TW201424834A - Photosensitive composition, gray curable film using the same, gray pixel and solid state imaging element - Google Patents

Abstract

The invention provides a composition, which contains a particle having a high refractive index, a black pigment, a dispersing agent and an organic solvent.

Description

Photosensitive composition, gray cured film using the same, gray pixel, and solid-state imaging element

The present invention relates to a photosensitive composition, a gray cured film using the same, a gray pixel, and a solid-state imaging element.

In order to improve the resolution of a video sensor (Charge-coupled Device (CCD), Complementary Metal-Oxide-Semiconductor (CMOS), the number of pixels is increased and the pixels are miniaturized. However, the opening portion is small and becomes a factor for reducing the sensitivity. Therefore, there has been proposed a technique of setting one color of a plurality of color pixels to white (transparent) in order to achieve sensitivity even if the size of the opening is limited (for example, In the case of the research of the molding material of the white pixel, the photosensitive composition of the following Patent Document 2 to Patent Document 4 has been proposed.

Furthermore, it has been attempted to increase the dynamic range of the image sensor by using the gray pixel with low transmittance or the use of the gray pixel (see Patent Document 5 and Patent Document 6).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-53153

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-49029

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-78729

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-127096

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-66637

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-74763

Regarding the above white pixels, research and development of the molding materials thereof are being carried out as described above. However, with regard to the gray pixel with low transmittance which was first proposed recently, even if the design of the component is being advanced, the research of the material is not yet in progress.

In view of the above, it is an object of the present invention to provide a composition which can produce a gray cured film having better light transmittance and refractive index. In addition, the above-described composition is used as a photosensitive composition for forming a pixel, and a composition excellent in photolithimetry is provided. Further, it is an object of the invention to provide a cured film, a pixel, and a solid-state imaging element formed using the photosensitive composition.

The means for solving the above problems are as follows.

[1] A composition comprising high refractive index particles, a black pigment, a dispersing agent, and an organic solvent.

[2] The composition according to [1], further comprising a polymerizable compound, a photopolymerization initiator, and an organic solvent.

[3] The composition according to [1] or [2] wherein the high refractive index particles are two Particles of titanium oxide or zirconia.

[4] The composition according to any one of [1] to [3] wherein the content of the high refractive index particles in the total solid content of the composition is from 5% by mass to 30% by mass.

[5] The composition according to any one of [1] to [4] wherein the black pigment is titanium black.

[6] The composition according to any one of [1] to [5] wherein, in the total solid content of the composition, the content of the black pigment is from 0.5% by mass to 20% by mass.

[7] The composition according to any one of [1] to [6] wherein the dispersing agent is an oligo imine dispersing agent or an acrylic dispersing agent.

[8] The composition according to any one of [1] to [7] further comprising a red pigment.

[9] The composition according to any one of [1] to [8] further comprising an ultraviolet absorber.

[10] The composition according to any one of [1] to [9] wherein the content of the dispersing agent in the total solid content is 0.05% by mass to 10% by mass.

[11] The composition according to any one of [1] to [10] wherein the dispersing agent is a dispersion resin, and the dispersing resin contains a repeating unit represented by the following formula (I-1) and a formula (I) -2) a repeating unit represented by the formula or a repeating unit represented by the formula (I-1) and a repeating unit represented by the formula (I-2a), [Chemical Formula 1]

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group; a each independently represents an integer of 1 to 5; * represents a linking moiety between repeating units; and R ⁸ and R ^{9 have the} same meaning as R ¹ . group; L is a single bond, alkylene linking group in combination, alkenylene group, an arylene group, extending heteroaryl group, an imino group, an ether group, a thioether group, a carbonyl group or a group of the plurality; L ^a A structural moiety which forms a ring structure together with CR ⁸ CR ⁹ and N; X represents a group having a functional group having a pKa of 14 or less; and Y represents a side chain having an atomic number of 40 to 10,000.

