JP2017057380A - Curable composition, cured film, display element and solid- state imaging device, and compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition having good dispersibility and storage stability, excellent in chromaticity property, heat resistance and solvent resistance and enabling a cured film having suppressed generation of debris to be formed.SOLUTION: There is provided the curable composition which contains (A) at least one kind selected from a pigment and a metal oxide particle, (B) a dispersant and (C) at least one kind selected from a binder resin and a polymerizable compound, and in which the (B) dispersant contains a compound represented by formula (1), where m is an integer of 1 or more, n is an integer of 2 or more, Pis a polymer chain having one or more kind of group selected from a specific property group α, Pis a polymer chain having no group selected from a specific property group α and X is a (m+n) valent connecting group.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, a cured film, a display element, a solid-state imaging element, and a compound, and more particularly, a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, and electronic paper. A compound suitably used for producing a cured film used in, etc., a curable composition containing the compound, a cured film produced using the curable composition, and a display element and a solid comprising the cured film The present invention relates to an image sensor.

  In manufacturing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. (Hereinafter, referred to as “exposure”) and a method of obtaining pixels of each color by development (Patent Documents 1 and 2) is known. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known. Furthermore, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known.

  By the way, in the field of color filters used for liquid crystal display elements and solid-state image sensors, pigments used tend to be increasingly atomized with the demand for higher brightness and higher contrast. It is known that the use of a dispersant is effective for realizing such stable and good dispersion of the atomized pigment. Various methods (Patent Documents 3 and 4) for improving the dispersibility of a pigment by using such a dispersant and improving not only contrast and dispersion stability but also developability have been proposed.

  Moreover, when manufacturing a color filter, since it passes through the post-baking process at the high temperature over 200 degreeC, high heat resistance is also calculated | required. If the heat resistance is insufficient, the color filter after the post-baking process may be discolored or foreign matter may be generated in the color filter.

JP-A-2-144502 JP-A-3-53201 JP 2003-26949 A JP 2009-25813 A

However, even with the conventional method, it is difficult to realize the recent demand for higher contrast of color liquid crystal display elements and higher definition of solid-state imaging elements, and high heat resistance of color filters cannot be expected. Is the actual situation. Therefore, in order to realize high contrast of liquid crystal display elements and high definition of solid-state imaging elements at a high level, it has good dispersibility and storage stability, and excellent chromaticity characteristics, heat resistance and solvent resistance. Development of a curable composition capable of forming a cured film in which the generation of foreign matters during the formation of a coating film is suppressed is strongly demanded.
Therefore, an object of the present invention is to provide a curable composition capable of forming a cured film having good dispersibility and storage stability, excellent chromaticity characteristics, heat resistance and solvent resistance, and suppressing generation of foreign matter. Is to provide. Another object of the present invention is to provide a compound useful for the curable composition, a cured film produced using the curable composition, and a display device and a solid-state imaging device including the cured film.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by including a dispersant having a specific structure in the curable composition.

That is, the present invention
(A) at least one selected from pigments and metal oxide particles,
A curable composition containing (B) a dispersant, and (C) at least one selected from a binder resin and a polymerizable compound, wherein (B) the compound represented by the following formula (1) ( Hereinafter, a curable composition containing a “specific dispersant” is also provided.

The present invention also provides a cured film produced using the above curable composition, and a display element and a solid-state imaging device comprising the cured film. Here, the “cured film” means each color pixel, protective film, black matrix, spacer, insulating film, and the like used for a display element or a solid-state imaging element.
The present invention further provides a compound represented by the following formula (1).

[In Formula (1),
m represents an integer of 1 or more,
n represents an integer of 2 or more,
P ¹ represents a polymer chain having at least one group selected from the following characteristic group α.
P ² represents a polymer chain having no group selected from the following characteristic group α.
X represents a (m + n) -valent linking group.
(Characteristic group α)
Sulfonic acid group, monosulfate group, phosphoric acid group, monophosphate group, boric acid group, urea group, urethane group, group having a coordinating oxygen atom, group having a basic nitrogen atom, alkylaminocarbonyl group, Sulfonamide group, oxygen-containing heterocyclic group, sulfur-containing heterocyclic group, imide group, alkoxysilyl group, oxiranyl group, isocyanate group, hydroxyl group. ]

  According to the present invention, there is provided a curable composition capable of forming a cured film having good dispersibility and storage stability, excellent chromaticity characteristics, heat resistance and solvent resistance, and suppressing generation of foreign matter. can do. Therefore, the curable composition of the present invention is suitable for producing various color filters including color liquid crystal display elements, color separation color filters for solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably.

Hereinafter, the present invention will be described in detail.
Curable composition The curable composition of this invention contains a component (A), a component (B), and a component (C). Hereafter, the structural component of the curable composition of this invention is demonstrated in detail.

-Component (A)-
Component (A) is at least one selected from pigments and metal oxide particles.
The pigment is preferably an organic pigment, and the color and material can be appropriately selected according to the use of the curable composition. You may use a pigment in combination of 1 type, or 2 or more types. Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), and more specifically, the following color index (C.I. ) Names can be mentioned.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Yellow pigments such as CI Pigment Yellow 215;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Orange pigments such as CI Pigment Orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 269, C.I. I. Red pigments such as CI Pigment Red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Purple pigments such as CI Pigment Violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment blue 79, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Green pigments such as CI Pigment Green 59;
C. I. Pigment brown 23, C.I. I. Brown pigments such as CI Pigment Brown 25;
C. I. Pigment black 1, C.I. I. Black pigments such as CI Pigment Black 7.

  In the present invention, lake pigments may be used alone or in combination of two or more. Here, “lake pigment” refers to a soluble dye made into an insoluble pigment by a precipitating agent. Examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, and lead acetate. Tannic acid, katanol, tamol, isopolyacid, heteropolyacid, and the like. Examples of lake pigments include those with the following color index (CI) names.

C. I. Pigment yellow 61, C.I. I. Pigment yellow 61: 1, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 133, C.I. I. Pigment yellow 169, C.I. I. Pigment yellow 183, C.I. I. Pigment yellow 191, C.I. I. Pigment yellow 191: 1, C.I. I. Pigment yellow 206, C.I. I. Pigment yellow 209, C.I. I. Pigment yellow 209: 1, C.I. I. Pigment yellow 212;

C. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 48: 5, C.I. I. Pigment red 49, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 49: 3, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 52: 2, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 54, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58, C.I. I. Pigment red 58: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 3, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 63: 3, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 68, C.I. I. Pigment red 81, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 200, C.I. I. Pigment red 237, C.I. I. Pigment red 239, C.I. I. Pigment red 247;

C. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 3: 1, C.I. I. Pigment violet 3: 3, C.I. I. Pigment violet 27, C.I. I. Pigment violet 39;
C. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 14, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 24, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 56, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62;
C. I. Pigment green 1, C.I. I. Pigment Green 4.

  Moreover, when using a pigment, a pigment can also be refine | purified and used by a recrystallization method, a reprecipitation method, a solvent washing | cleaning method, a sublimation method, a vacuum heating method, or these combinations as desired. Furthermore, the pigment may be used by modifying the particle surface with a resin if desired. Examples of the resin used for modifying the pigment include a vehicle resin described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. Further, the pigment may be used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be employed.

  Furthermore, in this invention, you may contain dye in the range which does not impair the effect of this invention. The dyes can be used alone or in combination of two or more. Examples of the dye include compounds having the following color index (CI) names.

C. I. Acid Yellow 1, C.I. I. Acid Yellow 3, C.I. I. Acid Yellow 11, C.I. I. Basic Yellow 1, C.I. I. Basic Yellow 11, C.I. I. Basic Yellow 13, C.I. I. Basic Yellow 21, C.I. I. Basic Yellow 28, C.I. I. Basic Yellow 51, C.I. I. Direct Yellow 12, C.I. I. Reactive Yellow 1, C.I. I. Reactive Yellow 2, C.I. I. Moldant Yellow 5, C.I. I. Solvent Yellow 33, C.I. I. Disperse Yellow 64, C.I. I. Disperse Yellow 42, C.I. I. Yellow dyes such as Disperse Yellow 201;
C. I. Acid Orange 7, C.I. I. Direct Orange 26, C.I. I. Disperse Orange 5, C.I. I. Orange dye such as Acid Orange 3;
C. I. Acid Red 37, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 180, C.I. I. Acid Red 289, C.I. I. Acid Red 388, C.I. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Basic Red 14, C.I. I. Basic Red 18, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Disperse thread 58, C.I. I. Molded Red 7, C.I. I. Red dye such as Disperse Red 60;
C. I. Acid Blue 7, C.I. I. Acid Blue 29, C.I. I. Acid Blue 40, C.I. I. Basic Blue 1, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Basic Blue 7, C.I. I. Basic Blue 9, C.I. I. Basic Blue 11, C.I. I. Basic Blue 26, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60, C.I. I. Pat Blue 4, C.I. I. Blue dyes such as pad blue 5;
C. I. Acid Green 25, C.I. I. Basic Green 1, C.I. I. Basic Green 4, C.I. I. Direct Green 28, C.I. I. Green dyes such as Direct Green 59;
C. I. Basic violet 1, C.I. I. Basic violet 3, C.I. I. Basic Violet 7, C.I. I. Basic Violet 11, C.I. I. Basic violet 14, C.I. I. Purple dye such as Basic Violet 16.
C. I. Reactive Black 5, C.I. I. Black dye such as Moldant Black 7.

