JP2018176035A - Polymer dispersant, color material dispersion liquid, colored resin composition, color filter, liquid crystal display device and light-emitting display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer dispersant capable of suppressing changes in chromaticity after high temperature heating, improving luminance and forming a thinned colored layer.SOLUTION: In a polymer dispersant being a copolymer having a constitutional unit expressed as formula (I) (where, R1 is H or methyl group; L1 is a divalent linking group; and Q is a nitrogen site and a primary to tertiary amino group without forming a ring or a nitrogen-containing heterocyclic group),: at least a part of the nitrogen site contained in the constitutional unit expressed as formula (I) may form a salt; and peak intensity derived from at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group is decreased and peak intensity derived from an acid anhydride group is increased in an infrared absorption spectrum before and after heating 5 minutes or more at 230°C.SELECTED DRAWING: None

Description

  Embodiments of the present disclosure relate to a polymer dispersant, a colorant dispersion, a colored resin composition, a color filter, a liquid crystal display, and a light emitting display.

Many thin image display devices represented by displays and the like, so-called flat panel displays, have been launched on the market, characterized by being thinner than a CRT display and taking up less space in the depth direction. The market price has become reasonable year by year with the evolution of production technology, the demand is further expanded, and the production volume is also increasing year by year. In particular, color LCD TVs almost reached the TV mainstream. Further, recently, a light emitting display device such as an organic light emitting display device such as an organic EL display having high visibility due to self light emission is attracting attention as a next generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used for these liquid crystal display devices and light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, and the amount of light is controlled by electrically driving the liquid crystal, and color representation is performed by passing the light through a color filter. Therefore, the color expression of the liquid crystal television must be a color filter, and plays a large role in determining the performance of the display. In addition, in the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.

As a trend in recent years, power saving of the image display apparatus is required, and in order to improve the utilization efficiency of the backlight, the luminance enhancement of the color filter is particularly required. This is particularly a big issue for mobile displays (mobile phones, smart phones, tablet PCs).
Although battery capacity has increased due to technological advances, mobile storage capacity remains the same, while power consumption tends to increase as screen size increases. An image display apparatus including a color filter influences the design and performance of the mobile terminal in order to directly connect to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and made of colored patterns of three primary colors of red, green and blue, and a transparent substrate so as to separate each colored pattern. And a light shielding portion formed.
In the formation method of such a colored layer, the pigment dispersion method using the pigment excellent in heat resistance or light resistance as a coloring material has been widely used. However, with color filters using pigments, it has become difficult to achieve the current demand for higher brightness.

  As one means for achieving high brightness, a colored resin composition using a dye has been studied. Dyes can generally produce color filters with high transmittance and high brightness compared to pigments, but their heat resistance and light resistance are poor, and the chromaticity is likely to change during high temperature heating in the color filter manufacturing process, etc. There was a problem. In addition, the colored resin composition using the dye has a problem that the solvent resistance of the cured coating film is poor, and the dye transfers color to the cured film containing no coloring agent such as adjacent adjacent color pixels or protective film. . Furthermore, the colored resin composition used by dissolving the dye is used as a color filter application, such as the problem that foreign matter is easily deposited on the surface of the cured coating film in the drying step, and the contrast is significantly reduced due to the fluorescence of the dye. Had many problems.

As a method of improving various resistance of a dye, a method of forming a salt of a dye is known. However, even if a dye is formed, in the conventional colored resin composition, the salt forming colorant of the dye is discolored by the high temperature heating performed in forming the colored layer, and the luminance of the colored layer actually decreases. Therefore, it has still been difficult to achieve high luminance. The applicant of the present invention is, in Patent Document 1, a color filter or the like using a salt-forming coloring material of a specific dye containing a divalent or higher cation and a divalent or higher anion in which a plurality of dye skeletons are crosslinked by a crosslinking group. Is disclosed. According to the salt-forming coloring material of the above-mentioned dye, it is disclosed that a molecular association is formed by containing a cation having a valence of 2 or more and an anion having a valence of 2 to improve heat resistance and solvent resistance.
However, for the colored resin composition containing a salt-forming coloring material for dyes, the heat resistance for achieving high brightness by suppressing the discoloration due to high-temperature heating performed in forming the colored layer is required to be further improved. It is done.

On the other hand, in colored resin compositions for color filters, improvement in developability and formation of high definition patterns have been attempted by using a resin that expresses a polar group in the side chain by the action of an acid (patent document 2 to 5).
Further, Patent Document 6 is a coloring composition containing a pigment, and a resin obtained by copolymerizing a specific polymerizable monomer such as butyl (meth) acrylate and another polymerizable monomer, and the specific composition Disclosed is a colored composition characterized in that the amount of components derived from the polymerizable monomer is 56% by weight or more in the total solid content of the resin, and the amount of components derived from the specific polymerizable monomer is the total solid of the resin It is described that the effect of light resistance improvement is acquired by sufficient interaction with a pigment by being 56 weight% or more in minutes.
In addition, Patent Document 7 discloses a pigment dispersion using a diketopyrrolopyrrole pigment, which has a structural unit having an amide group in its main chain for the purpose of forming a cured film having excellent heat resistance and excellent contrast. A pigment dispersant comprising a graft polymer containing a constituent unit derived from t-butyl methacrylate in a side chain, wherein the weight ratio of the main chain to the side chain in the graft polymer is a specific value, and a specific organic A pigment dispersion comprising a solvent is disclosed.
Further, Patent Documents 8 and 9 are directed by the present applicant to improve pigment dispersibility and alkali developability, and in a pigment dispersant containing a structural unit having an amino group, the amino group and a specific acidic phosphoric acid. There are disclosed a block copolymer in which a salt is formed with an ester, and a graft copolymer in which the amino group and a specific organic phosphoric acid compound form a salt.

International Publication No. 2012/144521 JP 10-160924 A Unexamined-Japanese-Patent No. 10-260532 Unexamined-Japanese-Patent No. 2000-221682 JP, 2014-170189, A JP, 2013-160817, A JP, 2013-125087, A JP 2008-242414 A JP, 2009-265649, A

  In the conventional colored resin composition, the chromaticity change due to high temperature heating performed at the time of formation of the colored layer may occur, and the brightness of the colored layer may be reduced. In addition, in color filters, it is required to produce a colored layer with a thinner film thickness.

  An embodiment of the present disclosure has been made in view of the above-mentioned problems, and a polymer dispersant capable of forming a colored layer which is reduced in chromaticity change after heating at high temperature, is improved in luminance, and is thinned. A coloring material dispersion containing the polymer dispersant, capable of suppressing a change in chromaticity after high temperature heating, improving luminance, and capable of forming a thinner colored layer, and containing the coloring material dispersion; A colored resin composition capable of suppressing a change in chromaticity after high temperature heating, improving luminance and forming a thinner colored layer, a color filter formed using the colored resin composition, and the color filter It is an object of the present invention to provide a liquid crystal display device and a light emitting display device.

  One embodiment of the present disclosure is a copolymer having a constitutional unit represented by the following general formula (I), and at least a part of the nitrogen moiety contained in the constitutional unit represented by the general formula (I) is The salt may be formed, and before and after heating at 230 ° C. for 5 minutes or more, in the infrared absorption spectrum, the peak intensity derived from at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group decreases, Polymeric dispersants are provided wherein the peak intensity from the anhydride group is increased.

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a divalent linking group, Q represents a nitrogen site, and the nitrogen site Q is represented by the following general formula (I-a) Or a nitrogen-containing heterocyclic group which may have a substituent.

(In the general formula (I-a), R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom.)

  In one embodiment of the present disclosure, it has a constitutional unit represented by the general formula (I) and a constitutional unit represented by the following general formula (II), and is represented by the general formula (I) It is a block copolymer in which at least a part of the nitrogen moiety contained in the constituent unit may form a salt, or a constituent unit represented by the above general formula (I) and a table represented by the following general formula (III) Polymer dispersant, which is a graft copolymer having a constituent unit and at least a part of the nitrogen moiety contained in the constituent unit represented by the general formula (I) may form a salt I will provide a.

(In General Formula (II), R ⁴ represents a hydrogen atom or a methyl group, and R ^P represents a monovalent protecting group represented by the following General Formula (A).
In formula (III), R ⁵ represents a hydrogen atom or a methyl group, L ² represents a direct bond or a divalent linking group, and Polymer has a polymer chain having a constitutional unit represented by the following formula (IV) Represent. )

(In general formula (A), R ^P1 represents a carbon atom or a silicon atom, R ^P2 , R ^P3 and R ^P4 each independently represent a hydrogen atom or a hydrocarbon group, R ^P5 represents a hydrocarbon group or a hydrocarbon group or It represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)

(In general formula (IV), R ⁶ represents a hydrogen atom or a methyl group, and R ^{P ′} represents a monovalent protecting group represented by the following general formula (A ′). N is an integer of 5 or more and 200 or less Represents

(In the general formula (A '), ^{R P'1} represents a carbon atom or a silicon atom, ^{R P'2, R P'3} and ^{R P'4} each independently represent a hydrogen atom or a hydrocarbon group , ^{R P'5} represents a hydrocarbon group or -OR ^{P'6, R P'6} is .R ^P'4 and ^{R P'5} represents a hydrocarbon group bonded to form a ring system with one another Also good.)

  In one embodiment of the present disclosure, the copolymer further comprises an -O- bond derived from a monomer whose glass transition temperature value (Tgi) for homopolymer is less than 50 ° C. A polymeric dispersant is provided, which has a structural unit containing a good hydrocarbon group in its side chain.

  In one embodiment of the present disclosure, the copolymer further contains a hydrocarbon group in a side chain derived from a monomer having a glass transition temperature value (Tgi) of 50 ° C. or higher for a homopolymer. A polymeric dispersant having a constitutional unit is provided.

  One embodiment of the present disclosure contains a colorant (A), a colorant (B), a dispersant (C), and a solvent (C), wherein the colorant (B) is the above-mentioned polymer dispersant. Provide a dispersion.

  In one embodiment of the present disclosure, provided is a colorant dispersion, wherein the (A) colorant is a metal lake color material of a dye.

  One embodiment of the present disclosure provides a colored resin composition containing the above-described colorant dispersion, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. .

  In one embodiment of the present disclosure, provided is a colored resin composition in which the (E) polyfunctional monomer contains a phosphorus atom-containing polyfunctional monomer.

  One embodiment of the present disclosure is a color filter comprising at least a transparent substrate and a colored layer on the transparent substrate, wherein at least one of the colored layers is a cured product of the colored resin composition described above. Provide a filter.

  One embodiment of the present disclosure provides a liquid crystal display device including the color filter described above, an opposing substrate, and a liquid crystal layer positioned between the color filter and the opposing substrate.

  One embodiment of the present disclosure provides a light emitting display including the color filter described above and a light emitter.

  The embodiment of the present disclosure contains a polymer dispersant capable of forming a colored layer which is reduced in chromaticity change after heating at high temperature, has improved luminance, and is capable of forming a thinner colored layer, and is heated at high temperature Color change after the color change is suppressed, brightness is improved, color material dispersion liquid capable of forming a thinner colored layer, and the color material dispersion liquid, color change after high temperature heating is suppressed, Provided are a colored resin composition capable of forming a thinner colored layer with improved luminance, a color filter formed using the colored resin composition, and a liquid crystal display and a light emitting display having the color filter. can do.

It is a schematic sectional drawing which shows an example of the color filter of this indication. It is a schematic sectional drawing which shows an example of the liquid crystal display device of this indication. It is a schematic sectional drawing which shows an example of the light emission display apparatus of this indication. 7 is an infrared absorption spectrum of the graft copolymer B obtained in Example 2 before and after post-baking. 7 is an infrared absorption spectrum of the graft copolymer C obtained in Example 3 before and after post-baking. FIG. 7 is an infrared absorption spectrum of the graft copolymer D obtained in Comparative Example 1 before and after post-baking. FIG. FIG. 18 is an infrared absorption spectrum of the block copolymer B obtained in Example 5 before and after post-baking. It is an infrared absorption spectrum before and behind the post-baking of block copolymer C obtained by the comparative example 2. FIG.

Hereinafter, the polymer dispersant, the colorant dispersion liquid, the colored resin composition, the color filter, the liquid crystal display device, and the light emitting display device according to the present disclosure will be described in order.
In the present specification, (meth) acrylic represents each of acrylic and methacrylic, (meth) acrylate represents each of acrylate and methacrylate, and (meth) acryloyl represents each of acryloyl and methacryloyl. .
In the present specification, light includes electromagnetic waves of wavelengths in the visible and non-visible regions, and also radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

1. Polymeric Dispersant The polymer dispersant of the present disclosure is a copolymer having a constitutional unit represented by the following general formula (I), and a nitrogen moiety contained in the constitutional unit represented by the general formula (I) The salt may be at least partially formed, and before or after heating at 230 ° C. for 5 minutes or more, a peak intensity derived from at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group in an infrared absorption spectrum Is a polymeric dispersant in which the peak intensity derived from the acid anhydride group is decreased.

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a divalent linking group, Q represents a nitrogen site, and the nitrogen site Q is represented by the following general formula (I-a) Or a nitrogen-containing heterocyclic group which may have a substituent.

(In the general formula (I-a), R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom.)

The infrared absorption spectrum of the polymer dispersant according to the present disclosure is a coating film formed by applying and drying a dispersant solution prepared by dissolving the polymer dispersant according to the present disclosure in a solvent, It is obtained by measuring an infrared absorption spectrum.
The solvent used for the dispersant solution can be appropriately selected from those that can dissolve the polymer dispersant according to the present disclosure and can be dried and removed by heating at less than 150 ° C. There is no particular limitation. Ether acetate, propylene glycol monomethyl ether etc. are mentioned.
The solid content concentration of the dispersant solution, that is, the concentration of the polymer dispersant according to the present disclosure is not particularly limited, but is usually about 10% by mass to about 30% by mass. The thickness of the coating after heating at 230 ° C. is not particularly limited, but is about 2.0 μm ± 0.5 μm.
The heating time at 230 ° C. is not particularly limited as long as it is 5 minutes or more, but it is usually about 10 minutes to 120 minutes.

In the infrared absorption spectrum of the polymer dispersant according to the present disclosure, a peak derived from a methylene group in the main chain is used as a reference peak, and the peak intensity of the reference peak is 1. In addition, the reference | standard peak derived from the methylene group of a principal chain is a peak which has a maximum value in 1455 +/- 10 cm < ^-1 >.
In the infrared absorption spectrum of the polymer dispersant according to the present disclosure, as a peak derived from an acid anhydride group, for example, a peak having a maximum at 1760 ± 5 cm ⁻¹ and a maximum at 1800 ± 5 cm ⁻¹ There is a peak having
In the polymer dispersant according to the present disclosure, the peak intensity of the peak having a maximum value at 1760 ± 5 cm ⁻¹ in the infrared absorption spectrum after the heating is preferably 1.1 or more, and 1.3 or more. It is more preferable that
Moreover, it is preferable that the peak intensity of the peak which has a maximum value in 1800 +/- 5 cm < ^-1 > in the infrared absorption spectrum after the said polymer dispersing agent which concerns on this indication is 0.50 or more.

  The polymer dispersant according to the present disclosure has the effect of improving the heat resistance of the colored layer using the colorant dispersion even when the colorant having a low heat resistance such as a lake color material is dispersed, and the post Even under high temperature heating such as baking, it is possible to suppress the color fading of the color material, so it is possible to form a colored layer with high brightness. In addition, the colored layer can be made thinner by using the polymer dispersant according to the present disclosure.

It is estimated as follows as an effect | action in which the polymer dispersing agent which concerns on this indication exhibits the above effects.
The polymer dispersant according to the present disclosure can be made excellent in dispersibility and dispersion stability of the coloring material because the constituent unit represented by the general formula (I) is easily adsorbed to the coloring material. . In addition, the polymer dispersant according to the present disclosure reduces peak intensity derived from at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group in an infrared absorption spectrum before and after heating at 230 ° C. for 5 minutes or more. Since the peak intensity derived from the acid anhydride group is increased, the protecting group containing at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group is released by the heating, whereby the carboxy group appears. Furthermore, the acid anhydride group has appeared by dehydration condensation. When dispersed, the polymer dispersant of the present disclosure has at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group, and has high solvent solubility and good dispersibility, while forming a colored layer. After post-baking, the protective group containing at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group is eliminated to appear a carboxy group and an acid anhydride group, whereby the glass transition temperature (Tg) is high. It can have a skeleton and is considered to improve heat resistance. Further, in the polymer dispersant of the present disclosure, the constituent unit represented by the general formula (I) is easily adsorbed to the coloring material, and thus easily exists in the vicinity of the coloring material in the coloring layer. It is presumed that the above-mentioned heat-resistant skeleton is easily expressed. As a result, since the molecular motion of the coloring material due to heating is suppressed and the fading of the coloring material is suppressed, it is considered that the reduction in the luminance of the colored layer is suppressed and a colored layer with high luminance can be formed.
Furthermore, the colored layer formed using the polymer dispersant according to the present disclosure has a protective group containing at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group, which is eliminated after post-baking, from within the colored layer. By removing and condensation between adjacent carboxy groups, it is possible to make the color layer thinner while increasing the color material concentration of the color layer.

<Constituent Unit Represented by General Formula (I)>
In the general formula (I), L ¹ is a divalent linking group. Examples of the divalent linking group for L ¹ include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (-R '-OR'-: R' and R '' each independently represent an alkylene group), a combination thereof and the like.
Among them, from the viewpoint of dispersibility, L ¹ in the general formula (I) is preferably a divalent linking group containing a -COO- group.