[12] The composition according to any one of [1] to [10] wherein the dispersing agent contains any repeating unit of the following formula (1) to formula (5),

In the formula, X ¹ to X ⁶ represent a hydrogen atom, a halogen atom or a monovalent organic group; Y ¹ to Y ⁵ represent a single bond or a divalent linking group; Z ¹ to Z ⁵ represent a hydrogen atom or a monovalent organic group; and R represents A hydrogen atom or a monovalent organic group may have a structurally different R in the copolymer; n, m, p, q, and r each represent an integer of 1 to 500; and j and k are each independently an integer of 2 to 8.

[13] The composition according to any one of [1] to [12] which is used for the formation of a pixel of a solid-state imaging device.

[14] A gray cured film obtained by curing the composition according to any one of [1] to [13].

[15] The gray cured film according to [14], wherein the cured film is gray, and the gray is defined as a difference between a maximum value and a minimum value of a transmittance in a visible light range of a wavelength of 400 nm to 700 nm. Coloring within %~30%.

[16] A gray pixel of a solid-state imaging device, which is a pixel of a solid-state imaging element comprising the cured film according to [14] or [15], and contains the above-mentioned high refractive index particles, a black pigment, and a dispersing agent.

[17] A solid-state imaging element comprising the gray pixel as described in [16].

In the present specification, when a plurality of substituents or a linking group represented by a specific symbol (hereinafter referred to as a substituent or the like) are present in the chemical formula, or when a plurality of substituents or the like are simultaneously or alternatively defined, each substituent is used. The same may be the same or different from each other. In this case, the same applies to the regulation of the number of substituents and the like. When the number of the predetermined substituents or the like is two or more, the two or more substituents may be different from each other or the same. Further, unless otherwise specified, when a plurality of substituents or the like are adjacent to each other, the groups may be bonded to each other or condensed to form a ring.

According to the composition of the present invention, it is possible to produce a light transmissive property and a fold Gray cured film with a rate of incidence. Further, the composition of the present invention can be set as a photosensitive composition for forming a pixel as needed, and the photosensitive composition is particularly excellent in light opacity. Further, according to the present invention, it is possible to provide a high-quality gray cured film, a pixel using the gray cured film, and a solid-state imaging element using the above composition.

The above and other features and advantages of the invention will be apparent from the description and appended claims.

Fig. 1 is a graph showing the transmittance (wavelength of 400 nm to 700 nm and temperature of 25 ° C) of a gray cured film produced in Examples.

2(a) to 2(b) are micrographs (20000 times) showing the appearance of the gray cured film ((a) test 101, (b) test C01) produced in the examples and the comparative examples.

The composition of the present invention is preferably a pixel shape set as a solid photographic element The photosensitive composition for use is preferably a high refractive index particle having a specific refractive index, a black pigment, a dispersant, a polymerizable compound, a photopolymerization initiator, and an organic solvent. Hereinafter, preferred embodiments of the present invention will be described focusing on the description of the composition of the components.

[High refractive index particles]

The high refractive index particles are preferably a refractive index of the constituent material (substance) of 1.8 or more, more preferably 1.9 or more, and still more preferably 2 or more. The upper limit is preferably 3 or less, more preferably It is 2.9 or less, and further preferably 2.8 or less. By setting the refractive index of the high refractive index particles to be equal to or lower than the above upper limit value, it is preferable to maintain the fluctuation amount of the transmittance of the cured film within a specific range and increase the refractive index. On the other hand, by setting the lower limit value to be equal to or higher than the above value, interference with other pixels described later can be suppressed and prevented, which is preferable. In addition, the method of measuring the refractive index of the high refractive index particles is set to a value measured in the examples described later unless otherwise specified.

The weight average particle diameter of the primary particles of the high refractive index particles is preferably 150 nm or less, more preferably 100 nm or less, and particularly preferably 80 nm or less. The lower limit value does not particularly exist, and is actually 1 nm or more. The weight average particle diameter of the high refractive index particles in the layer is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 80 nm or less. The lower limit is not particularly limited, and is preferably 1 nm or more, more preferably 5 nm or more, and still more preferably 10 nm or more. In view of the aggregation of primary particles in the layer, the particle size range of the primary particles is defined as a range different from the particle size range in the layer as described above. In addition, the weight average particle diameter of the high refractive index particle is set based on the value measured by the measuring method used by the Example mentioned later, unless it demonstrates especially.