Next, the metal oxide particles will be described.
The metal oxide constituting the metal oxide particles is an oxide with a metal that does not contain a nonmetallic element other than oxygen. Examples of the metal oxide include zinc oxide, silicon oxide, aluminum oxide, zirconium dioxide, titanium oxide, cerium dioxide, tungsten oxide, yttrium oxide, indium oxide, tin oxide, or these metal oxides doped with other metals. Can be mentioned. The metal oxide particles can be used alone or in combination of two or more. Among these, tungsten oxide is preferable as the metal oxide. Since infrared rays can be absorbed by containing tungsten oxide, infrared absorption can be imparted to the curable composition. Tungsten oxide is preferably cesium tungsten oxide or rubidium tungsten oxide, and more preferably cesium tungsten oxide. The composition formula of cesium tungsten oxide includes Cs _0.33 WO _{3 and the} like, and the composition formula of rubidium tungsten oxide includes Rb _0.33 WO _{3 and the} like. The tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd.

As for the particle diameter of the metal oxide particles, the average particle diameter (d ₅₀ ) of the primary particles is preferably 1 to 100 nm, more preferably 5 to 80 nm, and still more preferably 10 to ₅₀ nm. The “average particle diameter” as used herein refers to a particle diameter corresponding to a cumulative value of 50% (d ₅₀ ) in a volume-based cumulative particle size distribution measured using a dynamic light scattering method.

  When a pigment is included as the component (A), the content of the pigment is improved in dispersibility and storage stability, and is excellent in chromaticity characteristics, heat resistance and solvent resistance, and formation of a cured film in which the generation of foreign matter is suppressed. In view of the above, it is usually 5 to 70% by mass, preferably 10 to 60% by mass in the solid content of the curable composition. Further, when the metal oxide particles are included as the component (A), the content of the metal oxide particles is usually cured from the viewpoint of improving the dispersibility and storage stability and forming a cured film excellent in infrared shielding ability. It is 10-80 mass% in the solid content of an adhesive composition, Preferably it is 30-60 mass%. Here, solid content is components other than the solvent mentioned later.

-Component (B)-
The component (B) contains a specific dispersant, that is, a compound represented by the following formula (1).

[In Formula (1),
m represents an integer of 1 or more,
n represents an integer of 2 or more,
P ¹ represents a polymer chain having at least one group selected from the following characteristic group α (hereinafter also referred to as “polymer chain P ¹ ”),
P ² represents a polymer chain having no group selected from the following characteristic group α (hereinafter also referred to as “polymer chain P ² ”),
X represents a (m + n) -valent linking group.
(Characteristic group α)
Sulfonic acid group, monosulfate group, phosphoric acid group, monophosphate group, boric acid group, urea group, urethane group, group having a coordinating oxygen atom, group having a basic nitrogen atom, alkylaminocarbonyl group, Sulfonamide group, oxygen-containing heterocyclic group, sulfur-containing heterocyclic group, imide group, alkoxysilyl group, oxiranyl group, isocyanate group, hydroxyl group. ]

The compound represented by the formula (1) is a branched compound having, as branches, a core part X having three or more bonds, a polymer chain P ¹ and a polymer chain P ² linked to the core part. Since the polymer chain P ¹ has at least one group selected from the characteristic group α having the ability to adsorb to the component (A) (hereinafter also referred to as “characteristic group α”), the adsorption site for the component (A) The polymer chain P ² functions as a compatible site. Then, a plurality of polymer chains P ² repel each other, thereby improving the dispersibility of the component (A), since the aggregation or the like of the component (A) is suppressed, dispersion Ya comprising components (A) It is presumed that the dispersibility, storage stability, etc. of the curable composition are improved.

First, the polymer chain P ¹ represented by P ¹ in Formula (1) will be described.
The polymer chain P ¹ has a characteristic group α, that is, a sulfonic acid group, a monosulfate group, a phosphate group, a monophosphate group, a boric acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a base At least one group selected from a group having a reactive nitrogen atom, an alkylaminocarbonyl group, a sulfonamide group, an oxygen-containing heterocyclic group, a sulfur-containing heterocyclic group, an imide group, an alkoxysilyl group, an oxiranyl group, an isocyanate group, and a hydroxyl group It is what has. The characteristic group α may have a substituent.

As the monosulfate group, a monoalkyl sulfate group having 1 to 8 carbon atoms and a monoaryl sulfate group having 6 to 14 carbon atoms are preferable. Examples of the monoalkyl sulfate group having 1 to 8 carbon atoms include a monomethyl sulfate group, a monoethyl sulfate group, a monopropyl sulfate group, a monobutyl sulfate group, a monopentyl sulfate group, a monohexyl sulfate group, and a monoheptyl sulfate group. Examples include ester groups and monooctyl sulfate ester groups. Moreover, as a C6-C14 monoaryl sulfate group, a phenyl sulfate group is mentioned, for example.
As the monophosphate group, a monoalkyl phosphate group having 1 to 8 carbon atoms is preferable, and examples thereof include a phosphoric acid methyl ester group, a phosphoric acid ethyl ester group, a phosphoric acid propyl ester group, and a phosphoric acid butyl ester group. It is done.
As the urea group, for example, —NR ²¹ CONR ²² R ²³ (where R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 or more carbon atoms). Group hydrocarbon group). R ²¹ and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and R ²² is preferably a hydrogen atom, R ²¹ and R ²² are each a hydrogen atom, and R ²³ is more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

As the urethane group, for example, —NHCOOR ²⁴ , —NR ²⁵ COOR ²⁶ , —OCONHR ²⁷ , —OCONR ²⁸ R ²⁹ (however, R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are mutually independent). And an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 or more carbon atoms.). Among them, —NHCOOR ²⁴ and —OCONHR ²⁷ are preferable. In this case, R ²⁴ and R ²⁷ are each independently preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.

Examples of the group having a coordinating oxygen atom include an acetylacetonato group and a crown ether.
Examples of the group having a basic nitrogen atom include an amino group (—NH ₂ ), an N-substituted amino group (—NHR ³⁰ , —NR ³¹ R ³² , where R ³⁰ , R ³¹ , and R ³² are independent of each other. And a group having a chain or cyclic hydrocarbon group which may have a substituent.), A guanidyl group, a triazinyl group, an amidinyl group, and the like. The group having a basic nitrogen atom may be in the form of an ammonium salt, and R ³¹ and R ³² may be bonded to each other to form a cyclic structure. Examples of the chain or cyclic hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 14 carbon atoms. Examples of the substituent of the hydrocarbon group include those exemplified in the description of the repeating unit represented by the following formula (2) or formula (3).
The alkyl group moiety in the alkylaminocarbonyl group is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
In the sulfonamide group, a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group) or an acyl group (such as an acetyl group or a trifluoroacetyl group).

The oxygen-containing heterocyclic group and the sulfur-containing heterocyclic group may be monocyclic or polycyclic, and may be an unsaturated ring or a saturated ring. As the oxygen-containing heterocyclic group, an oxygen-containing heterocyclic group having 3 to 10 carbon atoms is preferable, and examples thereof include a furyl group, a pyranyl group, and a benzofuryl group. Moreover, as a sulfur-containing heterocyclic group, a C3-C10 sulfur-containing heterocyclic group is preferable, for example, a thienyl group, a dithiolanyl group, etc. are mentioned.
Examples of the imide group include succinimide, phthalimide, naphthalimide, and the like.

  Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. Of these, a trialkoxysilyl group is preferable, and examples thereof include a trimethoxysilyl group and a triethoxysilyl group.

Among them, the polymer chain P ¹ is preferably a polymer chain having a group having a basic nitrogen atom, and more preferably a polymer chain having a group having an amino group or an N-substituted amino group.

The characteristic group α of the polymer chain P ¹ may be bonded to a divalent linking group. Examples of the divalent linking group include a divalent hydrocarbon group, a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of the divalent hydrocarbon group, -O-, -S. -, - CO -, - COO -, - CONH -, - SO 2 - and the like.
Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be either linear or branched, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Good. The position of the unsaturated bond of the unsaturated hydrocarbon group may be either in the molecular chain or at the end of the molecular chain, and can be at any position. Here, in the present specification, the “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. In addition, in this specification, “alicyclic hydrocarbon group” and “aromatic hydrocarbon group” are not only a group consisting of only a ring structure, but also a divalent aliphatic hydrocarbon group substituted on the ring structure. In other words, the structure includes at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

  Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group. Carbon number of a bivalent aliphatic hydrocarbon group becomes like this. Preferably it is 1-30, More preferably, it is 2-20, More preferably, it is 2-10. Specific examples of the alkanediyl group include, for example, a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, Propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4 -Diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane- Specific examples of the alkenediyl group include, for example, ethene-1,1-diyl group, ethene-1,2-diyl group, propene-1,2-diyl group, propene- 1,3-diyl group, propene-2, -Diyl group, 1-butene-1,2-diyl group, 1-butene-1,3-diyl group, 1-butene-1,4-diyl group, 2-pentene-1,5-diyl group, 3- Examples include hexene-1,6-diyl group.

Examples of the divalent alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group. Carbon number of a bivalent alicyclic hydrocarbon group becomes like this. Preferably it is 3-20, More preferably, it is 3-12, More preferably, it is 3-6. Specific examples of the cycloalkylene group include, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and the like. Specific examples of the cycloalkenylene group include, for example, a cyclobutenylene group and a cyclopentenylene. Group, cyclohexenylene group and the like. The divalent alicyclic hydrocarbon group is a bridge of norbornylene group such as 1,4-norbornylene group or 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group or the like. It may be a cyclic hydrocarbon group.
Examples of the divalent aromatic hydrocarbon group include an arylene group. Carbon number of a bivalent aromatic hydrocarbon group becomes like this. Preferably it is 6-20, More preferably, it is 6-14, More preferably, it is 6-10. Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.

Examples of the linking group between the C—C bonds of the divalent hydrocarbon group include —O—, —S—, —CO—, —COO—, —CONH—, —SO ₂ — and the like. be able to. The divalent hydrocarbon group may have a substituent within a range not departing from the gist of the present invention. The position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different. Examples of the substituent include a halogen atom, hydroxyl group, cyano group, formyl group, nitro group, amino group, dialkylamino group, diarylamino group, alkoxy group, alkoxycarbonyl group, alkylthio group, arylthio group, and trialkylsilyl group. Etc.