In the general formula (I), Q represents a nitrogen site, and the nitrogen site Q is a group represented by the above general formula (I-a) or a nitrogen-containing heterocyclic group which may have a substituent. is there.
The hydrocarbon group in the hydrocarbon group which may contain a hetero atom of R ² and R ^{3 in} the general formula (I-a) is, for example, an alkyl group, an aralkyl group, an aryl group and the like.
As an alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group The carbon number of the alkyl group is preferably 1 or more and 18 or less, and more preferably a methyl group or an ethyl group.
As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, biphenyl methyl group etc. are mentioned, for example. The carbon number of the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
Also, examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group and the like. The carbon number of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. In addition, carbon number of a substituent is not contained in the said preferable carbon number.
The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the above-mentioned hydrocarbon group is replaced by 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.
The hydrogen atom in the hydrocarbon group may be substituted by a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom or a bromine atom.

The nitrogen-containing heterocyclic ring of the nitrogen-containing heterocyclic group which may have a substituent includes a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring thereof, and another hetero atom The nitrogen-containing heterocycle may have aromaticity.
Specific examples of the nitrogen-containing heterocyclic compound forming the nitrogen-containing heterocyclic ring include pyridine, piperidine, piperazine, morpholine, pyrrolidine, pyrrole, pyrroline, indole, carbazole, imidazole, pyrazole, triazole, tetrazole and benzimidazole. Etc. Among them, a nitrogen-containing heterocyclic ring containing only a nitrogen atom as a hetero atom such as pyridine, piperidine, piperazine and imidazole is preferable, and among these, a nitrogen-containing heterocyclic ring having aromaticity such as pyridine and imidazole is preferable .
Examples of the substituent which may be possessed in the nitrogen-containing heterocycle include, for example, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aralkyl group, an aryl group, F, Cl, Br and the like. And the like, and the like, and these can be used in combination. Moreover, the substitution position of these substituents and the number of substituents are not particularly limited.

As the structural unit represented by the above general formula (I), dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethyl piperidyl (meth) The structural units derived from nitrogen-containing (meth) acrylates such as acrylates; acrylamide monomers such as dimethylaminopropyl acrylamide etc. may be mentioned, but it is not limited thereto.
The structural unit represented by general formula (I) may consist of one type, and may contain two or more structural units.

  In the polymer dispersant of the present disclosure, at least a part of the nitrogen site Q contained in the constituent unit represented by the general formula (I) may form a salt. As a salt forming agent which forms a salt with the nitrogen site Q, for example, at least one salt forming agent selected from the group consisting of a halogenated hydrocarbon, an acidic phosphorus compound, and a sulfonic acid compound is dispersed in a coloring material It is preferably used from the point of having excellent properties and dispersion stability.

Examples of the halogenated hydrocarbon include those in which a halogen atom of any of a chlorine atom, a bromine atom and an iodine atom is substituted with a hydrogen atom of a saturated or unsaturated linear, branched or cyclic hydrocarbon. .
The carbon number of the halogenated hydrocarbon is preferably 1 or more and 30 or less, more preferably 1 or more and 25 or less, and still more preferably 1 or more and 18 or less.

  Among the above-mentioned halogenated hydrocarbons, examples of the halogenated alkyl include one having 1 to 18 carbon atoms, but are not particularly limited. Specifically, for example, methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride and the like It can be mentioned. Moreover, as the allyl halide, for example, allyl chloride, allyl bromide, allyl iodide and the like can be mentioned. Moreover, as an aralkyl group of the said halogenated aralkyl, although a C7-C18 thing is mentioned, it does not specifically limit. Specifically, for example, benzyl chloride, benzyl bromide, benzyl iodide, naphthylmethyl chloride, pyridylmethyl chloride, naphthylmethyl bromide, pyridylmethyl bromide and the like can be mentioned. Moreover, as a halogenated aryl, although a C6-C18 thing is mentioned, it does not specifically limit. Specifically, chlorobenzene etc. are mentioned, for example.

Among them, at least one of allyl halide and aralkyl halide is preferable, and allyl halide is more preferable, from the viewpoint of enhancing the dispersibility of the coloring material.
Specifically, at least one selected from the group consisting of allyl chloride, allyl bromide, allyl iodide, benzyl chloride, benzyl bromide, and benzyl iodide; It is preferable from the point which the produced | generated salt formation site | part is excellent in the adsorptivity to a coloring material.

  Examples of the acidic phosphorus compound include compounds represented by the following general formula (V), and examples of the sulfonic acid compound include compounds represented by the following general formula (VI).

(In the general formula (V) and the general formula (VI), R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, a hydrocarbon group,-[CH (R ^c ) -CH (R ^d ) -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e or ^a monovalent group represented by -O-R ^{a ′ ′} R ^{a ′ ′} is a hydrocarbon group, _{^{CH (R c) -CH (R}} d) -O] s -R e, - [(CH 2) t -O] u -R e, -C (R f) (R g) -C (R h) (R ⁱ ) —OH or a monovalent group represented by —CH ₂ —C (R ^j ) (R ^k ) —CH ₂ —OH.
R ^b is a hydrocarbon group,-[CH (R ^c ) -CH (R ^d ) -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e , or -O-R ^b It is a monovalent group represented by ^' . R ^{b ′} is a hydrocarbon group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — (CH ₂ ) _t —O] _u —R ^e is a monovalent group Of the
R ^c and R ^d each independently represent a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or a monovalent group represented by -CH ₂ COOR ^l R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^f , R ^g , R ^h , R ⁱ , R ^j and R ^k each independently represent a hydrogen atom, a hydrocarbon group, or a group formed by combining a hydrocarbon group with at least one of an ether bond and an ester bond R ^f and R ^h may be combined with each other to form a ring structure. When the above cyclic structure is formed, it may have a substituent R ⁿ , and R ⁿ is a hydrogen atom, a hydrocarbon group, or a group in which a hydrocarbon group is bound by at least one of ether bond and ester bond It is. In R ^a , R ^{a ′} and R ^b , each of the hydrocarbon groups may have a substituent.
s is an integer of 1 or more and 18 or less, t is an integer of 1 or more and 5 or less, and u is an integer of 1 or more and 18 or less. )

The hydrocarbon group in R ^a , R ^{a ′} , R ^{a ′ ′} , R ^b , R ^{b ′} and R ^e in the general formula (V) and the general formula (VI) has 1 to 18 carbon atoms It is preferable that it is the alkyl group of these, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group may be linear, branched or cyclic and, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, 2-ethoxy Ethyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group substituted adamantyl group and the like can be mentioned.
The alkenyl group may be linear, branched or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group etc. can be mentioned, for example. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the resulting polymer, it is preferable that a double bond be present at the end of the alkenyl group.
Examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl group and biphenylmethyl group. The carbon number of the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
Examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group and xylyl group. The carbon number of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less.
The hydrocarbon group in R ^f , R ^g , R ^h , R ⁱ , R ^j , R ^k , R ^l , and R ⁿ in the general formula (V) and the general formula (VI) has 1 or more carbon atoms It is preferable that it is an alkyl group of 18 or less, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group, and the alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group. The group and the aryl group may be the same as described above.
Among them, an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferably used in terms of the dispersibility of the color material. .
In R ^a , R ^{a ′} , R ^{a ′ ′} , R ^b and R ^{b ′} , s is an integer of 1 to 18; t is an integer of 1 to 5; u is an integer of 1 to 18; s is preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less, and t is preferably an integer of 1 or more and 4 or less, more preferably 2 or 3. u is preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less.

R ^f , R ^g , R ^h , R ⁱ , R ^j and R ^k , and a group in R ⁿ in which a hydrocarbon group is bound by at least one of an ether bond and an ester bond are —R′—O— R ", -R '-(C = O) -O-R", or -R'-O- (C = O) -R "(R' and R" each represent a hydrocarbon group or a hydrocarbon group Is a group bonded by at least one of an ether bond and an ester bond. One group may have two or more ether bonds and ester bonds. When the above hydrocarbon group is bonded by at least one of an ether bond and an ester bond, at least one is a divalent hydrocarbon group, in which case an alkyl group having 1 to 18 carbon atoms, an aralkyl group, and The aryl groups each become a divalent group of an alkylene group, an arylene group, and a combination thereof.

Moreover, specifically, the organic acid compounds described in, for example, WO2011 / 108495 and WO2013 / 179841 can also be preferably used as the salt forming agent.
The salt forming agents may be used alone or in combination of two or more.

  The content of the salt-forming agent is not particularly limited as long as good dispersion stability is exhibited, but from the viewpoint of improving the dispersion stability of the coloring material, it is represented by the general formula (I) The amount is preferably 0.05 molar equivalent or more, more preferably 0.1 molar equivalent or more, still more preferably 0.2 molar equivalent or more with respect to the nitrogen moiety contained in the constituent unit On the other hand, it is preferably 2.0 molar equivalents or less, more preferably 1.0 molar equivalents or less, and still more preferably 0.8 molar equivalents or less.

Further, in the polymer dispersant of the present disclosure, the content ratio of the constituent unit represented by the general formula (I) is 100% by mass of all constituent units from the viewpoint of dispersibility and dispersion stability. The content is preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.
In the present disclosure, the content ratio (% by mass) of the structural unit is calculated from the preparation amount at the time of synthesizing the copolymer.

<Thermal latent building block>
The polymer dispersant according to the present disclosure further decreases peak intensity derived from at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group in an infrared absorption spectrum before and after heating at 230 ° C. for 5 minutes or more Have a structure such that the peak intensity derived from the acid anhydride group is increased. As such a structure, a structure in which two or more heat latent structural units containing a carboxy group protected by a hydrocarbon group or a hydrocarbon group-substituted silyl group in a side chain are adjacent to each other is preferable.
When two or more of the heat latent structural units are positioned adjacent to each other, the heating causes the protective group containing at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group to be eliminated to become a carboxy group, An acid anhydride group is formed by dehydration condensation of the carboxy group possessed by the adjacent heat latent structural unit.
The heat latent structural unit is preferably a structural unit represented by the following general formula (II).

(In general formula (II), R ⁴ represents a hydrogen atom or a methyl group, and R ^P represents a monovalent protecting group represented by the following general formula (A).)

General formula (A)
(In general formula (A), R ^P1 represents a carbon atom or a silicon atom, R ^P2 , R ^P3 and R ^P4 each independently represent a hydrogen atom or a hydrocarbon group, R ^P5 represents a hydrocarbon group or a hydrocarbon group or It represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)

Among others, R ^{P1 in the} general formula (A) is preferably a carbon atom from the viewpoint of high versatility and the stability of the protective group itself.
The hydrocarbon group in R ^P2 , R ^P3 , R ^P4 , R ^P5 and R ^P6 in the general formula (A) may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is particularly limited Although not preferred, aliphatic hydrocarbon groups are preferred, and among them, linear, branched, cyclic and alkyl groups of these combinations are preferred. Examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, n-hexyl group, isopropyl group, t-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and the like. A cyclohexylmethyl group etc. are mentioned.
Among them, R ^P2 and R ^P3 in the general formula (A) are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. In R ^P2 and R ^P3, the alkyl group of 1 to 3 carbon atoms, among them, more preferably a methyl group and an ethyl group, a methyl group is particularly preferred.
R ^{P4 in the} general formula (A) is preferably an alkyl group having 1 to 3 carbon atoms, or forms a ring structure by bonding to R ^P5, and is an alkyl group having 1 to 3 carbon atoms Is more preferred. Among the alkyl groups having 1 or more and 3 or less carbon atoms in R ^P4 , a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
R ^{P5 in the} general formula (A) is an alkyl group having 1 or more and 3 or less carbon atoms, -OR ^P6 and the R ^P6 is bonded to an alkyl group having 1 or more and 18 or less carbon atoms or R ^P4 to form a ring structure The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Among the alkyl groups having 1 or more and 3 or less carbon atoms in R ^P5 , among these, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable. As for R ^P6 , an alkyl group having 3 to 10 carbon atoms is more preferable.
The fact that R ^P4 and R ^P5 are linked to each other to form a ring structure means that R ^P4 and R ^P5 form a ring structure via R ^P1 . When R ^P1 is a carbon atom, examples of the ring structure formed by bonding R ^P4 and R ^P5 to each other include a cycloalkane having 3 to 6 carbon atoms and adamantane. When R ^P1 is a silicon atom, for example, a heterocyclic ring in which a carbon atom located in R ^P1 of the above-mentioned ring structure is replaced by a silicon atom can be mentioned.

  Specific examples of the monovalent protecting group represented by the general formula (A) include t-butyl group, sec-butyl group, trimethylsilyl group, 2-methyl-2-adamantyl group, and the following general formula ( The structure derived from the vinyl ether compound represented by A-1), etc. are mentioned.

General formula (A-1)
(In General Formula (A-1), R ^P6 represents a hydrocarbon group.)

Examples of the hydrocarbon group for R ^P6 in the general formula (A-1), the general formula (A) the same as the hydrocarbon group in R ^P6 in. Among them, an alkyl having 1 to 18 carbon atoms A group is preferable, and an alkyl group having 3 to 10 carbon atoms is more preferable. Specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, cyclohexylmethyl group and the like are mentioned. Among them, from the viewpoint of solvent solubility, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, n-hexyl group and cyclohexyl group are preferable, methyl group, ethyl group, propyl group and isopropyl group, An n-butyl group is more preferred.

In the constitutional unit represented by the general formula (II), by heating at 230 ° C. for 5 minutes or more, R ^P is eliminated to be a carboxy group, and two constitutional units represented by the general formula (II) are obtained. By positioning adjacent to each other as described above, the carboxy groups possessed by the constituent units located adjacent to each other are dehydrated and condensed to form an acid anhydride group, and a structure represented by the following general formula (II-a) Become.

(In General Formula (II-a), R ⁴ is the same as General Formula (II). A plurality of R ⁴ may be the same or different.)

  In the polymer dispersant of the present disclosure, the content ratio of the heat latent structural unit is 10, based on 100% by mass of all structural units, from the viewpoints of heat resistance and luminance and thinning of the colored layer. It is preferable that it is mass% or more and 80 mass% or less, It is more preferable that it is 15 mass% or more and 75 mass% or less, It is still more preferable that it is 20 mass% or more and 70 mass% or less.

<Low Tg Building Unit>
The polymer dispersant according to the present disclosure may further contain a -O- bond derived from a monomer whose glass transition temperature value (Tgi) of the homopolymer is less than 50 ° C. It is preferable to have a structural unit containing a group in a side chain (herein referred to as "low Tg structural unit" in the present specification) from the viewpoint of achieving both the solvent solubility of the colored resin composition and the substrate adhesion of the colored layer. In the low Tg structural unit, the value (Tgi) of the glass transition temperature is not particularly limited, but is preferably −100 ° C. or higher from the viewpoint of securing the durability of the dispersant itself. It is preferable that it is -50 degreeC or more.
In addition, as the value (Tgi) of the glass transition temperature of a homopolymer of a monomer, the value of Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
Examples of the low Tg structural unit include structural units represented by the following general formula (VII).

(In the general formula (VII), R ⁷ represents a hydrogen atom or a methyl group, L ³ represents a direct bond or a divalent linking group, and R ⁸ represents a hydrocarbon group which may contain an —O— bond.)

In the general formula (VII), the divalent linking group in L ³ is the same as L ^{1 in the} general formula (I). The direct bond of L ³ means that R ⁸ is directly bonded to a carbon atom without a linking group. Among them, in view of dispersibility, L ³ in the general formula (VII) is preferably a divalent linking group containing a —COO— group.
Among them, the hydrocarbon group which may contain an —O— bond in R ⁸ of the general formula (VII) is a linear or branched C 4 or more and 10 or less carbon group which may contain an —O— bond, among others Alkyl group,-(CH ₂ -CH ₂ -O) _n -R ⁹ (R ⁹ represents a linear or branched alkyl group having 1 to 10 carbon atoms, and n is an integer of 2 to 10) The group represented by is preferable, and a linear or branched alkyl group having 4 to 10 carbon atoms is more preferable.

  Specific examples of the monomer for deriving the constituent unit represented by the general formula (VII) include n-butyl methacrylate (Tgi: 20 ° C.), isobutyl methacrylate (Tgi: 48 ° C.), and 2-ethylhexyl. Methacrylate (Tgi: -10 ° C), 2-ethoxyethyl methacrylate (Tgi: -16 ° C), isodecyl methacrylate (Tgi: -41 ° C), methoxy polyethylene glycol # 400 methacrylate (Tgi: -69 ° C), etc. may be mentioned. Among these, n-butyl methacrylate, 2-ethylhexyl methacrylate, and 2-ethoxyethyl methacrylate are preferable from the viewpoint of the durability of the dispersant.

  In the polymer dispersant of the present disclosure, the content ratio of the low Tg structural unit is 10% by mass or more when the total structural unit is 100% by mass from the viewpoint of solvent solubility and substrate adhesion of the colored layer. It is preferable that it is mass% or less, and it is more preferable that it is 20 mass% or more and 50 mass% or less.

<High Tg Building Unit>
The polymer dispersant according to the present disclosure, when having the low Tg structural unit, is further a hydrocarbon derived from a monomer having a glass transition temperature value (Tgi) of 50 ° C. or higher in a homopolymer. It is preferable from the viewpoint of the strength and solvent resistance of the colored film to have a structural unit containing a group in the side chain (referred to as “high Tg structural unit” in the present specification) in combination. Moreover, in the said high Tg structural unit, although the value (Tgi) of the said glass transition temperature is not specifically limited, It is preferable that it is 200 degrees C or less.
Examples of the high Tg structural unit include structural units represented by the following general formula (VIII).

