking group, and R ¹⁰ is a hydrogen atom or a hydrocarbon group which may contain a hetero atom.) The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer according to claim 4 or 5, further comprising a structural unit represented by the following general formula (IIIa) dispersant.

(in the general formula (IIIa), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, and m' is a number of 10 or less indicate.) The photosensitive colored resin composition containing the dispersing agent as described in any one of Claims 4-6, a color material, alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. A cured product of the photosensitive colored resin composition according to claim 7. A color filter comprising at least a substrate and a colored layer formed on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to claim 8 . A display device comprising the color filter according to claim 9 .

Images