The polymer chain P ¹ can adopt an appropriate structure as long as it has one or more characteristic groups α, but preferably has a monomer having an ethylenically unsaturated double bond group as a repeating unit together with the characteristic group α. Examples of the ethylenically unsaturated double bond group include a vinyl group, a propenyl group, a (meth) acryl group, a styryl group, an α-methylstyryl group, and among them, a (meth) acryl group is preferable. As such a monomer, an ethylenically unsaturated monomer having a characteristic group α can be appropriately selected and used. For example, as an ethylenically unsaturated monomer having a sulfonic acid group, 2- Acrylamide-2-methylpropanesulfonic acid and the like, and as the ethylenically unsaturated monomer having a phosphoric acid group, phosphoric acid mono (2-acryloyloxyethyl ester), phosphoric acid mono (1-methyl-2- Acryloyloxyethyl ester) and the like.

Among them, the polymer chain P ¹ has the characteristic group α from the viewpoint of forming a cured film that is excellent in dispersibility and storage stability, and excellent in chromaticity characteristics, heat resistance and solvent resistance, and in which generation of foreign matters is suppressed. The ethylenically unsaturated monomer having a repeating unit preferably has at least one selected from the group consisting of a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3). .

[In Formula (2),
R ^{1 to} R ³ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and two or more of R ^{1 to} R ³ are bonded to each other. To form a ring structure,
R ⁴ represents a hydrogen atom or a methyl group,
Q represents a divalent linking group,
Y ⁻ represents a counter anion. ]

[In Formula (3),
R ⁵ and R ⁶ each independently represent a hydrogen atom or a chain-like or cyclic hydrocarbon group which may have a substituent, and R ⁵ and R ⁶ are bonded to each other to form a cyclic structure You may,
R ⁷ represents a hydrogen atom or a methyl group,
Z represents a divalent linking group. ]

Examples of the hydrocarbon group of the ^{R 1} ~R ^3, R ⁵ and ^{R 6,} an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, a methyl group, an ethyl group, a propyl group More preferred are a butyl group and a benzyl group.
Among the substituents of the hydrocarbon group according to R ^{1 to} R ³ , R ⁵ and R ⁶ , examples of the substituent of the chain hydrocarbon group include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. Examples of the substituent for the cyclic hydrocarbon group include a chain alkyl group, a halogen atom, an alkoxy group, and a hydroxyl group. The chain hydrocarbon group includes both straight chain and branched chain groups.

Examples of the cyclic structure formed by bonding two or more of R ^{1 to} R ³ to each other include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done. Such nitrogen-containing heterocycle is preferably non-aromatic and more preferably a saturated ring. Specific examples include a cyclic structure represented by the following formula (I). These cyclic structures may have a substituent.

(In the formula (I), R is any one of R ^{1 to} R ^3. )

In the formula (2), examples of the cyclic structure formed by bonding R ⁵ and R ⁶ to each other include, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensation product of two of these. A ring is mentioned. Such nitrogen-containing heterocycle is preferably non-aromatic and more preferably a saturated ring. Specific examples include a cyclic structure represented by the following formula (II). These cyclic structures may have a substituent.

Examples of the divalent linking groups Q and Z include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a —CONH—R ¹¹ — group, a —COO—R ¹² — group (provided that R ¹¹ and R ¹² each independently represent a single bond, a divalent aliphatic hydrocarbon group, or a divalent hydrocarbon group having —O— between C—C bonds. Among these, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 14 carbon atoms, a —CONH—R ¹¹ — group, a —COO—R ¹² — group, and the like are preferable, and a —COO—R ¹² — group is preferable. More preferred. R ¹¹ and R ¹² are preferably a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an alkyloxyalkyl group having 2 to 10 carbon atoms.
Examples of Y ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

Examples of the monomer that gives the repeating unit represented by the formula (2) include (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (Meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride and the like.
Examples of the monomer that gives the repeating unit represented by the formula (3) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like. Is mentioned. The repeating unit represented by the formula (2) is obtained by polymerizing a monomer that gives the repeating unit represented by the formula (3) and then reacting the polymer with a halogenated hydrocarbon compound such as benzyl chloride. It can also be introduced by partially quaternizing the amino group.

The polymer chain P ¹ may have an ethylenically unsaturated monomer having a characteristic group other than the characteristic group α as a repeating unit. As a monomer that gives such a repeating unit, for example,
o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p -Aromatic vinyl compounds such as vinylbenzyl methyl ether;
Indene, indene compounds such as 1-methylindene;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) An ethylenically unsaturated monomer having an alkyloxycarbonyl group such as acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate;
Ethylenically unsaturated monomer having an alicyclic hydrocarbon group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate body;
Ethylenically unsaturated monomers having an aryloxycarbonyl group such as phenyl (meth) acrylate and benzyl (meth) acrylate;
An ethylenically unsaturated monomer having an alkyloxyalkyl group such as 2-methoxyethyl (meth) acrylate;
An ethylenically unsaturated monomer having an aryloxyalkyl group such as 2-phenoxyethyl (meth) acrylate;
Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, 3-[(meth) acryloyloxymethyl] -2-trifluoromethyloxetane, 3 Oxetanyl such as-[(meth) acryloyloxymethyl] -2-phenyloxetane, 2-[(meth) acryloyloxymethyl] oxetane, 2-[(meth) acryloyloxymethyl] -4-trifluoromethyloxetane An ethylenically unsaturated monomer having a group;
An ethylenically unsaturated monomer having a tetrahydrofuranyl group such as tetrahydrofurfuryl (meth) acrylate;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Polyethylene glycol (degree of polymerization 1-5) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 1-5) ethyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 1-5) propyl ether (meth) acrylate, polypropylene glycol (Polymerization degree 1-5) (poly) such as methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 1-5) ethyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 1-5) propyl ether (meth) acrylate Examples thereof include an ethylenically unsaturated monomer having an oxyalkylene alkyl ether group.
Monomers other than the ethylenically unsaturated monomer having the characteristic group α can be used alone or in combination of two or more, and are contained in any of random copolymerization and block copolymerization. It may be.

The proportion of the ethylenically unsaturated monomer having the characteristic group α in the polymer chain P ¹ is excellent in dispersibility and storage stability, and excellent in chromaticity characteristics, heat resistance and solvent resistance, and suppresses the generation of foreign matters. From the viewpoint of forming a cured film, 80% by mass or more is preferable, 90% by mass or more is more preferable, more preferably 100% by mass, that is, an ethylenically unsaturated monomer having a characteristic group α as a repeating unit. More preferably, it is a homopolymer.

The molecular weight of the polymer chain P ¹ is preferably 1000 to 20,000, more preferably 2000 to 15 in terms of Mw measured by gel permeation chromatography (GPC) from the viewpoint of improving dispersibility and storage stability. , 000. Further, the ratio (Mw / Mn) between Mw and Mn is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. As used herein, “Mw” refers to the polystyrene-equivalent weight average molecular weight measured with GPC (elution solvent: tetrahydrofuran), and “Mn” refers to the polystyrene equivalent measured with GPC (elution solvent: tetrahydrofuran). The number average molecular weight of

Next, the polymer chain P ² represented by P ² in the formula (1) will be described.
Polymer chains P ² is not particularly limited as long as it does not have a group selected from the characteristic group group alpha. Examples of the characteristic group other than the characteristic group α include, for example, a monovalent hydrocarbon group, alkoxy group, aryloxy group, carboxylic acid group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyloxyalkyl group, aryloxyalkyl group, An oxetanyl group, a tetrahydrofurfuryl group, a (poly) oxyalkylene alkyl ether group, and the like can be given.

  The monovalent hydrocarbon group may be any of a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. The monovalent aliphatic hydrocarbon group may be either linear or branched, and the monovalent aliphatic hydrocarbon group and the monovalent alicyclic hydrocarbon group are saturated carbon atoms. It may be a hydrogen group or an unsaturated hydrocarbon group. The position of the unsaturated bond of the unsaturated hydrocarbon group may be either in the molecular chain or at the end of the molecular chain, and can be at any position.

  Examples of the monovalent aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Carbon number of an aliphatic hydrocarbon group becomes like this. Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-12. Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, and nonyl. Group, decyl group, undecyl group, 1-methyldecyl group, dodecyl group, 1-methylundecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group, hexadecyl group And octadecyl group. Specific examples of the alkenyl group include, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, A 1-hexenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like can be mentioned. Specific examples of the alkynyl group include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, 2 -Octynyl group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like can be mentioned.

Examples of the monovalent alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. Can do. The number of carbon atoms of the monovalent aliphatic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, and still more preferably 3 to 12. Specific examples of the cycloalkyl group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Specific examples of the cycloalkenyl group include Examples thereof include a 1-cyclohexenyl group. Specific examples of the condensed polycyclic hydrocarbon group include tricyclodecanyl group, decahydro-2-naphthyl group, adamantyl group and the like. Specific examples of the bridged cyclic hydrocarbon group include, for example, Examples include tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, pentacyclopentadecanyl group, isobonyl group, dicyclopentenyl group, tricyclopentenyl group and the like. Furthermore, examples of the spiro hydrocarbon group include a monovalent group obtained by removing one hydrogen atom from spiro [3,4] heptane, spiro [3,4] octane, and the cyclic terpene hydrocarbon group. Examples thereof include a monovalent group obtained by removing one hydrogen atom from p-menthane, tsujang, curan and the like.

  Examples of the monovalent aromatic hydrocarbon group include an aryl group and an aralkyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylene group, an azulenyl group, and a 9-fluorenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, A trityl group etc. are mentioned.