(In general formula (VIII), R ¹⁰ represents a hydrogen atom or a methyl group, L ⁴ represents a direct bond or a divalent linking group, and R ¹¹ represents a hydrocarbon group.)

In the general formula (VIII), the divalent linking group in L ⁴ is the same as L ^{1 in the} general formula (I). The direct bond of L ⁴ means that R ¹¹ is directly bonded to a carbon atom without a linking group. Among them, in terms of dispersibility, L ⁴ in the general formula (VIII) is preferably a divalent linking group containing a -COO- group.
The hydrocarbon group for R ¹¹ in the general formula (VIII) is, among others, a linear or branched alkyl group having 1 to 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 4 to 10 carbon atoms, or a cyclic group A combination of an aliphatic hydrocarbon group and an alkyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 14 carbon atoms are preferable.
Examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group and an i-propyl group.
As a combination of a cyclic aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group having 4 to 10 carbon atoms or a cyclic aliphatic hydrocarbon group and an alkyl group, for example, an alkyl such as a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or 1-methylcyclohexyl group A substituted cycloalkyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group etc. are mentioned.
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
As a C7-C14 aralkyl group, a benzyl group, (alpha)-methyl benzyl group, (alpha), (alpha)-dimethyl benzyl group etc. are mentioned, for example.

  Specific examples of the monomer from which the structural unit represented by the general formula (VIII) is derived include methyl methacrylate (Tgi: 105 ° C.), cyclohexyl methacrylate (Tgi: 66 ° C.), and benzyl methacrylate (Tgi: 54 ° C.), isobonyl methacrylate (Tgi: 180 ° C.), adamantyl methacrylate (Tgi: 183 ° C.), etc., among which methyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate are preferable in terms of heat resistance and solvent solubility. .

  In the polymer dispersant of the present disclosure, the content ratio of the high Tg structural unit is 10% by mass or more and 60% by mass or less when the total structural unit is 100% by mass from the viewpoint of heat resistance and solvent resistance. Is preferably 20% by mass to 50% by mass.

  Among the polymer dispersants of the present disclosure, low Tg structural units derived from at least one monomer selected from the group consisting of n-butyl methacrylate, 2-ethylhexyl methacrylate and 2-ethoxyethyl methacrylate, among others It is preferable to have in combination with a low Tg structural unit derived from at least one monomer selected from the group consisting of methyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate.

  The polymer dispersant of the present disclosure has a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), among others, and is represented by the general formula (I). Or a block copolymer in which at least a part of the nitrogen site contained in the constituent unit may form a salt, or a constituent unit represented by the general formula (I) and a general formula (III) described later A graft copolymer in which at least a part of the nitrogen moiety contained in the constituent unit represented by the general formula (I) may form a salt. preferable.

<Block copolymer>
The block copolymer preferable as the polymer dispersant of the present disclosure has a constitutional unit represented by the general formula (I) and a constitutional unit represented by the general formula (II), and It is a block copolymer in which at least a part of the nitrogen site contained in the constituent unit represented by I) may form a salt.
The block copolymer has a block portion having a structural unit represented by the general formula (I) and a block portion having a structural unit represented by the general formula (II), and It is preferable that it is a block copolymer in which at least a part of the nitrogen site contained in the constituent unit represented by I) may form a salt. Further, in the block copolymer, at least a part of the nitrogen site contained in the constituent unit represented by the general formula (I) forms a salt, which means that the dispersibility and the dispersion stability of the color material are improved. It is more preferable from the point of improvement.

(Block part having constituent unit represented by formula (I))
The block copolymer preferably has a block portion having a constituent unit represented by the general formula (I). The structural unit represented by the general formula (I) is as described above, and thus the description thereof is omitted.
It is preferable that three or more structural units represented by said general formula (I) are contained in the block which has a structural unit represented by said general formula (I). Among them, from the viewpoint of improving the dispersibility and improving the heat resistance, it is preferable to include 3 or more and 200 or less, more preferably 3 or more and 50 or less, and further preferably 3 or more and 30 or less. Is even more preferred.
The structural unit represented by the general formula (I) may function as a colorant affinity site, and may be composed of one kind or may contain two or more kinds of structural units.

  The content ratio of the structural unit represented by the general formula (I) in the block copolymer is 5% by mass or more and 60% by mass or less, when the entire block copolymer is 100% by mass. Is preferable, and 10% by mass or more and 40% by mass or less is more preferable.

(Block part having structural unit represented by general formula (II))
The block copolymer has the structural unit represented by the general formula (II) in the block portion, thereby suppressing the color fading of the colored layer to improve the luminance, and further thinning the colored layer. In addition, the solvent affinity is improved, and the dispersibility and the dispersion stability of the coloring material are improved. The structural unit represented by the general formula (II) is as described above, and thus the description thereof is omitted.

In addition, the block part having the structural unit represented by the general formula (II) may further have both the solvent solubility of the colored resin composition and the close contact of the colored layer with the substrate having the low Tg structural unit. It is preferable from the viewpoint that the low Tg structural unit and the high Tg structural unit are present from the viewpoint of the solvent solubility of the colored resin composition and the substrate adhesion of the colored layer, and the solvent resistance.
The low Tg structural unit and the high Tg structural unit are as described above, and thus the description thereof is omitted.

  The block part which has a structural unit represented by said general formula (II) may further contain the other structural unit different from the structural unit mentioned above. As the other structural unit, for example, a structural unit containing, in the side chain, a hydrocarbon group substituted by a substituent such as an alkoxy group, a hydroxyl group, a carboxy group, an amino group, an epoxy group, an isocyanate group or a hydrogen bond forming group After synthesizing a block copolymer having such a substituent, a compound having a functional group capable of reacting with the substituent and a polymerizable group is reacted to form a structural unit to which a polymerizable group is added.

In the block part having the structural unit represented by the general formula (II), the content ratio of the structural unit represented by the general formula (II) is 10 mass% when the whole block part is 100% by mass % Or more and 80% by mass or less is preferable, 20% by mass or more and 70% by mass or less is more preferable, and 30% by mass or more and 50% by mass or less is still more preferable.
Moreover, in the block part which has a structural unit represented by the said general formula (II), the content rate of the said low Tg structural unit sets 10 mass% or more and 70 mass%, when the said block part makes the whole 100 mass%. It is preferable that it is the following and it is more preferable that it is 15 to 50 mass%.
Moreover, in the block part which has a structural unit represented by the said general formula (II), the content rate of the said high Tg structural unit is 10 mass% or more and 60 mass%, when the said block part makes the whole 100 mass%. It is preferable that it is the following and it is more preferable that it is 15 to 50 mass%.

  The number of structural units constituting the block having the structural unit represented by the general formula (II) is not particularly limited, but the solvent affinity site and the colorant affinity site are effectively improved while improving the heat resistance. It is preferable that it is 10 or more and 200 or less, more preferably 10 or more and 100 or less, and still more preferably 10 or more and 70 or less from the viewpoint of acting and improving the dispersibility of the colorant dispersion.

  The content ratio of the constituent unit represented by the general formula (II) in the block copolymer is 20% by mass or more and 95% by mass or less, when the entire block copolymer is 100% by mass. Preferably, the content is 30% by mass or more and 90% by mass or less.

  The block part having the structural unit represented by the general formula (II) may be selected to function as a solvent affinity site, and two or more kinds of structural units are randomly arranged in the block part. It may also be arranged in blocks.

  In the block copolymer, the number m of structural units of the block unit having the structural unit represented by the general formula (I) and the configuration of the block unit having the structural unit represented by the general formula (II) The ratio m / n of the unit number n is preferably in the range of 0.01 or more and 1 or less, and in the range of 0.05 or more and 0.7 or less, the dispersibility of the colorant and It is more preferable from the point of dispersion stability, as well as the point of heat resistance, and the point of luminance and thinning of the colored layer.

  As the bonding order of the block copolymer, it is possible to have a block portion having the structural unit represented by the general formula (I) and a block portion having the structural unit represented by the general formula (II); It is not particularly limited as long as it can disperse stably, and is not particularly limited, but a block part including the structural unit represented by the general formula (I) is bonded to only one end of the block copolymer. It is preferable from the point which is excellent in the interaction with a color material, and can suppress aggregation of dispersing agents effectively.

The mass average molecular weight of the block copolymer is not particularly limited, but is preferably 2500 or more and 20000 or less, more preferably 3000 or more and 12000 or less from the viewpoint of making the dispersibility good and making the heat resistance excellent. Preferably, it is more preferably 5,000 or more and 10,000 or less.
In the present disclosure, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For measurement, using HLC-8220 GPC manufactured by Tosoh Corporation, the elution solvent is N-methylpyrrolidone (NMP) to which 0.01 mol / liter of lithium bromide is added, and the polystyrene standard for calibration curve is Mw: 8 × 10 ⁵ ( F-80), Mw: 4 × 10 ⁵ (F-40), Mw: 2 × 10 ⁵ (F-20), Mw: 1 × 10 ⁵ (F-10), Mw: 4 × 10 ⁴ (F− 4), Mw: 2 × 10 ⁴ (F-2), Mw: 5 × 10 ³ (A-5000), Mw: 2.5 × 10 ³ (A-2500), Mw: 1 × 10 ³ (A− 1000), Mw: 5 × 10 ² (A-500) (all manufactured by Tosoh Corporation), and two measurement columns were used as TSK-GEL ALPHA-M × 2 (manufactured by Tosoh Corporation).

<Graft copolymer>
The graft copolymer preferable as the polymer dispersant of the present disclosure has a constituent unit represented by the general formula (I) and a constituent unit represented by the following general formula (III), and It is a graft copolymer in which at least a part of the nitrogen site contained in the constituent unit represented by I) may form a salt.

(In the general formula (III), R ⁵ represents a hydrogen atom or a methyl group, L ² represents a direct bond or a divalent linking group, and a polymer has a polymer chain having a structural unit represented by the following general formula (IV) Represents

(In general formula (IV), R ⁶ represents a hydrogen atom or a methyl group, and R ^{P ′} represents a monovalent protecting group represented by the following general formula (A ′). N is an integer of 5 or more and 200 or less Represents

(In the general formula (A '), ^{R P'1} represents a carbon atom or a silicon atom, ^{R P'2, R P'3} and ^{R P'4} each independently represent a hydrogen atom or a hydrocarbon group , ^{R P'5} represents a hydrocarbon group or -OR ^{P'6, R P'6} is .R ^P'4 and ^{R P'5} represents a hydrocarbon group bonded to form a ring system with one another Also good.)

In the graft copolymer, the dispersibility and the dispersion stability of the coloring material are improved because at least a part of the nitrogen site contained in the constituent unit represented by the general formula (I) forms a salt. It is more preferable from the point of view.
The structural unit represented by the general formula (I) is as described above, and thus the description thereof is omitted.

In the general formula (III), the divalent linking group in L ² is the same as L ^{1 in the} general formula (I). A direct bond of L ² means that the Polymer is directly bonded to a carbon atom without a linking group. Among them, from the viewpoint of dispersibility, L ² in the general formula (III) is preferably a divalent linking group containing a -COO- group.
The Polymer in the general formula (III) is a polymer chain having a structural unit represented by the general formula (IV). In the general formula (IV), R ^{P ′} represents a monovalent protecting group represented by the general formula (A ′). ^{R P'1} in the general formula ^{(A '), R P'2,} R P'3, R P'4 and ^{R P'5 is, R} P1, ^R P2 in each of the general formulas ^{(A), R P3} , R ^P4 and R ^P5 .

  The polymer chain may be a homopolymer or a copolymer of the constituent unit represented by the general formula (IV). In the graft copolymer, the polymer chain contained in the constituent unit represented by the general formula (III) may be used alone or in combination of two or more.

In addition to the constituent unit represented by the general formula (IV), the polymer in the general formula (III) is a polymer chain further having the low Tg structural unit, and the solvent solubility of the colored resin composition and It is preferable from the point that the adhesion of the colored layer to the substrate can be compatible, and further, that the polymer chain having the low Tg structural unit and the high Tg structural unit is solvent solubility and the adhesion of the colored layer to the substrate. And from the viewpoint of solvent resistance.
The low Tg structural unit and the high Tg structural unit are as described above, and thus the description thereof is omitted.

  The polymer chain may further include other constituent units different from the constituent units described above. As said other structural unit, the thing similar to the other structural unit which the block part which has a structural unit represented by said general formula (II) of the block copolymer mentioned above may contain is mentioned, for example .

In the polymer chain represented by Polymer in the general formula (III), the content ratio of the constituent unit represented by the general formula (IV) is 100% by mass of the entire polymer chain:
The content is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and still more preferably 30% by mass to 50% by mass.
The content of the low Tg structural unit in the polymer chain is preferably 10% by mass to 60% by mass, and 15% by mass to 50% by mass, based on 100% by mass of the entire polymer chain. It is more preferable that the content is less than%.
The content ratio of the high Tg structural unit in the polymer chain is preferably 10% by mass to 60% by mass, and 15% by mass to 50% by mass, based on 100% by mass of the entire polymer chain. It is more preferable that the content is less than%.

  The polymer chain having the constituent unit represented by the general formula (IV) may be selected to function as a solvent affinity site, and two or more kinds of constituent units are randomly arranged in the polymer chain. It may be arranged in blocks.

In the general formula (III), the mass average molecular weight Mw of the polymer chain in the Polymer is preferably in the range of 500 or more and 15000 or less, and more preferably in the range of 1000 or more and 8000 or less.
Further, as a standard, the polymer chain in Polymer preferably has a solubility at 23 ° C. of 50 (g / 100 g solvent) or more with respect to the organic solvent used in combination.
The solubility of the said polymer chain can make it a standard that the raw material which introduce | transduces the polymer chain at the time of preparing a graft copolymer has the said solubility. For example, when a polymerizable oligomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its end is used to introduce a polymer chain into a graft copolymer, the polymerizable oligomer has the above solubility. Just do it. In addition, after a copolymer is formed by a monomer containing a group having an ethylenically unsaturated double bond, a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer is used. When a polymer chain is introduced, the polymer chain containing the reactive group only needs to have the solubility.

In the graft copolymer, the total content of the constituent units represented by the general formula (I) is preferably 10% by mass to 45% by mass, and more preferably 15% by mass to 40% by mass. 20 mass% or more and 35 mass% or less are more preferable. If the total content of the constituent units represented by the general formula (I) in the graft copolymer falls within the above range, the ratio of the affinity site to the coloring material in the graft copolymer becomes appropriate, and the organic Since the decrease in the solubility in the solvent can be suppressed, the adsorptivity to the coloring material becomes good, and excellent dispersibility and dispersion stability can be obtained.
On the other hand, in the graft copolymer, the constituent unit represented by the general formula (III) is preferably contained in a proportion of 55% by mass to 90% by mass, and is 60% by mass to 85% by mass Is more preferable, and 65% by mass to 80% by mass is more preferable.

  Although the mass average molecular weight Mw of the graft copolymer is not particularly limited, it is preferably in the range of 1000 or more and 100000 or less, and 3000 or more and 30000 or less from the viewpoint of achieving good dispersibility and excellent heat resistance. Is more preferably in the range of 5,000 or more and 20,000 or less.

  The graft copolymer used in the present disclosure has other structural units in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (III) Also good. An ethylenically unsaturated double bond-containing monomer copolymerizable with an ethylenically unsaturated double bond-containing monomer or the like that derives the constitutional unit represented by the general formula (I) is appropriately selected and copolymerized, Can be introduced.

<Manufacture of polymeric dispersant>
The method for producing the polymer dispersant according to the present disclosure is not particularly limited. For example, a block copolymer preferable as the polymer dispersant according to the present disclosure derives a constituent unit represented by the general formula (I) And the monomer for deriving the constitutional unit represented by the general formula (II) are polymerized using a known polymerization means, and then dissolved or dispersed in a solvent described later, and the above-mentioned general formula (I) When salt formation of the nitrogen site contained in the structural unit to be formed, it can then be produced by adding the above-mentioned salt forming agent to the solvent and stirring. The polymerization method is not particularly limited as long as it can polymerize a desired constituent unit at a desired unit ratio to obtain a desired molecular weight, and is not particularly limited, and is generally used for polymerization of a compound having a vinyl group Methods such as anionic polymerization and living radical polymerization can be used. In the present disclosure, it is possible to use a method in which living polymerization proceeds as group transfer polymerization (GTP) disclosed in “J. Am. Chem. Soc.” 105, 5706 (1983), among others. preferable. According to this method, the molecular weight, the molecular weight distribution, and the like can be easily adjusted to the desired range, so that the characteristics of the polymer dispersant of the present disclosure can be made uniform. In the above polymerization, additives generally used for polymerization, such as a polymerization initiator, a dispersion stabilizer, a chain transfer agent and the like may be used.

  The graft copolymer preferable as the polymer dispersant according to the present disclosure has, for example, a monomer that derives a constituent unit represented by the general formula (I) and a constituent unit represented by the general formula (III) The polymer moiety and the polymerizable oligomer having an ethylenically unsaturated double bond-containing group at its terminal are graft polymerized using a known polymerization means, and the nitrogen moiety contained in the constituent unit represented by the above general formula (I) When forming a salt, it can then be prepared by adding the salt former into the solvent and stirring.

2. Colorant Dispersion The colorant dispersion according to the present disclosure contains (A) a colorant, (B) a dispersant, and (C) a solvent, and the (B) dispersant according to the present disclosure. It is a polymeric dispersant.