Examples of the high refractive index particles include particles containing a metal oxide having a selected from the group consisting of Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, and Al. At least one of Mg, Si, P, and S. Specific examples thereof include particles of titanium dioxide, zirconium oxide, tin oxide, indium oxide, zinc oxide, indium tin oxide (ITO), cerium oxide, aluminum oxide, magnesium oxide, vanadium oxide, and cerium oxide. Among them, particles of titanium oxide and zirconium oxide are particularly preferred. The metal oxide particles are mainly composed of oxides of these metals, and may further contain other elements. The main component refers to a component having the largest content (% by mass) of the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. The crystal structure of the inorganic fine particles having titanium dioxide as a main component is preferably a mixed crystal of rutile, rutile/anatase, anatase, and an amorphous structure as a main component, and particularly preferably a rutile structure.

The high refractive index particles are preferably surface treated. The surface treatment can be carried out using an inorganic compound or an organic compound. Examples of the inorganic compound used in the surface treatment include alumina, ceria, zirconia, and iron oxide. Among them, alumina and cerium oxide are preferred. Examples of the organic compound used in the surface treatment include a polyhydric alcohol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent.

In a preferred embodiment of the present invention, high refractive index particles containing at least one element selected from the group consisting of Co (cobalt), Al (aluminum), and Zr (zirconium) are contained in the inorganic fine particles containing titanium dioxide as a main component. Thereby, the photocatalytic activity of the titanium oxide can be suppressed, and the weather resistance of the high refractive index layer can be improved.

The high refractive index particles may also be treated by combining two or more surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the medium refractive index layer.

For the commercially available product of the titanium dioxide particles, for example, TTO series (TTO-51 (A), TTO-51 (C), etc.) manufactured by Ishihara Sangyo Co., Ltd., TTO-S, V series (TTO-S-1, TTO-S-2, TTO-V-3, etc., MT series (MT-01, MT-05, etc.) manufactured by Tayca.

Commercial products of the zirconium dioxide particles include, for example, UEP, UEP-100 (manufactured by the first rare element chemical industry), PCS (manufactured by Nippon Electric Co., Ltd.), JS-01, JS-03, JS- 04 (made by Nippon Electric Co., Ltd.), etc.

The content of the high refractive index particles in the composition is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more based on the total solid content. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less.

[black pigment]

Examples of the black pigment include carbon black as an inorganic pigment or a black metal-containing inorganic pigment shown below. The inorganic pigment containing a ferrous metal may, for example, be a metal oxide containing one or two or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. , metal nitride. These pigments may be used alone or in the form of a mixture of two or more. Further, it can also be prepared in such a manner that it has a desired light-shielding property by further using an inorganic pigment of another color tone in a black pigment. Examples of specific inorganic pigments that can be used in combination include, for example, zinc white, lead white, zinc antimony white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate, and barite powder, red dan, and iron oxide. Red, chrome yellow, zinc yellow (type 1 zinc yellow, type 2 zinc yellow), ultramarine blue, Prussian blue (ferric ferrocyanide potassium), zircon grey , Praseodymium yellow, chrome titanium yellow, chrome green, hole Green, Victoria green, iron blue (not related to Prussian blue), vanadium zirconium blue, chrome tin pink, manganese red, orange pink, etc. In particular, in order to exhibit light-shielding properties in a wide wavelength range from ultraviolet light to infrared light, not only these black pigments or inorganic pigments having other color tones can be used alone, but also a plurality of pigments can be used in combination.