As an alkoxy group, a C1-C6 alkoxy group is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group etc. can be mentioned.
The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group, a benzyloxy group, a tolyloxy group, a xylyloxy group, a naphthoxy group, and a dimethylnaphthoxy group.
The alkyloxycarbonyl group is preferably an alkyloxycarbonyl group having 2 to 7 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.
The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 6 to 15 carbon atoms, and examples thereof include a phenoxycarbonyl group, a p-methylphenoxycarbonyl group, a benzyloxycarbonyl group, and a naphthoxycarbonyl group.
The alkyloxyalkyl group is preferably an alkyloxyalkyl group having 2 to 10 carbon atoms, for example, a methoxymethyl group, a 2-methoxyethyl group, an ethoxymethyl group, a 2-ethoxyethyl group, or 2- (n-propoxy) ethyl. Group, 2- (n-isopropoxy) ethyl group, 2- (n-butoxy) ethyl group, 2-isobutoxyethyl group and the like.
The aryloxyalkyl group is preferably an alkyloxyalkyl group having 7 to 15 carbon atoms, and examples thereof include a phenoxymethyl group, a phenoxyethyl group, a benzyloxymethyl group, a benzyloxyethyl group, and a naphthyloxyethyl group.
Examples of the (poly) oxyalkylene alkyl ether group include polyethylene glycol (degree of polymerization 1 to 5) methyl ether group, polyethylene glycol (degree of polymerization 1 to 5) ethyl ether group, polyethylene glycol (degree of polymerization 1 to 5) propyl ether. Group, polypropylene glycol (degree of polymerization 1 to 5) methyl ether group, polypropylene glycol (degree of polymerization 1 to 5) ethyl ether group, polypropylene glycol (degree of polymerization 1 to 5) propyl ether group and the like.

Among them, the characteristic group other than the characteristic group α of the polymer chain P ² includes a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a carboxylic acid group, an alkyloxyalkyl group, an alkyloxycarbonyl group, It preferably has at least one group selected from the group consisting of an aryloxycarbonyl group, an oxetanyl group, a tetrahydrofurfuryl group, and a (poly) oxyalkylene alkyl ether group. A carboxylic acid group, an alkyloxycarbonyl group, an aryloxy group More preferably, it has at least one group selected from the group consisting of a carbonyl group, an oxetanyl group, a tetrahydrofurfuryl group, and a (poly) oxyalkylene alkyl ether group. A carboxylic acid group, an alkyloxycarbonyl group, an aryloxycarbonyl group. Group, oxetanyl group Tetrahydrofurfuryl group, and (poly) two or more selected from the group consisting of polyoxyalkylene alkyl ether groups, preferably more preferably has three or more groups.

Polymer chains P ^2, together with characteristic group other than characteristic group alpha, it is preferred to have as a repeating unit a monomer having an ethylenically unsaturated double bond group. Examples of the ethylenically unsaturated double bond group include those described above, and among them, a (meth) acryl group is preferable. Examples of the monomer that provides such a repeating unit include an ethylenically unsaturated monomer having a characteristic group other than the characteristic group α exemplified in the polymer chain P ¹ .
Among them, the polymer chain P ^2, ethylenically unsaturated monomer having a carboxylic acid group, ethylenically unsaturated monomer having an alkyloxycarbonyl group, an ethylenically unsaturated monomer having an aryloxycarbonyl group, A monomer selected from an ethylenically unsaturated monomer having an oxetanyl group, an ethylenically unsaturated monomer having a tetrahydrofurfuryl group, and an ethylenically unsaturated monomer having a (poly) oxyalkylene alkyl ether group It is preferable that the polymer has at least one type of repeating unit, more preferably an ethylenically unsaturated monomer having a carboxylic acid group, an ethylenically unsaturated monomer having an alkyloxycarbonyl group, and an aryloxycarbonyl. Ethylenically unsaturated monomer having oxetanyl group, ethylenically unsaturated monomer having oxetanyl group Two or more repeating units of a monomer selected from a monomer, an ethylenically unsaturated monomer having a tetrahydrofurfuryl group, and an ethylenically unsaturated monomer having a (poly) oxyalkylene alkyl ether group , Preferably it is a copolymer having 3 or more types. In this case, the ethylenically unsaturated monomer having a characteristic group other than the characteristic group α may be contained in any of random copolymerization and block copolymerization.

The proportion of the ethylenically unsaturated monomer having a characteristic group other than the characteristic group α in the polymer chain P ² can be set as appropriate, but the dispersibility and storage stability are improved, as well as the chromaticity characteristics and heat resistance. From the viewpoint of forming a cured film that is excellent in properties and solvent resistance and suppresses the generation of foreign substances, for example, the following embodiments are preferable.
The ratio of the ethylenically unsaturated monomer having an alkyloxycarbonyl group is preferably 25 to 99% by mass, more preferably 50 to 98% by mass, and still more preferably 75 to 96% by mass in all monomers. Moreover, it is preferable to contain the ethylenically unsaturated monomer whose carbon number of an alkyloxycarbonyl group is 2-4.
The proportion of the ethylenically unsaturated monomer having a (poly) oxyalkylene alkyl ether group may be 0% by mass, but when the monomer is included, 1-60% by mass in all monomers. % Is preferable, and 2-45 mass% is still more preferable.
The proportion of the ethylenically unsaturated monomer having a carboxylic acid group may be 0% by mass, but when the monomer is included, 1 to 20% by mass is preferable in all monomers. More preferably, it is 10 mass%.
The proportion of the ethylenically unsaturated monomer having an aryloxycarbonyl group may be 0% by mass, but when the monomer is included, 1 to 20% by mass is preferable in the total monomers, 2-15 mass% is still more preferable.
The proportion of the ethylenically unsaturated monomer having an oxetanyl group or the ethylenically unsaturated monomer having a tetrahydrofurfuryl group may be 0% by mass. 1-40 mass% is preferable in a body, and 5-30 mass% is still more preferable.

As a specific example of an ethylenically unsaturated monomer having a carboxylic acid group,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof;
Mono [(meth) acryloyloxyalkyl] of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Mention may be made of esters. In addition, the various ethylenically unsaturated monomers exemplified in the paragraph [0068], similar to those exemplified as the ethylenic unsaturated monomer having a characteristic group other than characteristic group α in the description of the polymer chain P ¹ Can be mentioned.

The molecular weight of the polymer chains ^{P 2,} from the viewpoint of improving the dispersibility and storage stability, Mw as measured by GPC, is preferably 1000 to 20,000, more preferably 3000～15,000. The ratio of Mw to Mn (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0.

Next, X in the formula (1) will be described.
X is a trivalent or higher group connecting the polymer chain P ¹ and the polymer chain P ² . In the following description, X is also referred to as “linking group X”. In the present invention, from the viewpoint of dispersibility and storage stability, the number m of the polymer chains P ¹ is 1 or more, but 1 is preferable, and the number n of the polymer chains P ² is 2 or more. 10 is preferable, 2-6 is more preferable, and 3-5 is still more preferable. Therefore, m + n is preferably 3 to 11, more preferably 3 to 7, and further preferably 4 to 6.

  Examples of the linking group X include trivalent or higher groups shown in the following linking group group β (hereinafter also referred to as “linking group β”), and the same or different linking groups β are bonded to each other to form a trivalent group. What formed the above group further may be used. Moreover, 1 or 2 or more selected from the bivalent coupling group group (gamma) shown below may couple | bond with the coupling group (beta), and may form trivalent or more group. In the formula, A represents a hydrogen atom or a monovalent hydrocarbon group. Specific examples of the monovalent hydrocarbon group include the same ones as described above.

  Specific examples of the linking group X formed by combining the linking group β and the linking group γ include the following. In the formula, A is as defined above, and * indicates a bond.

  Among them, the linking group X is preferably represented by any of the following (4a) to (4f), more preferably (4a) or (4b), from the viewpoints of dispersibility and storage stability. 4b) is more preferred. In the formula, A and * are as defined above.

(In the formulas (4a) to (4f),
A independently represents a hydrogen atom or a monovalent hydrocarbon group,
s and t each independently represent an integer of 1 to 10,
u and w each independently represent an integer of 1 to 30. )

A is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
s and t are each independently preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and still more preferably an integer of 1 to 4.
u and w are each independently preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and still more preferably an integer of 1 to 6.

The acid value of the specific dispersant is preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, and still more preferably 100 mgKOH / g or less, from the viewpoint of dispersibility and storage stability. In addition, there is no restriction | limiting in particular as a lower limit of an acid value, 0 mgKOH / g may be sufficient. When the specific dispersant having an acid value is used, the acid value is preferably 5 mgKOH / g or more, and more preferably 10 mgKOH / g or more. Here, the “acid value” represents the number of mg of KOH necessary for neutralizing 1 g of the solid content of the dispersant.
The amine value of the specific dispersant is preferably 10 to 250 mgKOH / g, more preferably 40 to 200 mgKOH / g, and still more preferably 70 to 180 mgKOH / g from the viewpoints of dispersibility and storage stability. Here, “amine value” represents the number of mg of KOH equivalent to the acid required to neutralize 1 g of the solid content of the dispersant.

The specific dispersant can be produced by a known method. For example, the living polymer is separately polymerized using an ethylenically unsaturated monomer having a desired characteristic group, and the polymer chain P ¹ and the polymer chain P ² are separated. After being obtained independently, these polymer chains can be produced by reacting with (m + n) -valent halogenated hydrocarbons. Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W .; R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be employed.

  Moreover, in this invention, a well-known dispersing agent and a dispersing aid can also be contained with a specific dispersing agent. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester dispersants, acrylic dispersants and the like can be mentioned, and examples of the dispersion aid include pigment derivatives.

  The content of the component (B) is excellent in dispersibility and storage stability, and is excellent in chromaticity characteristics, heat resistance and solvent resistance, and from the viewpoint of forming a cured film in which the generation of foreign matter is suppressed, the component (A ) 5 to 200 parts by mass, preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass, and still more preferably 20 to 70 parts by mass with respect to 100 parts by mass.

-Component (C)-
Component (C) contains at least one selected from a binder resin and a polymerizable compound.
The binder resin is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (c2)”). . Binder resin can be used 1 type or in mixture of 2 or more types.

Examples of the unsaturated monomer (c1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate and p-vinylbenzoic acid.
An unsaturated monomer (c1) can be used 1 type or in mixture of 2 or more types.