In the colorant dispersion according to the present disclosure, when the (B) dispersant is the polymer dispersant according to the present disclosure, the change in chromaticity after high-temperature heating is suppressed, the luminance is improved, and the thin film is further thin. It is possible to form a hardened coating film or colored layer.
The (B) dispersant contained in the colorant dispersion according to the present disclosure is the same as the polymer dispersant according to the present disclosure described above, and thus the description thereof is omitted here. Hereinafter, the (A) coloring material, the (C) solvent, and the other components which may be contained as necessary, which the coloring material dispersion liquid according to the present disclosure contains, will be described.

[(A) Color material]
The colorant (A) used in the colorant dispersion according to the present disclosure can be appropriately selected from those capable of obtaining a desired color tone, and examples thereof include known organic pigments, inorganic pigments, lake color materials and the like Be

As the organic pigment, for example, insoluble azo pigment, soluble azo pigment, phthalocyanine organic pigment, quinacridone organic pigment, perylene organic pigment, dioxazine organic pigment, nickel azo pigment, isoindolinone organic pigment, pyranthrone organic pigment As organic solid solution pigments such as thioindigo organic pigment, condensed azo organic pigment, benzimidazolone organic pigment, quinophthalone organic pigment, isoindoline organic pigment, quinacridone solid solution pigment, perylene solid solution pigment, and other pigments Carbon black etc. are mentioned.
When organic pigments are exemplified by color index (C.I.) numbers, C.I. I. Pigment yellow 1, 2, 3, 12, 13, 14, 15, 16, 17, 20, 24, 49, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 120, 123, 124, 125, 126, 127, 127, 127, 127, 128, 129, 130, 133, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 166, 167, 168, 169, 170, 172, 173, 175, 176, 179, 180, 181, 182, 183, 185, 191, 193, 194, 199, 213, 214, 215, 219; I. Pigment red 5, 7, 9, 12, 48, 49, 52, 53, 57, 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 83, 88, 89, 97, 112, 122, 123, 144, 146, 147, 149, 166, 169, 170, 171, 172, 175, 176, 177, 178, 179, 180, 181, 184, 185, 187, 190, 192, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 215, 216, 217, 220, 221, 223, 224, 227, 228, 238, 240, 242, 245, 247, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 268, 2 9,270,272,279; C. I. Pigment orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 24, 31, 34, 36, 38, 43, 46, 48, 51, 55, 59, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81; I. Pigment violet 1, 2, 3, 3: 1, 3: 3, 5, 13, 19, 23, 25, 27, 29, 30, 31, 32, 36, 37, 38, 40, 42, 50; I. Pigment blue 1, 15, 15: 1, 15: 3, 15: 4, 15: 6, 16, 17: 1, 22, 24, 24: 1, 25, 26, 56, 60, 61, 62, 63, C.I. 64, 75, 79, 80; I. Pigment green 1, 4, 7, 8, 10, 36, 58, 59; C.I. I. Pigment brown 5, 23, 25, 26, 41 and the like.

  Specific examples of the above-mentioned inorganic pigments are barium sulfate, iron oxide, zinc oxide, barium carbonate, barium sulfate, silica, clay, talc, titanium oxide, calcium carbonate, synthetic mica, alumina, zinc flower, lead sulfate, yellow lead, Zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, inorganic solid solution pigments and the like can be mentioned.

The coloring material dispersion liquid of the present disclosure can suitably use a lake color material having relatively poor heat resistance as the coloring material (A) from the viewpoint of being able to improve the heat resistance of the coloring layer. In terms of point, it is preferable to use a lake color material, and it is more preferable to use a metal lake color material of a dye.
In the present disclosure, a lake color material refers to a color material in which a solvent-soluble dye is insolubilized by forming a salt with a counter ion. The lake color material can be generally obtained by mixing a dye described later and a lake agent described later in a solvent. The metal lake color material of the dye refers to a lake color material obtained using a metal-containing lake agent.
The dye may be appropriately selected according to the desired color tone, and any basic skeleton (coloring site (coloring site, etc.) may be an azo dye, anthraquinone dye, triarylmethane dye, xanthene dye, cyanine dye, indigo dye, etc. And the like. Further, the dye may be a dye classified into any group such as an acid dye having an anionic substituent or a basic dye having a cationic substituent.
In the present disclosure, the (A) colorant is at least one colorant selected from the group consisting of triarylmethane colorants and xanthene colorants from the viewpoint of color developability, light transmittance, heat resistance, etc. It is preferable to use

  Specific examples of acid dyes include C.I. I. Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 25, 49, 72, C.I. I. Acid Blue 13, 5, 7, 9, 22, 22, 83, 90, 93, 100, 103, 104, 109, C.I. I. Triarylmethane-based acid dyes such as Acid Green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 18, 22, 50, 50: 1, etc .; I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, Sulforhodamine 101, C.I. I. Examples thereof include xanthene acid dyes such as Acid Blue 19 and the like. Among xanthene acid dyes, C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30, C.I. I. Rhodamine acid dyes such as Acid Blue 19 are preferred.

  The basic dye is an ionic dye in which the cation part is a chromophore, and, for example, azine dyes, oxazine dyes, thiazine dyes, azo dyes, anthraquinone dyes, xanthene dyes, triarylmethane dyes Dyes, phthalocyanine dyes, auramine dyes, acridine dyes, methine dyes and the like can be mentioned. Specifically, those having the following color index (CI) names can be mentioned.

C. I. Basic red 2, 5, 6, 10, C.I. I. Basic Violet 5, 6
8, 12, C.I. I. Azine dyes such as Basic Yellow 14;
C. I. Oxazine dyes such as Basic Blue 3, 6, 10, 12, 74, 122;
C. I. Basic Blue 9, 17, 24, C.I. I. Thiazine dyes such as Basic Green 5;
C. I. Basic reds 18, 22, 23, 24, 29, 30, 31, 32, 34, 38, 39, 46, 51, 54, 55, 62, 64, 76, 94, 111, 118, C.I. I. Basic Blue 41, 53, 54, 55, 64, 65, 66, 67, 162, C.I. I. Basic violet 15, 16, 18, 21, 22, 36, C.I. I. Basic yellow 15, 19, 24, 25, 28, 29, 38, 39, 49, 51, 52, 53, 57, 62, 73, C.I. I. Azo dyes such as Basic Orange 1, 2, 24, 25, 29, 30, 30, 33, 54, 69;
C. I. Anthraquinone dyes such as Basic Blue 22, 44, 47, 72;
C. I. Basic red 1, 1: 1, 3, 4, 8, 11, C.I. I. Xanthene dyes such as Basic Violet 10, 11, 11: 1, etc .;
C. I. Basic Red 9, C.I. I. Basic Blue 1, 2, 5, 7, 8, 11, 15, 18, 20, 23, 26, 35, 81, C.I. I. Basic violet 1, 2, 3, 4, 14, 23, C.I. I. Basic green 1, 4 etc. triarylmethane dyes;
C. I. Phthalocyanine dyes such as Basic Blue 140;
C. I. Basic yellow 2, 3, 37 auramine dyes such as;
C. I. Basic Yellow 5, 6, 7, 9, C.I. I. Acridine dyes such as Basic Orange 4, 5, 14, 15, 16, 17, 18, 19;
C. I. Basic red 12, 13, 14, 15, 27, 28, 37, 52, 90, C.I. I. Basic Blue 62, 63, C.I. I. Basic yellow 11, 13, 21, 22, 28, 29, 49, 51, 52, 53, C.I. I. Methine dyes such as Basic Violet 7, 15, 16, 20, 21, 22 and the like.
In addition, as the triarylmethane-based basic dye and the xanthene-based basic dye in the present disclosure, a cationic dye that constitutes a coloring material represented by General Formula (IX) described later can also be mentioned as a preferable example.
These dyes can be used singly or in combination of two or more.

  In the lake color material, the counter ion differs depending on the type of the dye, the counter ion of the acid dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the counter ion is appropriately selected and used according to the dye. That is, when the acid dye is to be insolubilized, a compound that generates a counter cation of the dye is used as a lake agent, and when the base dye is to be insolubilized, a counter anion of the dye is generated as a lake agent. Compounds are used.

As the counter cation of the acid dye, other than ammonium cation, calcium ion, barium ion, strontium ion, manganese ion, aluminum ion, cesium ion, lanthanum ion, neodymium ion, metal ion such as cerium ion, polyaluminum chloride and oxychloride Inorganic polymers such as zirconium can be mentioned.
As a compound which generate | occur | produces an ammonium ion, a primary amine compound, a secondary amine compound, a tertiary amine compound etc. are mentioned as a suitable thing, for example, Among them, the point which is excellent in heat resistance and light resistance, a secondary amine compound Alternatively, it is preferable to use a tertiary amine compound.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent. The Examples of the anionic group, for ^{_{example, -SO 2 N - SO 2 CH}} 3, -SO 2 N - COCH 3, -SO 2 N - SO 2 CF 3, -SO 2 N - COCF 3, -CF 2 SO 2 ^{_{N - SO 2 CH 3, -CF}} 2 SO 2 N - COCH 3, -CF 2 SO 2 N - SO 2 CF 3, -CF 2 SO 2 N - COCF 3 or imidate group such as, -SO ₃ ^{-, _{-CF 2 SO 3 -, -PO 3}} 2-, -COO -, -CF 2 PO 3 2-, -CF 2 COO - , and the like. Among these, from the viewpoint of heat resistance and light resistance, and imidate ^{_{groups, -SO 3 -, -CF 2 SO}} 3 - , more preferably a, -SO ₃ ^- (sulfonato group) is more preferable.
On the other hand, as the inorganic anion, for example, anion of oxo acid (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc., plural Examples thereof include inorganic anions such as polyacid anions in which oxo acids are condensed, and mixtures thereof.
The polyacid may be an isopolyacid anion (M _m O _n ) ^c- or a heteropolyacid anion (X _l M _m O _n ) ^c- . In the above ion formula, M represents a poly atom, X represents a hetero atom, 1 represents a composition ratio of hetero atoms, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. As poly atom M, Mo, W, V, Ti, Nb etc. are mentioned, for example. Moreover, as hetero atom X, Si, P, As, S, Fe, Co etc. are mentioned, for example.
Among them, from the viewpoint of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.

As polyacid anions containing at least one of molybdenum and tungsten, for example, tungstate ions [W ₁₀ O ₃₂ ] ⁴⁻ , molybdate ions [Mo ₆ O ₁₉ ] ²⁻ , which are isopoly acids, and heteropoly acids there, ion phosphotungstic acid _{[PW 12 O} ^{40] 3-,} silicotungstic acid ion _{[SiW 12 O} ^{40] 4-,} phosphomolybdic acid ion _{[PMo 12 O} ^{40] 3-,} phosphorus tongue strike molybdate _{[PW 12- x} Mo _x O _40] ^3-, Keita ring strike molybdate _{[SiW 12-x Mo x O} 40] 4- , and the like. The polyacid anion containing at least one of molybdenum and tungsten is preferably a heteropolyacid among the above from the viewpoint of heat resistance and easiness of obtaining raw materials, and is further a heteropolyacid containing phosphorus (P) It is more preferable that

Examples of the lake agent that generates an inorganic anion include alkali salts and alkali metal salts of the above-mentioned inorganic anions.
The counter anion of the basic dye in the lake color material can be used singly or in combination of two or more.

  In the present disclosure, the lake color material is preferably a metal lake color material of a basic dye from the viewpoint of heat resistance and light resistance, and at least one metal of a triarylmethane-based basic dye and a xanthene-based basic dye. It is more preferable that it is a lake color material, and further, it is preferable to contain a color material represented by the following general formula (IX) from the viewpoint of achieving high heat resistance and light resistance and achieving high brightness of the color filter.

(In general formula (IX), A is an a-valent organic group in which a carbon atom directly bonded to N does not have a π bond, and the organic group is a saturated aliphatic carbon group at the end directly linked to N It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, N may be contained in the carbon chain B ^c- is a c-valent poly R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure R ^vi and R ^vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen Ar ¹ represents a divalent aromatic group which may have a substituent.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. f and g represent integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less.
Plural R ^{i to} R ^vii , Ar ¹ , e, f and g may be the same or different. )

  Since the coloring material represented by the above general formula (IX) contains a divalent or higher anion and a divalent or higher cation, in the aggregate of the coloring material, only 1 molecule to 1 molecule of anion and cation are present. It is presumed that, rather than being ionically bonded, they form a molecular assembly in which a plurality of molecules associate via ionic bonding. Therefore, the apparent molecular weight of the colorant represented by the general formula (IX) is remarkably increased as compared with the molecular weight of the conventional lake colorant. The formation of such a molecular association further increases the cohesion in the solid state, reduces the thermal movement, can suppress the dissociation of the ion pair and the decomposition of the cation part, and is presumed to improve the heat resistance.

A in the general formula (IX) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is a saturated fat at the end directly linked to N Represents an aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and O (oxygen atom), S (sulfur atom), N (nitrogen atom) is contained in the carbon chain It may be Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic color forming site are not affected by the linking group A and other color forming sites, and the monomer Similar colors can be maintained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N has a linear, branched or cyclic structure if the terminal carbon atom directly bonded to N has no π bond. And any carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and O, S, N are contained in the carbon chain It is also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amido group or the like may be contained, and a hydrogen atom may be further substituted by a halogen atom or the like.
The aromatic group having the above aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N at least And may have a substituent, and may be a heterocyclic ring containing O, S and N.
Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of backbone fastness.
Among them, a bridged alicyclic hydrocarbon group is preferable as the cyclic aliphatic hydrocarbon group from the viewpoint of the fastness of the skeleton. The bridged alicyclic hydrocarbon group is a polycyclic aliphatic hydrocarbon group having a crosslinked structure in an aliphatic ring and having a polycyclic structure, and examples thereof include norbornane and bicyclo [2,2,2]. Examples include octane and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferred. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Especially, the group containing a benzene ring is preferable. For example, when A is a divalent organic group, a straight chain, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group having two alkylene groups of 1 to 20 carbon atoms such as xylylene group substituted Group groups and the like.

  The valence number a in the general formula (IX) is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more. In the color material of the present disclosure, since the valence number a of the cation is 2 or more, the heat resistance is excellent. The upper limit of a is not particularly limited, but in terms of easiness of production, a is preferably 4 or less, more preferably 3 or less.

The alkyl group in R ^{i to} R ^v is not particularly limited. Examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, and the like, among which a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and 1 to 5 carbon atoms. The following linear or branched alkyl groups are more preferable from the viewpoint of brightness and heat resistance. Among them, the alkyl group in R ^{i to} R ^v is particularly preferably an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and a substituted alkyl group includes a benzyl group and the like.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group etc. are mentioned. As a substituent which an aryl group may have, an alkyl group, a halogen atom, etc. are mentioned, for example.

The fact that R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v are combined to form a ring structure means that R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v are forming a ring structure via a nitrogen atom. Say The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring, morpholine ring and the like.

Among them, from the viewpoint of chemical stability, R ^{i to} R ^v each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v It is preferable that they combine to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

R ⁱ to R ^v may take the structure are each independently but, among them, it is preferable that in terms of color purity R ⁱ is a hydrogen atom, further R ⁱⁱ ~ in terms of manufacturing and ease of procurement of raw materials More preferably, all R ^v are identical.

Each of R ^vi and R ^vii independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom. The alkyl group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and is an alkyl having 1 to 4 carbon atoms. More preferred is a group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group, which may be linear or may have a branch. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group.
The alkoxy group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and 1 to 4 carbon atoms. More preferably, it is an alkoxy group of Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, which may be linear or may have a branch. Although it does not specifically limit as a substituent which an alkoxy group may have, For example, an aryl group, a halogen atom, a hydroxyl group etc. are mentioned.
As a halogen atom in R ^vi and R ^vii , a chlorine atom, a bromine atom, etc. are mentioned, for example.
Among them, R ^vi and R ^vii are preferably an electron donating group such as a methyl group or an ethyl group, a methoxy group or an ethoxy group from the viewpoint of heat resistance.
The substitution number of R ^vi and R ^vii , that is, f and g each independently represent an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0 or more and 1 or less.
Further, R ^vi and R ^vii may be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or xanthene skeleton, but among them, —NR ⁱⁱ R ⁱⁱⁱ or —NR ^iv It is preferable that the meta position is substituted based on the substitution position of the amino group represented by R ^v .

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group in Ar ¹ can be the same as those listed for the aromatic group in A.
Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a fused polycyclic carbon ring having 10 to 14 carbon atoms. Among them, a phenylene group or a naphthylene group is more preferable in view of the simple structure and the inexpensive raw materials.

Plural R ^{i to} R ^vii , Ar ¹ , e, f and g in one molecule may be the same or different. When a plurality of R ^{i to} R ^vii , Ar ¹ , e, f and g are identical to each other, the color forming site exhibits the same color development, so that the color similar to that of the single color forming site can be reproduced and the color purity It is preferable from the point of view. On the other hand, when at least one of R ^{i to} R ^vii , Ar ¹ , e, f and g is a different substituent, it is possible to reproduce a mixed color of plural kinds of monomers, and desired It can be adjusted to the color.