Further, as the unsaturated monomer (c2), for example, an ethylenically unsaturated group having a characteristic group other than the above-mentioned characteristic group α in addition to N-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide A monomer can be mentioned.
An unsaturated monomer (c2) can be used 1 type or in mixture of 2 or more types.

  In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (c1) in such a range, not only the chromaticity characteristics, heat resistance and solvent resistance of the cured film are improved, but also the dispersibility and storage stability of the curable composition. Therefore, the generation of foreign matter can be effectively suppressed.

  Specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has an Mw measured by GPC of usually 1,000 to 100,000, preferably 3,000 to 50,000. Further, the ratio of Mw to Mn (Mw / Mn is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. By adopting such an aspect, the cured film Since the chromaticity characteristics, heat resistance and solvent resistance are further enhanced, and the dispersibility and storage stability of the curable composition are also enhanced, the generation of foreign matters can be effectively suppressed.

  The binder resin can be produced by a known method, for example, by a method disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can also be controlled.

  In this invention, content of binder resin is 10-500 mass parts normally with respect to 100 mass parts of component (A), Preferably it is 20-200 mass parts. By adopting such an embodiment, not only the chromaticity characteristics, heat resistance and solvent resistance of the cured film can be improved, but also the dispersibility and storage stability of the curable composition can be improved, so that the generation of foreign matters is effective. Can be suppressed.

  In the present invention, the “polymerizable compound” refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. As the polymerizable compound, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable. A polymeric compound can be used 1 type or in combination of 2 or more types.

  Specific examples of the compound having two or more (meth) acryloyl groups include a reaction product (polyfunctional (meth) acrylate) of an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional (meta ) Acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, reaction product of (meth) acrylate having hydroxyl group and polyfunctional isocyanate [polyfunctional urethane (meth) acrylate], hydroxyl group-containing (meth) acrylate and acid anhydride And a reaction product with a product [polyfunctional (meth) acrylate having a carboxyl group].

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate. Etc. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The polyfunctional (meth) acrylate modified with alkylene oxide is modified with at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Pentamethyl modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Penta modified with at least one selected from erythritol tri (meth) acrylate, ethylene oxide and propylene oxide Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from lithitol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

  Among these polymerizable compounds, a reaction product [polyfunctional (meth) acrylate] of trivalent or higher aliphatic polyhydroxy compound and (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylate, polyfunctional urethane (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the reactants of trivalent or higher aliphatic polyhydroxy compounds and (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate has a carboxyl group. Among the polyfunctional (meth) acrylates, the reaction product of pentaerythritol triacrylate and succinic anhydride, the reaction product of dipentaerythritol pentaacrylate and succinic anhydride has a high strength of the cured film, and the surface of the cured film. It is particularly preferable in that it is excellent in smoothness and hardly generates foreign matter.

  10-400 mass parts is preferable with respect to 100 mass parts of components (A), and, as for content of a polymeric compound, 20-150 mass parts is more preferable. By adopting such an embodiment, not only the chromaticity characteristics, heat resistance and solvent resistance of the cured film can be improved, but also the dispersibility and storage stability of the curable composition can be improved, so that the generation of foreign matters is effective. Can be suppressed.

-Photopolymerization initiator-
The curable composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to the curable composition. The photopolymerization initiator is a compound that generates active species capable of initiating polymerization of a polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Can be used in combination.

  Examples of photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. Examples include compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds, and the like. Among these, at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds is preferable.

  Among preferred photopolymerization initiators, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4- Examples thereof include dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

  Specific examples of acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 Examples include ', 5,5'-tetraphenyl-1,2'-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include compounds described in paragraphs [0063] to [0065] of JP-B-57-6096 and JP-A-2003-238898.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As commercially available products of O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation), OXE-03, OXE-04 (manufactured by BASF Corporation), etc. may be used. it can.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of polymeric compounds, and, as for content of a photoinitiator, 1-100 mass parts is still more preferable. By setting it as such an aspect, not only the chromaticity characteristic of a cured film, heat resistance, and solvent resistance can be improved, but the generation | occurrence | production of a foreign material can also be suppressed effectively.

-Solvent-
The curable composition of the present invention contains the components (A) to (C) as well as other components that are optionally added, and is usually prepared as a liquid composition by blending an organic solvent. The
As the solvent, components (A) to (C) constituting the curable composition and other components are dispersed or dissolved, and do not react with these components, and have appropriate volatility. It can be appropriately selected and used. A solvent can be used 1 type or in mixture of 2 or more types.

Among such organic solvents, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, (poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Cyclic ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Fatty acid alkyl esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Among these solvents, at least one selected from (poly) alkylene glycol monoalkyl ether, lactic acid alkyl ester and (poly) alkylene glycol monoalkyl ether acetate from the viewpoints of solubility, pigment dispersibility, coatability and the like. preferable.

  Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the curable composition becomes 5-50 mass% is preferable, and the quantity used as 10-40 mass% Is more preferable. By adopting such an embodiment, the dispersibility and storage stability of the curable composition are improved, so that not only the cured film has excellent chromaticity characteristics, heat resistance and solvent resistance, but also the generation of foreign matters is effective. Can be suppressed.

-Additives-
The curable composition of this invention can also contain various additives as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicone surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropro Adhesion promoters such as rutrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butane Such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples include developability improvers.

  The curable composition of the present invention can be prepared by an appropriate method. For example, the components (A) to (C) are mixed with a solvent and other components optionally added. Can be prepared. When using a pigment as the component (A), the pigment is mixed and dispersed in a solvent in the presence of a specific dispersant, optionally together with a part of a binder resin, for example, using a bead mill, a roll mill or the like. A method of preparing a pigment dispersion, and then adding a polymerizable compound and, if necessary, a binder resin, a photopolymerization initiator, an additional solvent and other components to the pigment dispersion and mixing them. preferable.

Cured film and method for forming the cured film The cured film of the present invention can be produced using the curable composition of the present invention. Specific examples of the cured film include each color pixel, black matrix, spacer, insulating film, infrared cut filter, and the like used in display elements and solid-state imaging elements.

Hereinafter, a colored cured film used for a color filter constituting a display element or a solid-state imaging element and a method for forming the same will be described as an example.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a blue liquid-sensitive composition of the radiation-sensitive curable composition of the present invention on this substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Next, each of the radiation-sensitive curable compositions of green or red is used, and in the same manner as described above, each of the radiation-sensitive curable compositions is applied, pre-baked, exposed, developed, and post-baked to obtain a green pixel array. And a red pixel array are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of blue, green and red is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. However, it is a radiation sensitive material in which a black colorant is dispersed. Using the curable composition, it can be formed in the same manner as in the case of forming the pixel.

  Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying a radiation-sensitive curable composition to a substrate, an appropriate application such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. Although a method can be employed, it is particularly preferable to employ a spin coating method or a slit die coating method.

  The pre-baking is usually about 70 to 110 ° C. for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, and 1,8-diazabicyclo- [5.4.0] -7-undecene. An aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene is preferable.

For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, after the liquid composition of the thermosetting composition of the present invention containing, for example, a blue colorant is discharged into the formed partition wall by an inkjet apparatus, pre-baking is performed to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

  Subsequently, using each green or red thermosetting composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. As a result, a color filter in which the pixel patterns of the three primary colors of blue, green and red are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

In addition, since the partition plays not only a light shielding function but also a function for preventing color mixing of the thermosetting composition of each color discharged into the section, compared to the black matrix used in the first method described above, Thick film. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a radiation-sensitive colored composition in which a black colorant is dispersed is used, but the curable composition of the present invention can also be suitably used for forming such a black spacer.

  The curable composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in a color filter. Since the color filter having the colored cured film of the present invention thus formed has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of the colored cured films formed using the curable composition of this invention.

Display element The display element of this invention comprises the cured film of this invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Can be taken. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium oxide doped with tin) electrode or an IZO (mixture of acid value indium and zinc oxide) electrode It is also possible to adopt a structure in which the substrate on which the substrate is formed faces the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix or the black spacer may be formed on either the substrate side on which the color filter is formed, or on the substrate side on which the ITO electrode or IZO electrode is formed.

  The color liquid crystal display element including the cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display element having the cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.

  The organic EL display element having the cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242. Moreover, the electronic paper provided with the cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.

Solid-state image sensor The solid-state image sensor of the present invention comprises the cured film of the present invention. In addition, the solid-state imaging device of the present invention can take an appropriate structure. For example, as one embodiment, by using the curable composition of the present invention to form a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, color separation is performed. It is possible to produce a solid-state imaging device having excellent properties and color reproducibility. Alternatively, a curable composition containing a metal oxide having infrared shielding ability such as tungsten oxide is used as the component (A), and a cured film (infrared cut) is formed on a semiconductor substrate such as a CMOS substrate by the same operation as described above. By forming the filter, a solid-state imaging device with less noise can be manufactured.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Abbreviations of raw materials used in the following “synthesis of specific dispersant” and “synthesis of binder resin” are as follows.
THF: Tetrahydrofuran PGMEA: Propylene glycol monomethyl ether acetate AIBN: 2,2′-azobisisobutyronitrile EEMA: 1-ethoxyethyl methacrylate MA: Methacrylic acid MMA: Methyl methacrylate nBMA: Normal butyl Methacrylate, EHMA: 2-ethylhexyl methacrylate, THFMA: Tetrahydrofurfuryl methacrylate, PME-200: Methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name PME-200, degree of polymerization ≈4)
DAMA: dimethylaminoethyl methacrylate BzMA: benzyl methacrylate

<Measurement of Mw and Mw / Mn>
Mw and Mn in terms of polystyrene of the specific dispersant and binder resin obtained in each of the following synthesis examples were measured by gel permeation chromatography (hereinafter abbreviated as GPC) having the following specifications.
-Apparatus: GPC-104 (made by Showa Denko KK).
Column: KD-G, KF-603, KF-602, KF-601 were used in combination.
-Mobile phase: THF

<Synthesis of specific dispersant>
Synthesis example 1
To a 300 mL flask, 141.0 g of THF and 27.5 g of lithium chloride (2.6% by mass concentration THF solution) were added and cooled to −60 ° C. After adding 3.7 g of n-butyllithium (15.4 mass% hexane solution) and stirring for 5 minutes, 1.5 g of diphenylethylene was added and stirred for 15 minutes. After dropping DAMA 53.7g and continuing reaction for 30 minutes, gas chromatography (henceforth abbreviated as GC) was measured, the loss | disappearance of the monomer was confirmed, and the resin solution ((alpha) -1) was obtained. A part of the resin solution (α-1) was taken out with a syringe with a needle, deactivated with methanol, and then measured with GPC. The results were Mw = 7,700 and Mw / Mn = 1.20.
Subsequently, 423.0 g of THF and 82.4 g of lithium chloride (2.6% by mass concentration THF solution) were added to a 1500 mL flask and cooled to −60 ° C. After adding 11.0 g of n-butyllithium (15.4 mass% concentration hexane solution) and stirring for 5 minutes, 4.4 g of diphenylethylene was added and stirred for 15 minutes. A mixed solution of MMA 41.1 g, THFMA 52.2 g, and PME-200 85.0 g was added dropwise, and after the reaction was continued for 30 minutes, GC was measured to confirm the disappearance of the monomer to obtain a resin solution (β-1). It was. A part of the resin solution (β-1) was taken out with a syringe with a needle, deactivated with methanol, and then measured with GPC. The results were Mw = 9000 and Mw / Mn = 1.19.
While maintaining the obtained resin solution (α-1) at −60 ° C., it was quickly added to the resin solution (β-1) also maintained at −60 ° C. so as not to exceed the temperature −60 ° C. for 5 minutes. After stirring, 18.5 g of a THF solution containing 1.85 g of pentaerythrityl tetrachloride in 18.5 g was added dropwise over 30 minutes, and then returned to room temperature over 10 hours to complete the reaction. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. This is referred to as “dispersant (B-1) solution”. The dispersant (B-1) solution has a polymer chain P ¹ having a pentaerythrityl group as a core part and a DAMA-derived repeating unit in the core part, and a polymer having a repeating unit derived from MMA, THFMA and PME-200. It was confirmed that the branched compound having a structure in which the chain P ² was bonded at a ratio of 1: 3 was included.

Synthesis example 2
First, a resin solution (α-1) was obtained in the same manner as in Synthesis Example 1.
Subsequently, 423.0 g of THF and 82.4 g of lithium chloride (2.6% by mass concentration THF solution) were added to a 1000 mL flask and cooled to −60 ° C. After adding 11.0 g of n-butyllithium (15.4 mass% concentration hexane solution) and stirring for 5 minutes, 4.4 g of diphenylethylene was added and stirred for 15 minutes. A mixed solution of 24.3 g of EHMA, 58.1 g of nBMA, and 13.5 g of EEMA was added dropwise and the reaction was continued for 30 minutes. Then, GC was measured to confirm the disappearance of the monomer to obtain a resin solution (β-2). A part of the resin solution (β-2) was taken out with a syringe with a needle, deactivated with methanol, and then measured with GPC. The results were Mw = 9,400 and Mw / Mn = 1.19.
Subsequently, 3.41 g of pentaerythrityl tetrabromide and 34.1 g of THF were added to a 1000 mL flask and cooled to −60 ° C., and then the obtained resin solution (α-1) was kept at −60 ° C. over 2 hours. After the dropwise addition, the reaction was continued for 10 hours while maintaining at −60 ° C., and then the obtained resin solution (β-2) was added dropwise over 2 hours while maintaining at −60 ° C., and then maintained at −60 ° C. The reaction was continued for 2 hours as it was, and then returned to room temperature over 10 hours to complete the reaction. Thereafter, the PGMEA solution having a concentration of 30% by mass was adjusted by concentration under reduced pressure, and then adjusted to a PGMEA solution having a concentration of 40% by heating to 160 ° C. while reducing the pressure. This is designated as “dispersant (B-2) solution”. The dispersant (B-2) solution has a polymer chain P ¹ having a pentaerythrityl group as a core part and a DAMA-derived repeating unit in the core part, and a polymer chain P having a repeating unit derived from EHMA, nBMA, and MA. It was confirmed that 2 contained a branched compound having a structure in which ² was bonded at a ratio of 1: 3. The MA unit in the polymer chain P ² is produced by deprotecting the 1-ethoxyethyl group of the EEMA unit.

Synthesis example 3
To a 300 mL flask, 141.0 g of THF and 54.9 g of lithium chloride (2.6% by mass concentration THF solution) were added and cooled to −60 ° C. After adding 7.3 g of n-butyllithium (15.4 mass% hexane solution) and stirring for 5 minutes, 2.9 g of diphenylethylene was added and stirred for 15 minutes. After DAMA 53.7g was dripped and reaction was continued for 30 minutes, GC was measured and the loss | disappearance of the monomer was confirmed and the resin solution ((alpha) -2) was obtained. A part of the resin solution (α-2) was taken out with a syringe with a needle, deactivated with methanol, and then measured with GPC. The results were Mw = 3,400 and Mw / Mn = 1.20.
Subsequently, 423.0 g of THF and 164.7 g of lithium chloride (2.6% by mass concentration THF solution) were added to a 1500 mL flask and cooled to −60 ° C. n-Butyllithium 22.0g (15.4 mass% concentration hexane solution) was added, and after stirring for 5 minutes, diphenylethylene 8.8g was added and stirred for 15 minutes. A mixture of MMA 31.9 g, EHMA 36.5 g, nBMA 45.0 g, PME-200 27.9 g, and BzMA 18.0 g was dropped, and after the reaction was continued for 30 minutes, GC was measured to confirm the disappearance of the monomer. A solution (β-3) was obtained. A part of the resin solution (β-3) was taken out with a syringe with a needle, deactivated with methanol, and then measured with GPC. The results were Mw = 4,500 and Mw / Mn = 1.19.
While maintaining the obtained resin solution (α-2) at −60 ° C., it was quickly added to the resin solution (β-3) also kept at −60 ° C. so as not to exceed the temperature −60 ° C. for 5 minutes. After stirring, 36.9 g of a THF solution containing 3.69 g of pentaerythrityl tetrachloride in 10% was added dropwise over 30 minutes, and then returned to room temperature over 10 hours to complete the reaction. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. This is designated as “dispersant (B-3) solution”. The dispersant (B-3) solution has a pentaerythrityl group as a core part, a polymer chain P ¹ having a DAMA-derived repeating unit in the core part, and MMA, EHMA, nBMA, PME-200 and BzMA-derived repeats. polymer chains P ² having units 1: it was confirmed to contain the branched compound having a structure bonded at a ratio of 3.

Synthesis example 4
First, a resin solution (α-1) was obtained in the same manner as in Synthesis Example 1.
Subsequently, 211.5 g of THF and 82.4 g of lithium chloride (2.6% by mass concentration THF solution) were added to a 500 mL flask and cooled to −60 ° C. After adding 11.0 g of n-butyllithium (15.4 mass% concentration hexane solution) and stirring for 5 minutes, 4.4 g of diphenylethylene was added and stirred for 15 minutes. A mixture of MMA 20.0 g, EHMA 12.2 g, nBMA 29.0 g, and EEMA 6.8 g was added dropwise, and the reaction was continued for 30 minutes. Then, GC was measured to confirm the disappearance of the monomer, and the resin solution (β-4) Got. A part of the resin solution (β-4) was taken out with a syringe with a needle, deactivated with methanol, and then measured with GPC. The results were Mw = 4,500 and Mw / Mn = 1.19.
While maintaining the obtained resin solution (α-1) at −60 ° C., it was quickly added to the resin solution (β-4) also maintained at −60 ° C. so as not to exceed the temperature −60 ° C. for 5 minutes. After stirring, 18.5 g of a THF solution containing 1.85 g of pentaerythrityl tetrachloride in 18.5 g was added dropwise over 30 minutes, and then returned to room temperature over 10 hours to complete the reaction. Thereafter, the PGMEA solution having a concentration of 30% by mass was adjusted by concentration under reduced pressure, and then adjusted to a PGMEA solution having a concentration of 40% by heating to 160 ° C. while reducing the pressure. This is designated as “dispersant (B-4) solution”. The dispersant (B-4) solution has a polymer chain P ¹ having a pentaerythrityl group as a core part and a DAMA-derived repeating unit in the core part, and a polymer having MMA, EHMA, nBMA and MA-derived repeating units. It was confirmed that a branched compound having a structure in which the chain P ² was bonded at a ratio of 1: 3 was included. The MA unit in the polymer chain P ² is produced by deprotecting the 1-ethoxyethyl group of the EEMA unit.