In the colorant represented by the general formula (IX), the anion moiety (B ^c− ) is a polyacid anion having a valence of 2 or more. The polyacid anion may be isopolyacid ion (M _m O _n ) ^d- or heteropolyacid ion (X _l M _m O _n ) ^d- . In the above ion formula, M represents a poly atom, X represents a hetero atom, 1 represents a composition ratio of hetero atoms, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. As poly atom M, Mo, W, V, Ti, Nb etc. are mentioned, for example. Moreover, as hetero atom X, Si, P, As, S, Fe, Co etc. are mentioned, for example. In addition, a counter cation such as Na ⁺ or H ⁺ may be partially contained.
Among them, a polyacid anion containing at least one of tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of high brightness and excellent heat resistance and light resistance, and it contains at least tungsten and contains molybdenum. It is more preferable from the point of heat resistance that it is a good polyacid anion.

As a polyacid anion containing at least one of tungsten (W) and molybdenum (Mo), for example, isoporic acid, tungstate ion [W ₁₀ O ₃₂ ] ⁴⁻ , molybdate ion [Mo ₆ O ₁₉ ] ^{2 -} or a heteropoly acid, ion phosphotungstic acid ^{_{[PW 12 O 40] 3-,}} [P 2 W 18 O 62] 6-, silicotungstic acid ion _{[SiW 12 O} ^{40] 4-,} phosphomolybdic acid ion [ PMo ₁₂ O ₄₀ ] ³⁻ , silicomolybdate ion [SiMo ₁₂ O ₄₀ ] ⁴⁻ , lintungst molybdate ion [PW _12−x Mo _x O ₄₀ ] ³⁻ (x is an integer of 1 or more and 11 or less), [ P ₂ W _18-y Mo _y O ₆₂ ] ^6- (where y is an integer of 1 or more and 17 or less); Emissions _{[SiW 12-x Mo x O} 40] 4- (x is 1 to 11 integer), and the like. Among the polyacid anions containing at least one of tungsten (W) and molybdenum (Mo), heteropoly acids are preferable among the above from the viewpoints of heat resistance and availability of raw materials, and P More preferably, it is a heteropoly acid containing phosphorus.

  The polyacid anion in the colorant represented by the general formula (IX) can be used singly or in combination of two or more of the above anions, and when used in combination of two or more, the polyacid anion It is preferable from the viewpoint of heat resistance and light resistance that the ratio of tungsten to molybdenum in the whole is 90:10 to 100: 0.

  In the general formula (IX), b represents the number of cations, d represents the number of anions in the molecular assembly, and b and d each represent an integer of 1 or more. When b is 2 or more, a plurality of cations in the molecular association may be used alone or in combination of two or more. When d is 2 or more, one or more anions in the molecular association may be used alone or in combination of two or more, and organic and inorganic anions may be used in combination. .

  E in the general formula (IX) is an integer of 0 or 1. e = 0 represents a triarylmethane skeleton, and e = 1 represents a xanthene skeleton. The plurality of e may be the same or different. That is, for example, it may be a cation moiety having only a triarylmethane skeleton or only a xanthene skeleton, or may be a cation moiety containing both a triarylmethane skeleton and a xanthene skeleton in one molecule. From the viewpoint of color purity, it is preferable that the cation moiety has only the same skeleton. On the other hand, the coloring material represented by General Formula (IX) can be adjusted to a desired color by setting it as the cation part containing both a triarylmethane skeleton and a xanthene skeleton.

In addition, as a coloring material used in the present disclosure, a metal lake color material of a dye having a thermal decomposition temperature of 230 ° C. or more is faded by heating before the structure represented by the general formula (II-a) is developed. Since it is suppressed, it is preferable from the point which heat resistance and brightness tend to improve by the combination with the polymeric dispersing agent which concerns on this indication. As a metal lake color material of the dye whose thermal decomposition temperature is 230 ° C. or higher, for example, a color material described in Japanese Patent No. 5403175 can be mentioned.
The thermal decomposition temperature of the dye can be measured by thermogravimetric-differential thermal analysis (TG-DTA). Specifically, using, for example, DTG-60A manufactured by Shimadzu Corporation, the temperature is raised to 30 ° C. to 600 ° C. in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min, and the thermal decomposition temperature is measured.

  The average dispersed particle diameter of the colorant (A) is not particularly limited as long as it is capable of desired color development, and varies depending on the type of colorant to be used, but the dispersion stability of the colorant is good, From the viewpoint of obtaining sufficient coloring power, the thickness is preferably in the range of 5 nm to 300 nm, and more preferably in the range of 30 nm to 200 nm.

  The content of the color material (A) is not particularly limited as long as it can form a desired colored layer, and is appropriately adjusted. Specifically, although it varies depending on the type of the coloring material, it is preferably in the range of 0.05% by mass or more and 20% by mass or less, and is 1% by mass or more and 15% by mass or less It is more preferable to be in the range of

[(C) solvent]
The solvent (C) contained in the coloring material dispersion according to the present disclosure does not react with each component in the coloring material dispersion, and can be appropriately selected from solvents which can dissolve or disperse these. it can. Specifically, alcohol type; ether alcohol type; ester type; ketone type; ether alcohol acetate type; ether type; aprotic amide type; lactone type; unsaturated hydrocarbon type; organic solvent such as saturated hydrocarbon type Among them, it is preferable to use an ester solvent from the viewpoint of solubility at the time of dispersion and coating suitability.

Preferred ester solvents include, for example, methyl methoxypropionate, ethyl ethoxypropionate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl Acetate, ethoxyethyl acetate, ethyl cellosolve acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,6-hexanediol diacetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate etc. are mentioned.
Above all, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA) from the viewpoints of low danger to human body and low volatility at around room temperature but good heat drying property. In this case, there is an advantage that a special cleaning step is not required even when switching to a colored resin composition using conventional PGMEA.
These solvents may be used alone or in combination of two or more.

[Other ingredients]
In the coloring material dispersion according to the present disclosure, a dispersion assisting resin and other components may be blended as needed as long as the effects of the present disclosure are not impaired.
As a dispersion | distribution auxiliary | assistant resin, the alkali-soluble resin illustrated by the coloring resin composition mentioned later, for example is mentioned. The steric hindrance of the alkali-soluble resin makes it difficult for the coloring material particles to come in contact with each other, and there are cases where it is possible to reduce the dispersing agent by the dispersion stabilization or the dispersion stabilization effect.
Further, as other components, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, a repelling agent, an antioxidant, an aggregation inhibitor, and a UV absorber Etc.

The colorant dispersion according to the present disclosure is suitably used as a pre-preparation for preparing a colored resin composition described later. That is, with the colorant dispersion liquid, the mass of solid components other than the colorant components in the composition (mass of colorant components in the composition) / (prepared in the preparation of the colored resin composition described later) 2.) Colorant dispersion with high ratio. Specifically, the ratio (mass of color material component in the composition) / (mass of solid content other than the color material component in the composition) is usually 1.0 or more. By mixing the coloring material dispersion and at least the binder component, a colored resin composition having excellent dispersibility can be prepared.
In the present disclosure, solid content means all components other than the solvent.

[Method of producing colorant dispersion]
The method for producing a colorant dispersion according to the present disclosure contains (A) colorant, (B) dispersant, (C) solvent, and various additive components optionally used, and (A) colorant is Any method may be used as long as it can be uniformly dispersed in the solvent (C) by the dispersing agent (B), and can be uniformly dispersed by mixing using a known mixing means.
For example, after the dispersant (B) is mixed with the solvent (C) and stirred to prepare a dispersant solution, the dispersant solution is mixed with the colorant (A) and other components as needed, and is known And dispersion methods using a stirrer or a disperser of

  Examples of the disperser for performing the dispersion treatment include roll mills such as 2 rolls and 3 rolls, ball mills such as ball mill and vibration ball mill, paint conditioners, bead mills such as continuous disc type bead mill and continuous annular type bead mill. As a preferable dispersion condition of a bead mill, 0.03 mm or more and 2.00 mm or less of a bead diameter to be used are preferable, More preferably, they are 0.10 mm or more and 1.0 mm or less.

  Specifically, preliminary dispersion is performed using 2 mm zirconia beads having relatively large bead diameters, and further, main dispersion using 0.1 mm zirconia beads having relatively small bead diameters is mentioned. Moreover, it is preferable to filter with a membrane filter of 0.5 to 5.0 μm after dispersion.

  The viscosity of the coloring material dispersion according to the present disclosure is not particularly limited, but it is preferable that the shear viscosity at a shear rate of 60 rpm is 10 mPa · s or less from the viewpoint of good dispersibility and good handleability. And 7 mPa · s or less is more preferable. The shear viscosity can be measured using a known visco-elastic measurement device, and is not particularly limited. For example, the shear viscosity can be measured using "Rheometer MCR301" manufactured by Anton Paar.

3. Colored resin composition A colored resin composition according to the present disclosure contains the colorant dispersion according to the present disclosure, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. Do.
The colored resin composition according to the present disclosure contains the coloring material dispersion according to the present disclosure, so that the change in chromaticity after heating at high temperature is suppressed, the luminance is improved, and a thinner colored layer is formed. be able to.
The coloring material dispersion liquid contained in the colored resin composition according to the present disclosure is the same as the coloring material dispersion liquid according to the present disclosure described above, and thus the description thereof is omitted here. Hereinafter, the (D) alkali-soluble resin, the (E) multifunctional monomer, the (F) photoinitiator, and the optional additional components which may be optionally contained, which the colored resin composition according to the present disclosure contains, will be described.

[(D) alkali soluble resin]
The alkali-soluble resin in the present disclosure has an acidic group, acts as a binder resin, and is appropriately selected and used as long as it is soluble in a developer used when forming a pattern, particularly preferably an alkaline developer. be able to.
The preferred alkali-soluble resin in the present disclosure is preferably a resin having a carboxy group as an acidic group, and specifically, a (meth) acrylic copolymer having a carboxy group, an epoxy (meth) acrylate having a carboxy group Resin etc. are mentioned. Among these, particularly preferred are 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. It is because the film strength of the cured film formed by containing a photopolymerizable functional group is improved. Moreover, you may use these (meth) acrylic-type copolymers and epoxy (meth) acrylate resin in mixture of 2 or more types.

The (meth) acrylic copolymer having a carboxy group is obtained by copolymerizing a carboxy group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The (meth) acrylic copolymer having a carboxy group may further contain a structural unit having an aromatic carbon ring. The aromatic carbon ring functions as a component to improve the strength of the film in the colored resin composition.
The acrylic copolymer having a carboxy group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the colored resin composition, but also functions as a component that improves the solubility in a solvent and the solvent resolubility.

As a specific example of the (meth) acrylic copolymer having a carboxy group, for example, those described in WO 2012/144521 can be mentioned, and specifically, for example, methyl (meth) acrylate And copolymers comprising a monomer having no carboxy group, such as ethyl (meth) acrylate, and one or more selected from (meth) acrylic acid and its anhydride. In addition, for example, polymers in which an ethylenically unsaturated bond is introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above-mentioned copolymer can be exemplified, but the present invention is limited thereto It is not something to be done.
Among these, polymers or the like into which an ethylenically unsaturated bond is introduced by addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to a copolymer are polymerized with a polyfunctional monomer described later at the time of exposure. Is particularly preferable in that the colored layer is more stable.

  The copolymerization ratio of the carboxy group-containing ethylenic unsaturated monomer in the carboxy group-containing copolymer is 5% by mass or more from the viewpoint that the solubility of the obtained coating film in an alkali developing solution is good and pattern formation becomes easy. Is preferably 10% by mass or more. In addition, the copolymerization ratio of the carboxy group-containing ethylenic unsaturated monomer in the carboxy group-containing copolymer is from the viewpoint of suppressing the detachment of the formed pattern from the substrate and the film surface roughness at the time of development with an alkaline developer. And 50% by mass or less, and more preferably 40% by mass or less.

  The preferred mass average molecular weight of the carboxy group-containing copolymer is preferably 1,000 or more, more preferably 3,000 or more, from the viewpoint of suppressing the decrease in binder function after curing, and development with an alkaline developer It is preferably at most 200,000, more preferably at most 50,000, in order to facilitate pattern formation sometimes. The mass average molecular weight is determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.

The epoxy (meth) acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth) obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used. As a specific example, the thing etc. which are described in international publication 2012/144521 gazette are mentioned, for example. The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride may be used alone or in combination of two or more.

  The alkali-soluble resin used in the colored resin composition may be used singly or in combination of two or more, and the content thereof may be colored in order to obtain sufficient alkali developability. Preferably, the amount is 10 parts by mass or more, more preferably 25 parts by mass or more, based on 100 parts by mass of the coloring material contained in the resin composition, and the coloring material can be sufficiently contained to obtain sufficient coloring density. The content of the alkali-soluble resin is preferably 500 parts by mass or less, and more preferably 300 parts by mass or less, with respect to 100 parts by mass of the coloring material contained in the colored resin composition.

[(E) multifunctional monomer]
The polyfunctional monomer used in the colored resin composition of the present disclosure may be any monomer that can be polymerized by the later-described photoinitiator, and usually, a compound having two or more ethylenic unsaturated double bonds is used, and in particular It is preferable that it is polyfunctional (meth) acrylate which has two or more (meth) acryloyl groups.
As polyfunctional (meth) acrylate, it may select suitably from what is conventionally known, and may be used. As a specific example, the thing etc. which are described in international publication 2012/144521 gazette are mentioned, for example. Moreover, as a polyfunctional monomer, it is preferable to use the polyfunctional (meth) acrylate which does not have an acidic group from the point of solvent resistance.

  One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. In addition, when excellent photocurability (high sensitivity) is required for the colored resin composition of the present disclosure, the polyfunctional monomer has three or more polymerizable double bonds (trifunctional) or more. Are preferable, and poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Succinic acid derivative of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid of dipentaerythritol penta (meth) acrylate Modified product, dipentaerythritol hexahydrate Meth) acrylate are preferable.

<Phosphorus atom-containing polyfunctional monomer>
In addition, the polyfunctional monomer used in the colored resin composition of the present disclosure contains a phosphorus atom-containing polyfunctional monomer, whereby the change in chromaticity after heating at high temperature is further suppressed, the luminance is improved, and the solvent resistance is improved. It is preferable from the point of improving. Under high temperature heating, active oxygen is increased, while vibration due to heat is transmitted to the colorant molecules, and the molecular motion of the colorant molecules becomes intense. It is presumed that the colorant molecules in such molecular motion are likely to be oxidized by the surrounding active oxygen and to be discolored by the decomposition of the colorant molecules. On the other hand, the phosphorus atom-containing polyfunctional monomer has an antioxidizing function such as stabilizing the hydroperoxide generated from active oxygen, and the phosphorus atom is heavier than the carbon atom and the frequency due to heat is smaller. It is presumed that the color material has a function of making it difficult to transmit vibration due to heat. In addition, since the phosphorus atom-containing polyfunctional monomer has a large specific gravity, the phosphorus atom density around the color material is increased, and further, vibration due to heat is difficult to be transmitted to the color material, and oxidation is suppressed. Presumed. Usually, under high temperature heating, the active oxygen increases, but as described above, the effect of reducing the hydroperoxide etc. in the coating film by the phosphorus atom-containing polyfunctional monomer and the effect of suppressing the vibration due to the heat of the coloring material As a result of the synergetic effect thereof, it is presumed that it contributes to suppression of color fading of the color material even under post-baking by heating at a high temperature of 230 ° C. or more after forming a coating, and a colored layer having very high luminance is obtained. In addition, since the phosphorus atom-containing polyfunctional monomer contains a phosphorus atom, the specific gravity is large, and as a result of the cross-linking reaction being performed at a higher density in the cured film, the permeation of the solvent is suppressed, so it is estimated that the solvent resistance is improved. Be done.
On the other hand, when the colored resin composition contains a phosphorus atom-containing polyfunctional monomer, the formed colored layer tends to have poor adhesion to the substrate. On the other hand, the colored resin composition according to the present disclosure suppresses degradation of substrate adhesion even if it contains a phosphorus atom-containing polyfunctional monomer by containing the polymer dispersant according to the present disclosure described above. be able to. This is because the protective group containing at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group possessed by the polymer dispersant according to the present disclosure is released during the post-baking when forming the colored layer to express a carboxy group As a result, the affinity between the colored layer and the substrate is improved, and further, the developed carboxy group is dehydrated and condensed with a polar group such as a hydroxyl group possessed on the substrate surface, whereby the adhesion between the colored layer and the substrate is further enhanced. It is estimated to improve.

In the present disclosure, the phosphorus atom-containing polyfunctional monomer may be a compound containing a phosphorus atom and containing two or more polymerizable functional groups in one molecule.
As a polymerizable functional group which the said phosphorus atom containing polyfunctional monomer has, a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, an allyl group etc. are mentioned. In the present disclosure, the (meth) acrylamide group is a group represented by the general formula CH ₂ CRCCRCONR ′ ′, in which R is a hydrogen atom or a methyl group, and R ′ is a hydrogen atom or an alkyl It is a group. R is preferably a hydrogen atom from the viewpoint of high sensitivity in photo radical polymerization and improvement of the heat resistance and solvent resistance of the colored layer. In addition, R ′ is preferably a hydrogen atom from the viewpoint of being able to improve the heat resistance and solvent resistance of the colored layer by forming a hydrogen bond to crosslink more strongly.
As the polymerizable functional group, (meth) acryloyl group and (meth) acrylamide group from the viewpoint of high sensitivity in photo radical polymerization, and improvement of heat resistance of the colored layer, solvent resistance and pattern adhesion at the time of alkali development. It is preferable to contain at least (meth) acryloyl group from the viewpoint of solvent solubility.

Among the above-mentioned phosphorus atom-containing polyfunctional monomers, phosphorus atom-containing polyfunctional monomers having no acidic group are preferable from the viewpoint of further improving the solvent resistance. In the case of not having an acidic group, it is presumed that since the affinity to a highly polar solvent such as NMP is low, it is possible to further suppress the permeation of the solvent.
Moreover, as said phosphorus atom containing polyfunctional monomer, (i) It has a polyphosphate ester structure which two or more phosphorus atoms couple | bonded by -O- bond, (ii) phosphorus atom and a (meth) acrylamide group Also preferred is a phosphorus atom-containing polyfunctional monomer having at least one structure selected from the group consisting of and (iii) a phosphorus atom and an isocyanurate group. In the case of a polyphosphate structure in which two or more phosphorus atoms are bonded by an -O- bond, the content of phosphorus atoms is increased, so the specific gravity is further increased and the resin is crosslinked at a high density, or polymerizable Since it is possible to increase the number of functional groups and the crosslinking reaction is performed at a higher density, it is presumed that the permeation of the solvent can be further suppressed. Moreover, in the case of containing a (meth) acrylamide group, hydrogen bonds are formed at the NH site to crosslink more strongly, so it is presumed that permeation of the solvent can be further suppressed. In addition, when it contains an isocyanurate group, the molecule becomes rigid, and the solubility in a solvent such as NMP decreases due to the influence of the hydrophobicity of the isocyanurate group, so it is possible to further suppress the permeation of the solvent. It is estimated that
Examples of these suitable phosphorus atom-containing polyfunctional monomers include those described in WO 2017/022790.

  In the (E) polyfunctional monomer used in the colored resin composition of the present disclosure, the total content of the phosphorus atom-containing polyfunctional monomer is preferably 20% by mass or more in the total amount of the (E) polyfunctional monomer. And 50% by mass or more.

  Further, the content of the (E) polyfunctional monomer used in the colored resin composition of the present disclosure is not particularly limited, but from the viewpoint of sufficiently advancing photocuring and suppressing elution of the exposed portion, the alkali Preferably it is 5 mass parts or more with respect to 100 mass parts of soluble resin, More preferably, it is 20 mass parts or more. In addition, the content of the (E) polyfunctional monomer is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, with respect to 100 parts by mass of the alkali-soluble resin, from the viewpoint of improving alkali developability. It is.

  In the colored resin composition of the present disclosure, the total content of the (E) polyfunctional monomer is preferably 5% by mass or more and 70% by mass or less, and 10% by mass or less in the total solid content of the colored resin composition. It is more preferable that it is 50 mass% or less.

The acid value of the phosphorus atom-containing monomer contained in the colored resin composition of the present disclosure is preferably 35 mg KOH / g or less, more preferably 20 mg KOH / g or less, and further preferably 13 mg KOH / g or less Is preferred. The phosphorus atom-containing monomer herein includes not only polyfunctional (meth) acrylates having two or more (meth) acryloyl groups, but also (meth) acrylates having one (meth) acryloyl group.
In addition, the said acid value represents the mass (mg) of potassium hydroxide required in order to neutralize the acidic component contained in solid content 1g of a phosphorus atom containing monomer, and is measured by the method as described in JIS K 0070. It is a value.
In the present disclosure, when the acid value of the phosphorus atom-containing monomer contained in the colored resin composition is too high, a salt is formed with a commonly used basic photoinitiator to generate aggregated foreign matter in the colored resin composition. In addition, it may form a salt with the basic pigment dispersant in the colorant dispersion to deteriorate the dispersibility of the colorant and reduce the contrast. If the total acid value of the phosphorus atom-containing monomer is too high, the solubility in an alkali developer becomes too high to make it difficult for the pattern to remain at the time of development, or the crosslink density decreases to significantly deteriorate the solvent resistance. There is a fear.
Even if it is a commercial product, some acid groups may be left at the time of synthesis, or some acid groups may be generated at the time of storage, but the acid value of the phosphorus atom-containing monomer is 35 mg KOH / g or less. Such problems when the acid value is too high are suppressed, and are suitable for the colored resin composition of the present disclosure.

[(F) photoinitiator]
There is no restriction | limiting in particular as a photoinitiator used in the coloring resin composition of this indication, It can be used combining 1 type, or 2 or more types out of conventionally known various photoinitiators. As a specific example, the thing etc. which are described in international publication 2012/144521 gazette are mentioned, for example.

  The content of the photoinitiator used in the colored resin composition is preferably 0 with respect to 100 parts by mass of the polyfunctional monomer from the viewpoint of sufficiently causing a polymerization reaction and making the hardness of the colored layer sufficient. The content is 0.11 parts by mass or more, more preferably 5 parts by mass or more. In addition, the content of the photo initiator is 100 parts by mass of the above-mentioned polyfunctional monomer in order to make the content of the coloring material etc. in the solid content of the colored resin composition sufficient and to obtain a sufficient coloring concentration. Preferably it is 100 mass parts or less, More preferably, it is 60 mass parts or less.

[Optional Additives]
The colored resin composition of the present disclosure may contain various additives as needed, as long as the effects of the colored resin composition of the present disclosure described above are not impaired.

(Antioxidant)
It is preferable that the colored resin composition further contains an antioxidant from the viewpoint of heat resistance and light resistance. The antioxidant may be appropriately selected from those known in the art. Specific examples of the antioxidant include, for example, hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. From the point of view, it is preferable to use a hindered phenolic antioxidant.
A hindered phenolic antioxidant contains at least one phenol structure, and a structure in which at least one of the 2- and 6-positions of hydroxyl groups of the phenol structure is substituted with a substituent having 4 or more carbon atoms It means the antioxidant which it has. Moreover, the latent antioxidant in which the hindered phenol as described in Unexamined-Japanese-Patent No. 2015-132791 was latent may be sufficient.

  When using antioxidant, the compounding quantity will not be specifically limited if the effect of the colored resin composition of this indication is not impaired. The compounding amount of the antioxidant is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more based on the total solid content in the colored resin composition, from the viewpoint of excellent heat resistance. Is more preferably 5.0% by mass or less, and 4.0% by mass or less based on the total solid content in the colored resin composition, from the viewpoint that the colored resin composition can be made highly sensitive. It is more preferable that

(Other additives)
As the additive, in addition to the above-mentioned antioxidants, for example, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet light absorbers, adhesion promoters, etc. Can be mentioned.
Specific examples of the surfactant and the plasticizer include, for example, those described in WO 2012/144521.

<Mixing ratio of each component in colored resin composition>
In the colored resin composition of the present disclosure, the total amount of (D) an alkali soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator serving as a binder component relative to the total solid content of the colored resin composition is The content is preferably 10% by mass or more, more preferably 30% by mass or more from the viewpoint that a colored layer having sufficient hardness and adhesion to a substrate can be obtained, and further, it is excellent in developability and heat. The amount is preferably 90% by mass or less, and more preferably 80% by mass or less, from the viewpoint of suppressing the generation of minute wrinkles due to contraction.

  The content of the solvent may be appropriately set within the range in which the colored layer can be formed with high accuracy. From the viewpoint of making the coating property excellent with respect to the total amount of the colored resin composition containing the solvent, it is usually preferably in the range of 55% by mass to 95% by mass, and in particular, 65% by mass It is more preferable to be in the range of 88% by mass or less.

<Method of producing colored resin composition>
The method for producing a colored resin composition of the present disclosure comprises optionally using the colorant dispersion according to the present disclosure, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. No particular limitation is imposed as long as the coloring material can be dispersed more uniformly in the solvent than the dispersing agent, and it is possible to prepare by mixing using known mixing means. it can.
As a method for preparing the colored resin composition, for example, (1) a binder component containing an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and various additive components optionally used in a colorant dispersion liquid (2) A colorant dispersion prepared by dispersing two or more colorants separately in a solvent together with a dispersant, or dissolving other colorants in a solvent without using a dispersant. And a method of mixing a binder component optionally containing a coloring material solution, an alkali soluble resin, a polyfunctional monomer, and a photoinitiator, and various additive components optionally used; (3) color in a solvent A method of simultaneously charging and mixing materials, dispersants, binder components, and various additive components optionally used; (4) in the solvent, the dispersant, the binder components, and optionally, That were added and various additive components, were mixed, a method of mixing by adding a colorant; and the like.
Among these methods, the method of preparing the colorant dispersion in advance of the above (1) or (2) is preferable from the viewpoint of effectively preventing aggregation of the colorant and enabling uniform dispersion.

4. Color filter A color filter according to the present disclosure is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and a colored layer which is a cured product of the colored resin composition according to the present disclosure. Have.
Further, a method of manufacturing a color filter of the present disclosure is a method of manufacturing a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate,
And forming at least one of the colored layers by curing the colored resin composition according to the present disclosure.

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

(Colored layer)
At least one of the colored layers used in the color filter of the present disclosure is a cured product of the colored resin composition according to the present disclosure.
The colored layer is usually formed at an opening of a light shielding portion on a transparent substrate described later, and is usually formed of a coloring pattern of three or more colors.
Moreover, it does not specifically limit as arrangement | sequence of the said colored layer, For example, it can be set as general arrangement, such as stripe type, mosaic type, triangle type, 4 pixel arrangement | positioning type | mold. In addition, the width, area, and the like of the colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration of the colored resin composition, the viscosity, and the like, but generally, it is preferably in the range of 1 μm to 5 μm.

The colored layer can be formed by the following method.
First, the colored resin composition is coated on a transparent substrate to be described later using a coating method such as a spray coating method, dip coating method, bar coating method, roll coating method, spin coating method, slit coating method or die coating method. , To form a wet coating.
Next, the wet coating film is dried using a hot plate, an oven or the like, exposed to light through a mask of a predetermined pattern, and photopolymerized with an alkali-soluble resin, a polyfunctional monomer, etc. It is a photosensitive coating film. As a light source used for exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, an electron beam etc. are mentioned, for example. The exposure amount is appropriately adjusted depending on the light source to be used, the thickness of the coating film, and the like.
Further, heat treatment may be performed to promote the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, development processing is performed using a developer, and the unexposed area is dissolved and removed to form a coating film in a desired pattern. As a developing solution, usually, a solution in which an alkali is dissolved in water or a water-soluble solvent is used. An appropriate amount of surfactant or the like may be added to the alkaline solution. Moreover, the developing method can employ | adopt a general method.
After the development processing, washing of the developing solution and drying of the cured coating film of the colored resin composition are usually performed to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. There is no limitation in particular as heating conditions, According to the use of a coating film, it selects suitably.

(Light blocking part)
The light shielding portion in the color filter of the present disclosure is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding portion 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 stripe form and a matrix form, are mentioned. Examples of the light shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film, CrO _x film (x is an arbitrary number) may be one and the Cr film is two-layered, also, CrO _x film (x is an arbitrary number) with reduced more reflectivity Alternatively, three layers of CrN _y films (y is an arbitrary number) and Cr films may be stacked.
When the light shielding portion is obtained by dispersing or dissolving a black color material in a binder resin, a method of forming the light shielding portion is not particularly limited as long as the light shielding portion can be patterned. For example, the photolithography method, the printing method, the inkjet method etc. using the coloring resin composition for light-shielding parts can be mentioned.

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

(Transparent substrate)
The transparent substrate in the color filter of the present disclosure is not particularly limited as long as it is a transparent substrate to visible light, and a transparent substrate used for a general color filter can be used. Specifically, it has flexibility and flexibility such as transparent non-flexible rigid material such as quartz glass, non-alkali glass, synthetic quartz plate, or transparent resin film, resin plate for optics, flexible glass, etc. A transparent flexible material is mentioned.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this indication, the thing of about 50 micrometers or more and 1 mm or less can be used, for example.
In the color filter of the present disclosure, in addition to the transparent substrate, the light shielding portion, and the colored layer, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, and columnar spacers are formed. It may be done. The color filter of the present disclosure is not limited to the configuration exemplified above, and a known configuration generally used for the color filter can be appropriately selected and used.

5. Liquid Crystal Display Device The liquid crystal display device of the present disclosure includes the color filter according to the present disclosure described above, a counter substrate, and a liquid crystal layer positioned between the color filter and the counter substrate.
Such a liquid crystal display device of the present disclosure will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present disclosure. As exemplified in FIG. 2, the liquid crystal display device 40 of the present disclosure includes a color filter 10, an opposing substrate 20 having a TFT array substrate and the like, a liquid crystal layer 15 positioned between the color filter 10 and the opposing substrate 20. And. In FIG. 2, an example in which the alignment film 13a is located on the colored layer 3 side of the color filter 10 and the alignment film 13b is located on the opposite substrate 20 side, and the liquid crystal layer 15 is located between the two alignment films 13a and 13b. Is shown. Furthermore, in FIG. 2, the liquid crystal display device 40 includes the polarizing plate 25 a located outside the color filter 10, the polarizing plate 25 b located outside the counter substrate 20, and the liquid crystal display device 40 facing the counter substrate 20. The example which has the back light 30 located outside the polarizing plate 25b located is shown.
The liquid crystal display device of the present disclosure is not limited to the configuration shown in FIG. 2 and can be generally known as a liquid crystal display device using a color filter.

The drive method of the liquid crystal display device of the present disclosure is not particularly limited, and a drive method generally used for a liquid crystal display device can be adopted. As such a driving method, for example, a TN method, an IPS method, an OCB method, an MVA method and the like can be mentioned. In the present disclosure, any of these systems can be suitably used.
In addition, the opposite substrate can be appropriately selected and used in accordance with the driving method and the like of the liquid crystal display device of the present disclosure.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy, and a mixture thereof can be used according to the driving method and the like of the liquid crystal display device of the present disclosure.

As a method of forming a liquid crystal layer, a method generally used as a method of manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and an opposite substrate, and the liquid crystal is heated to be an isotropic liquid, and the liquid crystal cell is isotropic liquid is made using the capillary effect. The liquid crystal layer can be formed by injecting in the state of and sealing with an adhesive. Thereafter, by gradually cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.
In the liquid crystal dropping method, for example, a sealing agent is applied to the peripheral edge of the color filter, the color filter is heated to a temperature at which the liquid crystal is isotropic, and the liquid crystal is dropped in the isotropic liquid state using a dispenser or the like. The liquid crystal layer can be formed by overlapping the color filter and the opposite substrate under reduced pressure and adhering them through a sealing agent. Thereafter, by gradually cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.

Moreover, as a backlight used for the liquid crystal display device of this indication, according to the use of a liquid crystal display device, it can select suitably and can use. As the backlight, for example, a cold cathode fluorescent lamp (CCFL), a backlight unit using a white LED or a white organic EL as a light source can be provided in addition to a cold cathode fluorescent lamp (CCFL).
As the white LED, for example, a white LED which obtains white light by color mixing by combining red LED, green LED and blue LED, a white LED which obtains white light by color mixing combining blue LED, red LED and green phosphor, blue LED White LED to obtain white light by color mixing by combining red, green and red light emitting phosphors, White LED to obtain white light by mixing blue LED and YAG phosphor, ultraviolet light LED and red light emitting phosphor and green light emitting fluorescent light A white LED etc. which obtain white light by color-mixing combining a body and a blue light emission fluorescent substance can be mentioned. A quantum dot may be used as the phosphor.

6. Light Emitting Display Device A light emitting display device according to the present disclosure includes the color filter according to the present disclosure described above and a light emitter. Examples of the light emitting display device according to the present disclosure include an organic light emitting display device having an organic light emitting body as the light emitting body. A light-emitting body is not limited to an organic light-emitting body, An inorganic light-emitting body can also be used suitably.
Such a light emitting display device of the present disclosure will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of the light emitting display device of the present disclosure. As illustrated in FIG. 3, the light emitting display device 100 of the present disclosure includes a color filter 10 and a light emitter 80. The organic protective layer 50 or the inorganic oxide film 60 may be provided between the color filter 10 and the light emitter 80.

As a method of laminating the light emitter 80, for example, a method of sequentially forming 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 on the color filter Alternatively, the light-emitting body 80 formed on another substrate may be attached to the inorganic oxide film 60. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and the other components in the light emitting body 80 may be appropriately known ones. The light emitting display device 100 manufactured in this manner is applicable to, for example, an organic EL display of a passive drive system and an organic EL display of an active drive system.
Note that the light emitting display device of the present disclosure is not limited to the light emitting display device having the configuration shown in FIG. 3, and can generally have a known configuration as a light emitting display device using a color filter. .

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

Example 1
(1) Synthesis of macromonomer MM-1 80.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) is charged in a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer. The mixture was heated to a temperature of 100 ° C. while stirring under a nitrogen stream. 20.0 parts by mass of methyl methacrylate, 30.0 parts by mass of t-butyl methacrylate, 15.0 parts by mass of n-butyl methacrylate, 15.0 parts by mass of benzyl methacrylate, 2-ethoxyethyl methacrylate 20. A mixed solution of 0 parts by mass, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, and 1.30 parts by mass of α, α′-azobisisobutyronitrile (AIBN) is dropped over 1.0 hour, It reacted for another 3 hours. Next, the nitrogen gas flow is stopped, the reaction solution is cooled to 80 ° C., 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko), 0.10 parts by mass of dibutyltin dilaurate, 0.10 parts by mass of p-methoxyphenol A 52.5 mass% solution of macromonomer MM-1 was obtained by adding 3 parts of PGMEAs and stirring for 3 hours. The obtained macromonomer MM-1 was confirmed by GPC (gel permeation chromatography) under the conditions of NMP, 0.01 mol / L lithium bromide addition / polystyrene standard, mass average molecular weight (Mw) 3600, The number average molecular weight (Mn) 1500 and the molecular weight distribution (Mw / Mn) were 2.40.