Synthesis example 5
To a 300 mL flask, 141.0 g of THF and 18.3 g of lithium chloride (2.6% by mass concentration THF solution) were added and cooled to −60 ° C. n-Butyllithium 2.4g (15.4 mass% concentration hexane solution) was added, and after stirring for 5 minutes, 1.0 g of diphenylethylene was added and stirred for 15 minutes. After DAMA 53.7g was dripped and reaction was continued for 30 minutes, GC was measured and the loss | disappearance of the monomer was confirmed and the resin solution ((alpha) -3) was obtained. A part of the resin solution (α-3) was taken out with a syringe with a needle, deactivated with methanol, and measured by GPC. As a result, Mw = 11,560 and Mw / Mn = 1.21.
Subsequently, 423.0 g of THF and 54.9 g of lithium chloride (2.6% by mass concentration THF solution) were added to a 500 mL flask and cooled to −60 ° C. After adding 7.3 g of n-butyllithium (15.4 mass% hexane solution) and stirring for 5 minutes, 2.9 g of diphenylethylene was added and stirred for 15 minutes. A mixed solution of MMA 40.0 g, EHMA 24.3 g, nBMA 58.1 g, and EEMA 13.5 g was dropped, and after the reaction was continued for 30 minutes, GC was measured to confirm the disappearance of the monomer and to confirm the resin solution (β-5) Got. A part of the resin solution (β-5) was taken out with a syringe with a needle, deactivated with methanol, and measured by GPC. As a result, Mw = 13,000 and Mw / Mn = 1.19.
While maintaining the obtained resin solution (α-3) at −60 ° C., it was quickly added to the resin solution (β-5) also kept at −60 ° C. so that the temperature did not exceed −60 ° C. for 5 minutes. After stirring, 12.3 g of a THF solution containing 1.23 g of pentaerythrityl tetrachloride in 10% was added dropwise over a period of 30 minutes while maintaining at −60 ° C., and then the reaction was returned to room temperature over 10 hours to complete the reaction. Thereafter, the PGMEA solution having a concentration of 30% by mass was adjusted by concentration under reduced pressure, and then adjusted to a PGMEA solution having a concentration of 40% by heating to 160 ° C. while reducing the pressure. This is designated as “dispersant (B-5) solution”. Dispersant (B-5) solution comprises a polymer chain P ¹ having a pentaerythrityl group as a core part and having a DAMA-derived repeating unit in the core part, and a polymer having MMA, EHMA, nBMA and MA-derived repeating units. It was confirmed that a branched compound having a structure in which the chain P ² was bonded at a ratio of 1: 3 was included. The MA unit in the branched chain B is produced by deprotecting the 1-ethoxyethyl group of the EEMA unit.

Synthesis Example 6
First, a resin solution (α-1) was obtained in the same manner as in Synthesis Example 1.
Subsequently, 282.0 g of THF and 54.9 g of lithium chloride (2.6 mass% THF solution) were added to a 1500 mL flask, and the mixture was cooled to −60 ° C. After adding 7.3 g of n-butyllithium (15.4 mass% hexane solution) and stirring for 5 minutes, 2.9 g of diphenylethylene was added and stirred for 15 minutes. A mixed solution of MMA 27.4 g, THFMA 34.8 g, and PME-200 56.6 g was dropped, and after continuing the reaction for 30 minutes, GC was measured to confirm the disappearance of the monomer to obtain a resin solution (β-6). It was. A part of the resin solution (β-6) was taken out with a syringe with a needle, deactivated with methanol, and measured by GPC. As a result, Mw = 9000 and Mw / Mn = 1.19.
While maintaining the obtained resin solution (α-1) at −60 ° C., it was quickly added to the resin solution (β-6) also maintained at −60 ° C. so as not to exceed the temperature −60 ° C. for 5 minutes. After stirring, 15.4 g of a THF solution containing 10% of 1,1,1, -tris (chloromethyl) ethane (1.54 g) was added dropwise over 30 minutes while maintaining at -60 ° C., and then over 10 hours. The reaction was terminated by returning to room temperature. Then, it adjusted to the PGMEA solution of a 56.5 mass% density | concentration by vacuum concentration. This is designated as “dispersant (B-6) solution”. The dispersant (B-6) solution has a polymer chain P ¹ having an ethylidene trismethylene group as a core and a DAMA-derived repeating unit in the core, and a repeating unit derived from MMA, THFMA, and PME-200. polymer chains P ² is 1: was confirmed to contain the branched compound having a structure bonded at a ratio of 2.

Comparative Synthesis Example 1
To a 300 mL flask, 118.0 g of THF and 109.8 g of lithium chloride (2.6% by mass concentration THF solution) were added and cooled to −60 ° C. n-Butyllithium 14.6g (15.4 mass% concentration hexane solution) was added and, after stirring for 5 minutes, diphenylethylene 5.9g was added and stirred for 15 minutes. DAMA 238.2 g, MMA 54.8 g, THFMA 69.6 g, and PME-200 113.3 g were added dropwise, and the reaction was continued for 30 minutes. Then, GC was measured to confirm the disappearance of the monomer to obtain a resin solution (γ). . A part of the resin solution (γ) was taken out with a syringe with a needle, deactivated with methanol, and then measured by GPC. As a result, Mw = 8,500 and Mw / Mn = 1.20.
Subsequently, while the resin solution (γ) was kept at −60 ° C., 18.5 g of a THF solution containing 1.85 g of pentaerythrityl tetrachloride was kept dropwise at 30 ° C. over 30 minutes. Thereafter, the temperature was returned to room temperature over 10 hours to complete the reaction. Then, it adjusted to the PGMEA solution of 40 mass% concentration by concentration under reduced pressure. This is designated as “dispersant (B-7) solution”. The dispersant (B-7) solution has a structure in which a pentaerythrityl group is a core part, and four polymer chains γ having DAMA, MMA, THFMA, and PME-200-derived repeating units are bonded to the core part. It was confirmed that the compound was contained.

In the above synthesis example, the type and copolymerization ratio of in the polymer chain P ¹ of the monomers contained in the polymer chain P ¹ (wt%), and the type and polymer chain of each monomer included in the polymer chain P ² copolymerization ratio of in P ² (mass%) shown in Table 1. The dispersion agent in Comparative Synthesis Example 1 (B-7) solution is not applicable to a particular dispersing agent of the present invention, DAMA100 parts by mass copolymerization ratio of monomer other than DAMA in the column of the polymer chain P ² It shows in Table 1 as a copolymerization ratio with respect to.

Comparative Synthesis Example 2
A hetero arm star copolymer was synthesized according to Production Example 1 of JP 2010-111781 A, and adjusted to an anisole solution having a concentration of 40% by mass. This is designated as “dispersant (B-8) solution”.

<Measurement of acid value>
The acid value of the dispersant obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the dispersant solution was precisely weighed to a unit of 1 mg and separated into a glass container. After diluting to 50 mL with propylene glycol monomethyl ether acetate, phenolphthalein was added, titrated with 0.1 N ethanolic potassium hydroxide aqueous solution, and the point colored in pink was the end point. Similarly, a blank test was performed. The acid value (unit: mgKOH / g) was calculated from the dispersant and the dropwise addition amount of 0.1N ethanolic potassium hydroxide aqueous solution in the blank test.

<Measurement of amine value>
The amine value of the dispersant obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the dispersant solution was precisely weighed to a unit of 1 mg and separated into a glass container. Acetic anhydride / acetic acid = 9/1 mixed solvent (volume ratio) 20 mL was added and dissolved, and left at room temperature for 3 hours. Thereafter, 30 mL of acetic acid was further added, and titration was performed with a 0.1 mol / L perchloric acid / acetic acid solution using a potentiometer AT-510 (manufactured by Kyoto Electronics Co., Ltd.). Similarly, a blank test was performed. The amine value (unit: mg KOH / g) was calculated from the dispersant and the drop amount of 0.1 mol / L perchloric acid / acetic acid solution in the blank test.

<Synthesis of binder resin>
Synthesis example 7
In a flask equipped with a condenser and a stirrer, 44.0 g of p-vinylbenzylglycidyl ether, 40.0 g of N-phenylmaleimide, and 16.0 g of BzMA are dissolved in 300 g of PGMEA, and further 8.0 g of AIBN and 8.0 g of α-methylstyrene dimer. And then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours.
Next, 17.0 g of MA, 0.5 g of p-methoxyphenol and 4.4 g of tetrabutylammonium bromide were added to this reaction solution, and reacted at 120 ° C. for 9 hours. Further, 18.5 g of succinic anhydride was added and reacted at 100 ° C. for 6 hours, then washed twice with the liquid temperature kept at 85 ° C., and concentrated under reduced pressure to obtain binder resin (C-1). Was obtained. This binder resin (C-1) had Mw = 7,800 and Mw / Mn = 2.8.

Synthesis Example 8
In a flask equipped with a condenser and a stirrer, BzMA 30.0 g, nBMA 20.0 g, hydroxyethyl methacrylate 15.0 g, styrene 20.0 g and MA 15.0 g were dissolved in propylene glycol monomethyl ether acetate 200 g, and AIBN 3.0 g and α -5.0 g of methylstyrene dimer was charged and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a solution containing 33% by mass of binder resin (C-2). This binder resin (C-2) had Mw = 10,000 and Mw / Mn = 2.5.

Synthesis Example 9
In a flask equipped with a condenser and a stirrer, 2- (methacryloyloxymethyl) -3-ethyloxetane 25.0 g, MA 18.0 g, succinic acid mono-2-acryloxyethyl 9.0 g, N-phenylmaleimide 10.0 g, 24.0 g of BzMA and 14.0 g of hydroxyethyl methacrylate were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 6.0 g of AIBN and 6.0 g of α-methylstyrene dimer were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a precursor copolymer solution.
To 200 g of the obtained precursor copolymer solution, 13.4 g of 2-methacryloyloxyethyl isocyanate and 0.2 g of 4-methoxyphenol as a polymerization inhibitor were added and reacted at 90 ° C. for 2 hours. This reaction solution was washed twice with 75 g of ion exchange water once and concentrated under reduced pressure to obtain a solution containing 33% by mass of the binder resin (C-3). Binder resin (B-3) was Mw = 11,000 and Mw / Mn = 1.9.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. C.I. Pigment Green 58 and 12 parts by mass of C.I. I. 3 parts by weight of Pigment Yellow 150, 12.5 parts by weight of the dispersant (B-1) solution (nonvolatile component 40% by weight), 64.5 parts by weight of propylene glycol monomethyl ether acetate and 8 parts by weight of propylene glycol monomethyl ether as a solvent Then, it was processed by a bead mill to prepare a pigment dispersion (p-1).

Preparation Examples 2 to 10 and Comparative Preparation Examples 1 to 3
In Preparation Example 1, pigment dispersions (p-2) to (p-13) were prepared in the same manner as Preparation Example 1, except that the types and amounts of the colorant, the dispersant solution and the solvent were changed as shown in Table 2. Was prepared.