(2) Synthesis of Graft Copolymer A 85.0 parts by mass of PGMEA was charged in a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, The temperature was raised to 85 ° C. 127.0 parts by mass (the effective solid content 66.7 parts by mass) of the macromonomer MM-1 solution obtained above, 33.33 parts by mass of 2- (dimethylamino) ethyl methacrylate, 2.48 parts by mass n-dodecyl mercaptan A mixed solution of 40.0 parts by mass of PGMEA and 1.0 parts by mass of AIBN is added dropwise over 1.5 hours, heated and stirred for 3 hours, and then 0.20 parts by mass of AIBN and 20.0 parts by mass of PGMEA are mixed for 10 minutes. The reaction solution was added dropwise over 1 hour and further stirred at the same temperature for 1 hour to obtain a 25.3% by mass solution of graft copolymer A. As a result of GPC measurement, the obtained graft copolymer A had a mass average molecular weight (Mw) 8900, a number average molecular weight (Mn) 5100, and a molecular weight distribution (Mw / Mn) of 1.75.
Also, using a thermogravimetric analyzer (DTG-60A, manufactured by Shimadzu Corporation), the temperature rising rate is 10 ° C./min for 6 mg of graft copolymer A, and the temperature is raised from room temperature (23 ° C.) to 230 ° C. When a weight change was measured for 30 minutes at 230 ° C. and under a nitrogen atmosphere, a weight loss derived from the t-butyl group was confirmed.

(Example 2)
(1) Synthesis of Macromonomer MM-2 Macromonomer MM-1 except that in the synthesis of macromonomer MM-1, 50.0 parts by mass of t-butyl methacrylate was added without adding methyl methacrylate. In the same manner as in the synthesis of (5), a 53.0% by mass solution of macromonomer MM-2 was obtained. As a result of GPC measurement, the obtained macromonomer MM-2 had a mass average molecular weight (Mw) 4100, a number average molecular weight (Mn) 1700, and a molecular weight distribution (Mw / Mn) of 2.32.

(2) Synthesis of Graft Copolymer B In the synthesis of graft copolymer A, 125.8 parts by mass of the solution of macromonomer MM-2 obtained above instead of the solution of macromonomer MM-1 (effective solid content 66 A 25.4 mass% solution of graft copolymer B was obtained in the same manner as in the synthesis of graft copolymer A, except that 7 parts by mass) was used. As a result of GPC measurement, the obtained graft copolymer B had a mass average molecular weight (Mw) of 10,000, a number average molecular weight (Mn) of 5100, and a molecular weight distribution (Mw / Mn) of 1.98.
Also, using a thermogravimetric analyzer (DTG-60A manufactured by Shimadzu Corporation), the temperature rising rate is 10 ° C./min for a sample of 6 mg of graft copolymer B, and the temperature is raised from room temperature (23 ° C.) to 230 ° C. When a weight change was measured for 30 minutes at 230 ° C. and under a nitrogen atmosphere, a weight loss derived from the t-butyl group was confirmed.

(Example 3)
(1) Synthesis of macromonomer MM-3 In the synthesis of macromonomer MM-1, without adding methyl methacrylate, n-butyl methacrylate, benzyl methacrylate or 2-ethoxyethyl methacrylate, methacrylic acid -t In the same manner as in the synthesis of the macromonomer MM-1 except that 100.0 parts by mass of -butyl was added, a 50.1% by mass solution of the macromonomer MM-3 was obtained. As a result of GPC measurement, the obtained macromonomer MM-3 had a mass average molecular weight (Mw) of 3600, a number average molecular weight (Mn) of 1,500 and a molecular weight distribution (Mw / Mn) of 2.35.

(2) Synthesis of Graft Copolymer C In the synthesis of graft copolymer A, 133.1 parts by mass of the macromonomer MM-3 solution obtained above is used instead of the macromonomer MM-1 solution (effective solid content 66 A 26.0 mass% solution of graft copolymer C was obtained in the same manner as in the synthesis of graft copolymer A, except that 7 parts by mass) was used. As a result of GPC measurement, the obtained graft copolymer C had a mass average molecular weight (Mw) of 9500, a number average molecular weight (Mn) of 5800, and a molecular weight distribution (Mw / Mn) of 1.63.
Also, using a thermogravimetric analyzer (DTG-60A manufactured by Shimadzu Corporation), the temperature rising rate is 10 ° C./min for 6 mg of the graft copolymer C, and the temperature is raised from room temperature (23 ° C.) to 230 ° C. When a weight change was measured for 30 minutes at 230 ° C. and under a nitrogen atmosphere, a weight loss derived from the t-butyl group was confirmed.

(Comparative example 1)
(1) Synthesis of macromonomer MM-4 In the synthesis of macromonomer MM-1, the macromonomer MM is used except that the amount of methyl methacrylate added is changed to 50.0 parts by mass and no t-butyl methacrylate is added. Analogously to the synthesis of -1, a 48.7% by weight solution of macromonomer MM-4 was obtained. As a result of GPC measurement, the obtained macromonomer MM-4 had a mass average molecular weight (Mw) of 4,000, a number average molecular weight (Mn) of 1,900, and a molecular weight distribution (Mw / Mn) of 2.11.

(2) Synthesis of Graft Copolymer D In the synthesis of graft copolymer A, 137.0 parts by mass of the macromonomer MM-4 solution obtained above is used instead of the macromonomer MM-1 solution (effective solid content 66 A 24.7 mass% solution of graft copolymer D was obtained in the same manner as in the synthesis of graft copolymer A, except that 7 parts by mass) was used. The obtained graft copolymer D had a mass average molecular weight (Mw) 11500, a number average molecular weight (Mn) 4700, and a molecular weight distribution (Mw / Mn) of 2.45 as a result of GPC measurement.

(Example 4)
(1) Synthesis of block polymer intermediate 1 In a reactor equipped with a cooling pipe, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 185.0 parts by mass of NMP and dimethylketene methyl trimethylsilyl acetal as an initiator 5.87 parts by mass was added through an addition funnel to carry out sufficient nitrogen substitution. A funnel for adding 50.0 parts by mass of methyl methacrylate and 50.0 parts by mass of t-butyl methacrylate by injecting 0.5 parts by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate using a syringe Was added dropwise over 60 minutes. The reaction flask was cooled with an ice bath to keep the temperature below 40 ° C. and stirred to obtain a block polymer intermediate 1 solution. As a result of GPC measurement, the block polymer intermediate 1 obtained had a mass average molecular weight (Mw) of 5300, a number average molecular weight (Mn) of 4300, and a molecular weight distribution (Mw / Mn) of 1.23.

(2) Synthesis of block copolymer A 33.3 parts by mass of 2- (dimethylamino) ethyl methacrylate was added to the solution of block polymer 1 obtained above (66.7 parts by mass of effective solid content). The solution was dropped over 20 minutes. After reacting for 1 hour, 0.7 parts by mass of methanol was added to stop the reaction. The obtained block copolymer NMP solution was once distilled off with an evaporator, and the residue was reprecipitated with pure water, filtered and vacuum dried to obtain block copolymer A. As a result of GPC measurement, the block copolymer A thus obtained had a weight average molecular weight (Mw) of 7700, a number average molecular weight (Mn) of 6100, and a molecular weight distribution (Mw / Mn) of 1.26.
Further, using a thermogravimetric analyzer (DTG-60A manufactured by Shimadzu Corporation), the temperature rising rate is 10 ° C./min for 6 mg of the block copolymer A, and the temperature is raised from room temperature (23 ° C.) to 230 ° C. When a weight change was measured for 30 minutes at 230 ° C. and under a nitrogen atmosphere, a weight loss derived from the t-butyl group was confirmed.

(Example 5)
(1) Synthesis of block polymer intermediate 2 Block polymer intermediate except that in the synthesis of block polymer intermediate 1, 100.0 parts by mass of t-butyl methacrylate was added without adding methyl methacrylate. In the same manner as in the synthesis of 1, a block polymer intermediate 2 was obtained. As a result of GPC measurement, the block polymer intermediate 2 obtained had a mass average molecular weight (Mw) of 5800, a number average molecular weight (Mn) of 4600, and a molecular weight distribution (Mw / Mn) of 1.26.

(2) Synthesis of block copolymer B In the synthesis of block copolymer A, instead of the solution of block polymer intermediate 1, the solution of block polymer intermediate 2 obtained above (effective solid content 66.7 parts by mass) Using the same method as in the synthesis of block copolymer A except that the amount of 2- (dimethylamino) ethyl methacrylate added was changed to 33.3 parts by mass and the amount of methanol added was changed to 0.8 parts by mass. Thus, block copolymer B was obtained. As a result of GPC measurement, the obtained block copolymer B had a mass average molecular weight (Mw) 8400, a number average molecular weight (Mn) 6600, and a molecular weight distribution (Mw / Mn) of 1.27.
Also, using a thermogravimetric analyzer (DTG-60A manufactured by Shimadzu Corporation), the temperature rising rate is 10 ° C./min for a sample of 6 mg of block copolymer B, and the temperature is raised from room temperature (23 ° C.) to 230 ° C. When a weight change was measured for 30 minutes at 230 ° C. and under a nitrogen atmosphere, a weight loss derived from the t-butyl group was confirmed.

(Comparative example 2)
(1) Synthesis of block polymer intermediate 3 In the synthesis of block polymer intermediate 1, except that the amount of methyl methacrylate added is changed to 100.0 parts by mass and no t-butyl methacrylate is added, an intermediate of the block polymer is prepared. In the same manner as in the synthesis of body 1, block polymer intermediate 3 was obtained. As a result of GPC measurement, the block polymer intermediate 3 obtained had a mass average molecular weight (Mw) of 5700, a number average molecular weight (Mn) of 4900, and a molecular weight distribution (Mw / Mn) of 1.16.

(2) Synthesis of block copolymer C In the synthesis of block copolymer A, instead of the solution of block polymer intermediate 1, the solution of block polymer intermediate 3 obtained above (effective solid content 66.7 parts by mass) Using the same method as in the synthesis of block copolymer A, except that the amount of 2- (dimethylamino) ethyl methacrylate added was changed to 33.3 parts by mass and the amount of methanol added was changed to 0.9 parts by mass. Thus, block copolymer C was obtained. As a result of GPC measurement, the obtained block copolymer C had a mass average molecular weight (Mw) 8700, a number average molecular weight (Mn) 6500, and a molecular weight distribution (Mw / Mn) of 1.34.

(Example 6)
(1) Synthesis of block polymer intermediate 4 In the synthesis of block polymer intermediate 1, methyl methacrylate is not added, the amount of t-butyl methacrylate added is changed to 30.0 parts by mass, and methacrylic acid-n is further added. -A block polymer intermediate 4 solution was obtained in the same manner as in the synthesis of the block polymer intermediate 1 except that 70.0 parts by mass of butyl was added. As a result of GPC measurement, as a result of GPC measurement, the block polymer intermediate 4 obtained had a mass average molecular weight (Mw) 4900, a number average molecular weight (Mn) 4200, and a molecular weight distribution (Mw / Mn) of 1.17. .

(2) Synthesis of block copolymer D In the synthesis of block copolymer A, instead of the solution of block polymer intermediate 1, the solution of block polymer intermediate 4 obtained above (effective solid content 66.7 parts by mass) The amount of 2- (dimethylamino) ethyl methacrylate added is changed to 33.3 parts by mass, the amount of methanol added is changed to 0.9 parts by mass, and after reprecipitation, the PGMEA solution is recovered at the time of recovery of the obtained compound. A 28.5% by mass solution of block copolymer D was obtained in the same manner as in the synthesis of block copolymer A, except that the solution was recovered. As a result of GPC measurement, the obtained block copolymer D had a mass average molecular weight (Mw) of 7,000, a number average molecular weight (Mn) of 5800, and a molecular weight distribution (Mw / Mn) of 1.21.
Also, using a thermogravimetric analyzer (DTG-60A manufactured by Shimadzu Corporation), the temperature rising rate is 10 ° C./min for 6 mg of the block copolymer C, and the temperature is raised from room temperature (23 ° C.) to 230 ° C. When a weight change was measured for 30 minutes at 230 ° C. and under a nitrogen atmosphere, a weight loss derived from the t-butyl group was confirmed.

(Comparative example 3)
(1) Synthesis of block polymer intermediate 5 In the synthesis of block polymer intermediate 1, except that methyl methacrylate and t-butyl methacrylate were not added, and 100.0 parts by mass of n-butyl methacrylate was added. Similarly to the synthesis of block polymer intermediate 1, a solution of block polymer intermediate 5 was obtained. As a result of GPC measurement, the block polymer intermediate 5 obtained had a mass average molecular weight (Mw) of 5400, a number average molecular weight (Mn) of 4500, and a molecular weight distribution (Mw / Mn) of 1.20.

(2) Synthesis of block copolymer E In the synthesis of block copolymer A, instead of the solution of block polymer intermediate 1, the solution of block polymer intermediate 5 obtained above (effective solid content 66.7 parts by mass) The amount of 2- (dimethylamino) ethyl methacrylate added was changed to 33.3 parts by mass, the amount of methanol added was changed to 0.9 parts by mass, and after reprecipitation, the resulting compound was recovered into a PGMEA solution A 36.9% by mass solution of block copolymer E was obtained in the same manner as in the synthesis of block copolymer A, except for recovery. As a result of GPC measurement, the obtained block copolymer E had a mass average molecular weight (Mw) 7800, a number average molecular weight (Mn) 6200, and a molecular weight distribution (Mw / Mn) of 1.26.

(Examples 7-9, Comparative Example 4, Examples 10-11, Comparative Example 5, Example 12, Comparative Example 6)
The graft copolymers A to D obtained in Examples 1 to 3 and Comparative Example 1, the block copolymers A to E obtained in Examples 4 to 5, Comparative Examples 2 and 6, and Comparative Example 3 Each is dissolved in PGMEA, and phenylphosphonic acid is added so as to be 0.5 molar equivalent with respect to 1 mol of 2- (dimethylamino) ethyl methacrylate, and stirred at 40 ° C. for 30 minutes for each salt type. An amine graft copolymer A to D solution and a salt type amine block copolymer A to E solution (all solids 25% by mass) were prepared.

(Example 13, Comparative Example 7)
The block copolymers D and E obtained in Example 6 and Comparative Example 3 are each dissolved in PGMEA, and the molar amount is 0.3 molar equivalent to 1 mole of 2- (dimethylamino) ethyl methacrylate (DMA). Thus, by adding phenylphosphonic acid (product name "PPA" manufactured by Nissan Chemical Co., Ltd.) and stirring at 40 ° C. for 30 minutes, salt type amine block copolymers F and G solutions (all solids 25% by mass) Was prepared.

Here, each abbreviation in the table is as follows.
MMA: methyl methacrylate tBMA: methacrylic acid-t-butyl nBMA: methacrylic acid n-butyl BzMA: benzyl methacrylate EEMA: 2-ethoxyethyl methacrylate DMA: 2- (dimethylamino) ethyl methacrylate PPA: phenylphosphonic acid

(Evaluation)
<Measurement of infrared absorption spectrum>
The solid content concentration of each of the graft copolymers A to D, block copolymers A to E, salt type amine graft copolymers A to D, and salt type amine block copolymers A to G It diluted using propylene glycol monomethyl ether acetate or propylene glycol monomethyl ether so that it might be 10 to 20 mass%, and the diluted solution was obtained. The diluted solution obtained was coated on a transparent glass substrate and dried to form a coating film so that the film thickness after heating at 230 ° C. for 20 minutes was 2.00 μm ± 0.5 μm. The infrared absorption spectrum (IR spectrum) of this coating film was measured before and after heating at 230 ° C. for 20 minutes. In addition, as a measuring apparatus of IR spectrum, JASCO Ltd. FT / IR-6100 was used.
In each copolymer, the peak around 2960 cm ^-1 derived from a t- butyl group, and Table 3 the values before and after heating of the peak of the peak and 1800 ± ^{5 cm -1} of 1760 ± ^{5 cm -1} derived from an acid anhydride group Shown in. In addition, the peak shown in Table 3 is a peak having a maximum value at 1455 ± 10 cm ⁻¹ which is derived from the methylene group of the main chain in each copolymer as a reference peak, and the peak intensity before and after heating of the reference peak is 1 It is the hour value.
Moreover, as a representative example of the result of IR spectrum, graft copolymer B of Example 2, graft copolymer C of Example 3, graft copolymer D of Comparative Example 1, block copolymer B of Example 5 The IR spectrum of the block copolymer C of Comparative Example 2 is shown in FIGS. In FIGS. 4-8, IR spectrum before heating (before baking) is shown as a continuous line, and IR spectrum after heating (after baking) is shown by a dotted line.
Graft copolymers A, B and C, block copolymers A, B and D, and salt type amine graft copolymers A, B and C, salt type amine block obtained in each example shown in Table 3 The copolymers A, B, D, and F decrease in peak intensity around 2960 cm ⁻¹ derived from t-butyl group before and after heating at 230 ° C. for 20 minutes, and 1760 ± 5 cm ⁻ derived from acid anhydride group The peak intensity of ¹ was 1.1 or more and was significantly increased. Moreover, the increase of the peak intensity of 1800 +/- 5 cm < ^-1 > originating in an acid anhydride group was also confirmed, and the intensity | strength was 0.5 or more.
On the other hand, the graft copolymer D, block copolymers C and E, salt type amine graft copolymer D, and salt type amine block copolymers C, E and G obtained in each comparative example are 230 Before and after heating at 20 ° C. for 20 minutes, no decrease in peak intensity derived from at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group was confirmed. Furthermore, it was confirmed that the peak intensity of 1760 ± 5 cm ⁻¹ derived from the acid anhydride group is less than 1.1, and the peak intensity of 1800 ± 5 cm ⁻¹ is also less than 0.50.