Evaluation of Initial Viscosity and Storage Stability of Pigment Dispersion The viscosity of the obtained pigment dispersion was measured using an E-type viscometer (manufactured by Tokyo Keiki). The obtained pigment dispersion was filled in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki). Then, the increase rate of the viscosity after storage for 14 days with respect to the viscosity immediately after the preparation is calculated. When the increase rate is less than 5%, “A”, when 5% or more and less than 10%, “B”, 10% or more The case was evaluated as “C”. The evaluation results are shown in Table 2.

Comparative Preparation Example 4
In Preparation Example 1, an attempt was made to prepare a pigment dispersion (p-14) in the same manner as in Preparation Example 1, except that the dispersant (B-8) solution was used instead of the dispersant (B-1) solution. . However, it was judged that the pigment dispersion (p-14) could not be prepared due to the extremely high viscosity that prevented separation from the bead mill. Therefore, the initial viscosity and storage stability were not evaluated. Moreover, preparation and evaluation of the colored curable composition mentioned later were abandoned.

In Table 2, each component is as follows.
G58: C.I. I. Pigment Green 58
G7: C.I. I. Pigment Green 7
Y129: C.I. I. Pigment Yellow 129
Y150: C.I. I. Pigment Yellow 150
Y138: C.I. I. Pigment Yellow 138
R177: C.I. I. Pigment Red 177
R254: C.I. I. Pigment Red 254
R264: C.I. I. Pigment Red 264
-B15: 6: C.I. I. Pigment Blue 15: 6
V23: C.I. I. Pigment Violet 23
-PGMEA: Propylene glycol monomethyl ether acetate-PGME: Propylene glycol monomethyl ether-LPN6919: BYK-LPN6919 (manufactured by BYK (BYK), a dispersant containing a (meth) acrylic block copolymer, solid concentration 60 mass%)
LPN21116: BYK-LPN21116 (Bikchemy (BYK), manufactured by a dispersant containing a (meth) acrylic block copolymer, solid concentration 40% by mass)

<Preparation and evaluation of colored curable composition>
Preparation Example 1 of Colored Curable Composition
100 parts by mass of the pigment dispersion (p-1), 30.3 parts by mass of the binder resin (C-1) solution as the binder resin, and M-402 (dipentaerythritol hexaacrylate and dipenta as a polymerizable compound) manufactured by Toagosei Co., Ltd. Mixture of erythritol pentaacrylate) 6.7 parts by mass, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one (trade name) as a photopolymerization initiator Irgacure 379 (manufactured by BASF) 3.3 parts by mass, 0.05 parts by mass of MegaFac F-554 (manufactured by DIC Corporation) as a fluorosurfactant and 122 parts by mass of ethyl 3-ethoxypropionate as a solvent Thus, a liquid colored curable composition was prepared.

Evaluation of chromaticity characteristics The obtained colored curable composition was applied on a glass substrate using a spin coater and then pre-baked on a hot plate at 100 ° C. for 2 minutes. A film was formed. Next, after these substrates are cooled to room temperature, a high-pressure mercury lamp is used for the coating film on the substrate, and radiation including each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without passing through a photomask. The exposure was performed at an exposure amount of 1,000 J / m ² . Thereafter, post-baking was performed at 220 ° C. for 20 minutes to form a cured film on the substrate. Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. From the measurement result, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.59 were obtained. The evaluation results are shown in Table 3.

Contrast Evaluation The contrast of the three cured films obtained in the above “ evaluation of chromaticity characteristics” was measured using a contrast meter (contrast measuring device CT-1 manufactured by Aisaka Electric Co., Ltd.). From the measurement result, the contrast when the chromaticity coordinate value y = 0.59 was obtained. The evaluation results are shown in Table 3.

Evaluation of solvent resistance One of the substrates obtained in the above “ Evaluation of chromaticity characteristics” was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes. And the color change (DELTA ⁾ Eab ^* before and behind immersion was calculated | required. The case where ΔEab ^* was less than 3 was evaluated as “A”, the case where it was 3 or more and less than 5 was evaluated as “B”, and the case where it was 5 or more was evaluated as “C”. The evaluation results are shown in Table 3.

Evaluation of Heat Resistance One of the substrates obtained in the above “ Evaluation of chromaticity characteristics” was further heated at 250 ° C. for 30 minutes. Then, the substrate surface was observed with an optical microscope having an eyepiece magnification of 10 times and an objective lens magnification of 10 times. “A” when 3 or less foreign objects are confirmed in one field of view, “B” when 4 or more foreign objects are confirmed in 1 field of view, and “B” when 1 foreign object is confirmed in 1 field of view The case where there were 10 or more foreign materials was evaluated as “C”. The evaluation results are shown in Table 3.

Foreign matter evaluation After coating on an 8-inch wafer to a film thickness of 0.6 μm, soft baking was performed at 80 ° C. for 1 minute, and then the foreign matter was measured using KLA 2351 manufactured by KLA-Tencor. The case where the number of foreign matters having a size of 0.2 to 1.0 μm is 100 or less is “A”, the case where it is 100 to 10,000 is “B”, and the case where it is 10,000 or more is “ The determination was made as “C”. The evaluation results are shown in Table 3.

Examples 2 to 10 and Comparative Examples 1 to 3
In Example 1, the color curable composition was changed in the same manner as in Example 1 except that the types and amounts of the pigment dispersion, binder resin, crosslinking agent, photopolymerization initiator, and solvent were changed as shown in Table 3. Preparation and evaluation were performed.
Regarding Example 2, as in Example 1, the chromaticity coordinate value x, the stimulus value (Y), and the contrast at the chromaticity coordinate value y = 0.590 were obtained, and Examples 3, 6-7, 10 For Comparative Example 1, the chromaticity coordinate value x at the chromaticity coordinate value y = 0.570, the stimulus value (Y), and the contrast are obtained. For Example 9 and Comparative Example 3, the chromaticity coordinate value y = The chromaticity coordinate value x, stimulus value (Y) and contrast at 0.650 were determined. For Example 4, chromaticity coordinate value y, stimulus value (Y) and contrast at chromaticity coordinate value x = 0.640 are obtained, and for Example 8 and Comparative Example 2, chromaticity coordinate value x = 0. The chromaticity coordinate value y, stimulus value (Y) and contrast at. For the blue colored curable composition (Example 5), the chromaticity coordinate value x, the stimulation value (Y), and the contrast at the chromaticity coordinate value y = 0.090 were determined. The evaluation results are shown in Table 3.

In Table 3, each component is as follows.
D-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toagosei Co., Ltd.)
D-2: monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate, and mixture of dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)
E-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OXE02, manufactured by BASF )
E-2: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 379, manufactured by BASF)
-EEP: ethyl 3-ethoxypropionate-MBA: 3-methoxybutyl acetate

Claims (8)

(A) at least one selected from pigments and metal oxide particles,
(B) a dispersant, and (C) a curable composition containing at least one selected from a binder resin and a polymerizable compound,
(B) The curable composition in which a dispersing agent contains the compound represented by following formula (1).

[In Formula (1),
m represents an integer of 1 or more,
n represents an integer of 2 or more,
P ¹ represents a polymer chain having at least one group selected from the following characteristic group α.
P ² represents a polymer chain having no group selected from the following characteristic group α.
X represents a (m + n) -valent linking group.
(Characteristic group α)
Sulfonic acid group, monosulfate group, phosphoric acid group, monophosphate group, boric acid group, urea group, urethane group, group having a coordinating oxygen atom, group having a basic nitrogen atom, alkylaminocarbonyl group, Sulfonamide group, oxygen-containing heterocyclic group, sulfur-containing heterocyclic group, imide group, alkoxysilyl group, oxiranyl group, isocyanate group, hydroxyl group. ] The curable composition according to claim 1, wherein X is a group represented by any of the following formulas (4a) to (4f).

[In Formula (4a)-(4f),
A independently represents a hydrogen atom or a monovalent hydrocarbon group,
s and t each independently represent an integer of 1 to 10,
u and w each independently represent an integer of 1 to 30. ] 3. The polymer chain according to claim ¹ , wherein P ¹ is a polymer chain having at least one selected from the group consisting of a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3). Curable composition.

[In Formula (2),
R ^{1 to} R ³ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and two or more of R ^{1 to} R ³ are bonded to each other. To form a ring structure,
R ⁴ represents a hydrogen atom or a methyl group,
Q represents a divalent linking group,
Y ⁻ represents a counter anion. ]

[In Formula (3),
R ⁵ and R ⁶ each independently represent a hydrogen atom or a chain-like or cyclic hydrocarbon group which may have a substituent, and R ⁵ and R ⁶ are bonded to each other to form a cyclic structure You may,
R ⁷ represents a hydrogen atom or a methyl group,
Z represents a divalent linking group. ] P ² is a polymer chain having at least one group selected from the group consisting of a carboxylic acid group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an oxetanyl group, a tetrahydrofurfuryl group, and a (poly) oxyalkylene alkyl ether group. The curable composition according to any one of claims 1 to 3, wherein   The cured film produced using the curable composition of any one of Claims 1-4.   A display element comprising the cured film according to claim 5.   A solid-state imaging device comprising the cured film according to claim 5. A compound represented by the following formula (1).

[In Formula (1),
m represents an integer of 1 or more,
n represents an integer of 2 or more,
P ¹ represents a polymer chain having at least one group selected from the following characteristic group α.
P ² represents a polymer chain having no group selected from the following characteristic group α.
X represents a (m + n) -valent linking group.
(Characteristic group α)
Sulfonic acid group, monosulfate group, phosphoric acid group, monophosphate group, boric acid group, urea group, urethane group, group having a coordinating oxygen atom, group having a basic nitrogen atom, alkylaminocarbonyl group, Sulfonamide group, oxygen-containing heterocyclic group, sulfur-containing heterocyclic group, imide group, alkoxysilyl group, oxiranyl group, isocyanate group, hydroxyl group. ]