Synthesis Example 1: Synthesis of Blue Color Material α
(1) Synthesis of Intermediate 1 With reference to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 parts by mass of Intermediate 1 represented by the following Chemical Formula (1) (Yield 70%) was obtained.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), Divalent Elemental Analysis: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (7)
8.06%, 7.75%, 7.69%)
Further, the thermal decomposition temperature of the obtained compound was measured by DTG-60A manufactured by Shimadzu Corporation, and it was 239 ° C. as determined from the intersection of tangents near the weight loss temperature.

(2) Synthesis of blue color material α Add 15.00 parts by mass of Intermediate 1 to 300 parts by mass of water, and dissolve at 90 ° C. to obtain an Intermediate 1 solution. Next, 10.44 parts by mass of phosphotungstic acid · n-hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) are added to 100 parts by mass of water, The mixture was stirred to prepare an aqueous solution of phosphotungstic acid. The prepared phosphotungstic acid aqueous solution was mixed with the above Intermediate 1 solution at 90 ° C., and the formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 parts by mass of a blue coloring material α of a metal lake color material of a triarylmethane basic dye represented by the following chemical formula (2).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 510 (+), Divalent Elemental Analysis: CHN found (41.55%, 5.34%, 4.32%); theoretical value (41.66%) , 5.17%, 4.11%)

Synthesis Example 2 Synthesis of Binder Resin A
In a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 120 parts by mass of PGMEA is charged as a solvent, heated to 90 ° C. under a nitrogen atmosphere, and 32 parts by mass of methyl methacrylate A mixture containing 10 parts by mass, 22 parts by mass of cyclohexyl methacrylate, 24 parts by mass of methacrylic acid, 2.0 parts by mass of AIBN as an initiator, and 4.5 parts by mass of n-dodecyl mercaptan as a chain transfer agent over 1.5 hours Dripped into the
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 2 parts after completion of the dropwise addition, 0.05 parts by mass of p-methoxyphenol was added as a polymerization inhibitor.
Next, 22 parts by mass of glycidyl methacrylate is added while blowing in air, and the temperature is raised to 110 ° C. 0.2 parts by mass of triethylamine is then added to cause addition reaction at 110 ° C. for 15 hours. The solid content was 45% by mass).
The obtained binder resin A had a weight average molecular weight (Mw) of 8900, a number average molecular weight (Mn) of 4200, a molecular weight distribution (Mw / Mn) of 2.11 and an acid value of 78 mg KOH / g.

Preparation Example 1 Preparation of Binder Composition A
20.22 parts by mass of PGMEA, 17.78 parts by mass of binder resin A (solid content 45% by mass) of Synthesis Example 2; 8.00 parts by mass of 5- to 6-functional acrylate monomer (trade name: Alonix M 403, manufactured by Toagosei Co., Ltd.) -Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF) 3.00 parts by mass, 2,4 diethylthioxanthone (trade name: Kayacure DETX) Binder composition A (solid content: 40% by mass) was prepared by mixing 1.00 parts by mass of -S (manufactured by Nippon Kayaku Co., Ltd.).

Preparation Example 2 Preparation of Binder Composition B
44.36 parts by mass of PGMEA, 28.44 parts by mass of binder resin A (solid content 45% by mass) of Synthesis Example 2, phosphorus atom-containing polyfunctional (meth) acrylate (trade name: Biscoat # 3PA, manufactured by Osaka Organic Chemical Industry, acid When confirmed by the measurement of ³¹ P-NMR, it was found that the phosphate triester was the main component and a trace amount of phosphate diester was detected, and the peak integral ratio of the phosphate triester was 95% or more. 12.80 parts by mass, multifunctional acrylate monomer (trade name: ALONIX M402, manufactured by Toagosei Co., Ltd.) 6.40 parts by mass, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- ON (trade name: Irgacure 907, manufactured by BASF) 6.00 parts by mass, 2,4 diethylthioxanthone (trade name: Kayacure DETX-S, Binder composition B (solid content: 40% by mass) was prepared by mixing 2.00 parts by mass of Nippon Kayaku Co., Ltd.).

Preparation Example 3 Preparation of Binder Composition C
51.33 parts by mass of PGMEA, 4.18 parts by mass of binder resin A (solid content 45% by mass) of Synthesis Example 2, 4.39 parts by mass of multifunctional acrylate monomer (trade name: ARONIX M305, manufactured by Toagosei Co., Ltd.), alkylphenone 0.47 parts by mass of a photoinitiator (trade name: Irgacure 907, manufactured by BASF), 0.94 parts by mass of an imidazole-based photoinitiator (trade name: biimidazole, manufactured by Kurogane Kasei), 2,4 diethylthioxanthone (trade name) Binder composition C (solid content: 17.5% by mass) by mixing 1.57 parts by mass of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) and 0.15 parts by mass of 2-mercaptobenzothiazole (manufactured by Tokyo Kasei Co., Ltd.) Was prepared.

(Example 14)
(1) Preparation of Colorant Dispersion Liquid 10.00 parts by mass of blue coloring material α of Synthesis Example 1 as a colorant and 19.76 parts by mass of a salt type amine graft copolymer A solution (solid content: 5.00 parts by mass B) 6.67 parts by mass (solid content: 3.00 parts by mass) of binder resin A of Synthesis Example 2 and 63.57 parts by mass of PGMEA are mixed and 1 mm with 2 mm zirconia beads as preliminary dispersion with a paint shaker (manufactured by Asada Iron Works) Further, the resultant was dispersed for 3 hours with 0.1 mm zirconia beads as main dispersion, to obtain a colorant dispersion.
(2) Preparation of colored resin composition 41.70 parts by mass of the obtained coloring material dispersion, 24.24 parts by mass of binder composition A of Preparation Example 1, 34.01 parts by mass of PGMEA, surfactant R08MH (manufactured by DIC) 0.05 parts by mass was added and mixed, and pressure filtration was performed to obtain a colored resin composition.

(Examples 15-18, comparative examples 8-9)
(1) Preparation of Colorant Dispersion In preparation of the colorant dispersion of Example 14, a dispersant solution containing a dispersant shown in Tables 4 and 5 in place of the salt type amine graft copolymer A solution A colorant dispersion was obtained in the same manner as in Example 14 except that the above was used.
(2) Preparation of Colored Resin Composition In the preparation of the colored resin composition of Example 14, the colored resin composition of Example 14 was used except that the colorant dispersion containing the dispersant shown in Table 4 and Table 5 was used. A colored resin composition was obtained in the same manner as in the preparation of the product.

(Examples 19 to 20, Comparative Example 10)
(1) Preparation of Colorant Dispersion In preparation of the colorant dispersion of Example 14, a dispersant solution containing a dispersant shown in Table 6 was used in place of the salt type amine graft copolymer A solution. A colorant dispersion was obtained in the same manner as in Example 14 except for the above.
(2) Preparation of colored resin composition 41.70 parts by mass of the obtained coloring material dispersion, 24.24 parts by mass of binder composition B of Preparation Example 2, 34.01 parts by mass of PGMEA, surfactant R08MH (manufactured by DIC) 0.05 parts by mass was added and mixed, and pressure filtration was performed to obtain a colored resin composition.

(Example 21)
(1) Preparation of Colorant Dispersion Liquid 10.00 parts by mass of FASTOGEN Green A110 manufactured by DIC as a colorant and 16.00 parts by mass of a solution of salt type amine block copolymer F (solid content: 4.00 parts by mass) A binder resin A 8.89 parts by mass (solid content: 4.00 parts by mass) of Synthesis Example 2 and 65.11 parts by mass of PGMEA are mixed, and pre-dispersed in a paint shaker (Asada Iron Works) for 1 hour with 2 mm zirconia beads. Further, as a main dispersion, dispersion was performed with 0.1 mm zirconia beads for 2 hours to obtain a colorant dispersion.
(2) Preparation of colored resin composition 42.86 parts by mass of the obtained coloring material dispersion, 41.63 parts by mass of binder composition C of Preparation Example 3, 15.46 parts by mass of PGMEA, surfactant R08MH (manufactured by DIC) 0 05 parts by mass was added and mixed, and pressure filtration was performed to obtain a colored resin composition.

(Comparative example 11)
The procedure of Example 21 is repeated, except that 16.00 parts by mass (solid content: 4.00 parts by mass) of the salt type amine block copolymer G solution is used instead of the salt type amine block copolymer F solution. In the same manner as in Example 21, a colorant dispersion and a colored resin composition were obtained.

(Evaluation)
<Colorant dispersion stability>
As evaluation of colorant dispersion stability, the blue colorant dispersion obtained in Examples and Comparative Examples shown in Table 4 is allowed to stand at 40 ° C. for one week, and the color in the above colorant dispersion before and after standing. The average particle size and shear viscosity of the wood particles were measured. Measure the average particle size using Nikkiso "Nanotrack particle size distribution meter UPA-EX150", for viscosity measurement using Anton Paar "Rheometer MCR301", measure the shear viscosity at a shear rate of 60 rpm did. The results are shown in Table 4.

<Optical performance evaluation, heat resistance evaluation>
The colored resin compositions obtained in the examples and comparative examples shown in Tables 4, 5 and 6 were applied on a glass substrate having a thickness of 0.7 mm (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd.) using a spin coater. Applied. Then, it heat-dried on the 80 degreeC hotplate for 3 minutes. The cured film was obtained by irradiating an ultraviolet ray of 40 mJ / cm ² using an extra-high pressure mercury lamp. The film thickness after drying and curing is adjusted to achieve the target chromaticity y = 0.082, and the chromaticity (x, y), luminance (Y), L, a, b (L ₀ ) of the obtained colored substrate are obtained. , A ₀ , b ₀ ) were measured using a “microspectroscopic measurement apparatus OSP-SP200” manufactured by Olympus. The above colored substrate was post-baked for 60 minutes in a clean oven at 230 ° C., and the contrast and chromaticity (x, y), luminance (Y) and L, a, b (L ₁ , a ₁ ) of the obtained colored film were obtained , B ₁ ) was measured. For the measurement of contrast, “Contrast measurement apparatus CT-1B” manufactured by Takasaka Electric Co., Ltd.
As evaluation of heat resistance was calculated color difference before and after post-baking the (AEab ₁₎ from the following equation.
ΔEab ₁ = {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² } ^1/2
The results are shown in Tables 4, 5 and 6.

<Optical performance evaluation, heat resistance evaluation>
For the colored resin compositions obtained in Examples and Comparative Examples shown in Table 7, the film thickness after drying and curing should be the target chromaticity y = 0.500 in the above-mentioned optical performance evaluation and heat resistance evaluation. And the post-baking treatment was performed at 230 ° C. for 30 minutes in the same manner as the above-described optical performance evaluation and heat resistance evaluation, except that the contrast and chromaticity (x, y) and luminance ( Y) was measured, and a color difference (ΔEab ₁ ) before and after post-baking was determined as heat resistance evaluation. The results are shown in Table 7.

<Evaluation of adhesion>
In the colored resin compositions obtained in Examples and Comparative Examples shown in Tables 6 and 7, the colored film after post-baking treatment obtained in the above-described optical performance evaluation and heat resistance evaluation is based on JIS K5600. The cross cut tape peeling test was performed, and the adhesion was evaluated according to the following evaluation criteria.
(Adhesive evaluation criteria)
A: Cross-cut grid-like eyes remain.
B: The film itself peels off.

<Solvent resolubility evaluation>
The colored resin compositions obtained in Examples and Comparative Examples shown in Table 7 are applied by dip coating on the surface of a glass substrate (100 mm × 5 mm × 0.7 mm), and 30 at a temperature of 23 ° C. and a humidity of 80% RH. It was dried by standing for a minute to form a dried coating. The obtained glass test piece (dried coating film) was immersed in PGMEA, and the dried coating film was redissolved by stirring for 15 seconds. The state of re-dissolution of the dried coating was visually confirmed, and the solvent re-solubility was evaluated according to the following evaluation criteria.
(Solvent resolubility evaluation criteria)
A: Dissolve in PGMEA solution without peeling off.
B: Peeling pieces remain or do not dissolve in PGMEA solution.

<Evaluation of solvent resistance>
In the colored resin compositions obtained in the Examples and Comparative Examples shown in Table 7, after the post-baking colored film obtained in the above-described optical performance evaluation and heat resistance evaluation, the film is immersed in NMP for 30 minutes, and then the film The surface was observed, and the solvent resistance was evaluated according to the following evaluation criteria.
(Standard for evaluating solvent resistance)
A: No change.
B: The film surface peels off.

(Summary of results)
As shown in Tables 4 to 7, the colored layer of the example formed using the polymer dispersant of the present disclosure has high luminance and small change in chromaticity before and after post-baking as compared with the comparative example. , Was thinner. Furthermore, among the examples, the polymer dispersion used has a large content ratio of t-butyl group, and the stronger the IR peak intensity derived from the acid anhydride group after heating, the obtained colored layer has heat resistance It was revealed that the thickness was high, the change in chromaticity before and after post-baking was small, and the film was thinned. Further, as shown in Table 6, the colored layer of the example formed using the polymer dispersant of the present disclosure is excellent in adhesion to the substrate even when using a phosphorus atom-containing polyfunctional monomer. It was In addition, as shown in Table 7, the colored layer of the example formed using the polymer dispersant of the present disclosure has excellent solvent resolubility while having solvent resistance and adhesion to a substrate. It was also excellent.

DESCRIPTION OF SYMBOLS 1 transparent substrate 2 light-shielding part 3 colored layer 10 color filter 13a, 13b alignment film 15 liquid crystal layer 20 opposing substrate 25a, 25b polarizing plate 30 back light 40 liquid crystal display 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 Light emitter 100 Light emitting display

Claims (11)

It is a copolymer having a constitutional unit represented by the following general formula (I), and at least a part of the nitrogen moiety contained in the constitutional unit represented by the above general formula (I) may form a salt. Before and after heating at 230 ° C. for 5 minutes or more, in the infrared absorption spectrum, the peak intensity derived from at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group decreases, and the peak intensity derived from the acid anhydride group Polymeric dispersants to increase.
(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a divalent linking group, Q represents a nitrogen site, and the nitrogen site Q is represented by the following general formula (I-a) Or a nitrogen-containing heterocyclic group which may have a substituent.
(In the general formula (I-a), R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom.) At least a nitrogen portion contained in the constituent unit represented by the general formula (I), which has a constituent unit represented by the general formula (I) and a constituent unit represented by the following general formula (II) It is a block copolymer which may partially form a salt, or has a constitutional unit represented by the above general formula (I) and a constitutional unit represented by the following general formula (III), The polymer dispersing agent of Claim 1 which is a graft copolymer in which at least one part of the nitrogen site | part contained in the structural unit represented by the said General formula (I) may have formed the salt.
(In General Formula (II), R ⁴ represents a hydrogen atom or a methyl group, and R ^P represents a monovalent protecting group represented by the following General Formula (A).
In formula (III), R ⁵ represents a hydrogen atom or a methyl group, L ² represents a direct bond or a divalent linking group, and Polymer has a polymer chain having a constitutional unit represented by the following formula (IV) Represent. )
(In general formula (A), R ^P1 represents a carbon atom or a silicon atom, R ^P2 , R ^P3 and R ^P4 each independently represent a hydrogen atom or a hydrocarbon group, R ^P5 represents a hydrocarbon group or a hydrocarbon group or It represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)
(In general formula (IV), R ⁶ represents a hydrogen atom or a methyl group, and R ^{P ′} represents a monovalent protecting group represented by the following general formula (A ′). N is an integer of 5 or more and 200 or less Represents
(In the general formula (A '), ^{R P'1} represents a carbon atom or a silicon atom, ^{R P'2, R P'3} and ^{R P'4} each independently represent a hydrogen atom or a hydrocarbon group , ^{R P'5} represents a hydrocarbon group or -OR ^{P'6, R P'6} is .R ^P'4 and ^{R P'5} represents a hydrocarbon group bonded to form a ring system with one another Also good.)   The copolymer further contains a hydrocarbon group which may contain an -O- bond, which is derived from a monomer having a glass transition temperature (Tgi) of a homopolymer of less than 50 ° C. The polymeric dispersing agent of Claim 1 or 2 which has a structural unit to contain.   The copolymer according to claim 3, wherein the copolymer further has a structural unit containing a hydrocarbon group in a side chain, which is derived from a monomer having a glass transition temperature (Tgi) of 50 ° C or higher for a homopolymer. Polymeric dispersant as described.   The polymer dispersant according to any one of claims 1 to 4, which contains (A) a colorant, (B) a dispersant, and (C) a solvent, and the (B) dispersant is any one of claims 1 to 4. , Colorant dispersion.   The color material dispersion liquid according to claim 5, wherein the (A) color material is a metal lake color material of a dye.   A colored resin composition comprising the coloring material dispersion according to claim 5 or 6, (D) an alkali soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator.   The colored resin composition according to claim 7, wherein the (E) polyfunctional monomer contains a phosphorus atom-containing polyfunctional monomer.   A color filter comprising: a transparent substrate; and a colored layer on the transparent substrate, wherein at least one of the colored layers is a cured product of the colored resin composition according to claim 7 or 8.   A liquid crystal display device comprising the color filter according to claim 9, a counter substrate, and a liquid crystal layer positioned between the color filter and the counter substrate.   A light emitting display device comprising the color filter according to claim 9 and a light emitter.