Further, from the viewpoint of light blocking property and hardenability, the black pigment is preferably a metallic pigment of silver and/or tin, From the viewpoint of light-shielding properties in a wide wavelength range from ultraviolet light to infrared light, titanium black is particularly preferable. The term "titanium black" refers to black particles containing titanium atoms. It is preferably low-valent titanium oxide or titanium oxynitride. For the titanium black particles, the surface may be modified as needed in order to improve dispersibility, suppress cohesiveness, and the like. The coating can be carried out by using cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide or zirconium oxide, or by using a water-repellent substance as shown in JP-A-2007-302836. The titanium black may contain one or a composite oxide of Cu, Fe, Mn, V, Ni or the like, cobalt oxide, iron oxide, or the like in order to adjust dispersibility, coloring property, and the like. In the case of a black pigment such as carbon black, titanium black particles are set to be 50% by mass or more of the pigment. Examples of the commercially available product of titanium black include titanium black 10S, titanium black 12S, titanium black 13R, titanium black 13M, titanium black 13M-C, titanium black 13R, and titanium black 13R manufactured by Mitsubishi Material Co., Ltd. N, Tilack D of Akasaka Chemicals Co., Ltd., etc.

The method for producing titanium black has the following method: a method in which a mixture of titanium dioxide and titanium metal is heated in a reducing environment for reduction (Japanese Patent Special Opening) (No. 49-5432); a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a hydrogen-containing reducing environment (Japanese Patent Laid-Open Publication No. SHO 57-205322); titanium dioxide in the presence of ammonia Or a method of high-temperature reduction of titanium hydroxide (Japanese Patent Laid-Open Publication No. SHO-60-65069, JP-A-61-201610), and titanium dioxide or titanium hydroxide is attached to a vanadium compound in the presence of ammonia. A method of high-temperature reduction (Japanese Patent Laid-Open No. 61-201610) and the like. However, the invention is not limited to the methods.

The particle diameter of the black pigment is preferably an average primary particle diameter of 5 nm or more, and the average primary particle diameter is preferably 10 nm or more from the viewpoint of dispersibility, light blocking property, and time-dependent sedimentation property. From the same viewpoint, the upper limit is preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 100 nm or less. The particle size of the black pigment is set to a value measured in Examples described later unless otherwise specified.

The specific surface area of titanium black is not particularly limited, and in order to achieve a predetermined water repellency after surface treatment of the titanium black with a water repellent, it is preferably measured by a Brunauer-Emmett-Teller (BET) method. value is usually about ^{5m 2 / g ~ 150m 2 /} g, particularly preferably of about ^{20m 2 / g ~ 100m 2 /} g.

The black pigment may be used singly or in combination of plural kinds.

In the total solid content, the content of the black pigment in the composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, and still more preferably 20% by mass or less.

Comparison of the blending of black pigments with respect to 100 parts by mass of the above high refractive index particles Preferably, it is 1 part or more, more preferably 2 parts or more, and particularly preferably 5 parts or more. The upper limit is preferably 100 parts or less, more preferably 70 parts or less, and particularly preferably 50 parts or less.

The blending of titanium black is preferably 1 part or more, more preferably 2 parts or more, and particularly preferably 5 parts or more, based on 100 parts by mass of the above titanium oxide. The upper limit is preferably 100 parts or less, more preferably 70 parts or less, and particularly preferably 50 parts or less.

[Dispersant]

The dispersant is not particularly distinguished from the composition, but in view of its function, it is distinguished from those in which the dispersibility of the high refractive index particles is high and the dispersibility of the black pigment is high. However, the invention is not to be construed as limited by the description.

(Dispersant for dispersing high refractive index particles)

. Specific dispersion resin A

In the present invention, a dispersion resin represented by the following formula (A1) is preferably used as a dispersant for dispersing a high refractive index particle.

The substituents and the linking group are described in order, and the substituent A ¹ interacts with the high refractive index particles, and the dispersing agent represented by the above formula (A1) has n (1 to 9) substituents A ¹ It can act as a resin and strongly interact with high refractive index particles. Further, the polymer chain P ¹ functions as a steric repulsion group, and by having m polymer chains P ¹ , it is possible to exhibit a good steric repulsive force and uniformly disperse the high refractive index particles. Further, it is presumed that the dispersant represented by the above formula (A1) does not cause a problem such as aggregation of particles due to cross-linking between particles which may occur in the conventional graft-dispersed dispersant in the molecular structure. Hereinafter, each group of the above formula (A1) will be described in detail. Further, the dispersing agent represented by the formula (A1) is also disclosed in Japanese Patent Laid-Open No. Hei. No. 2007-277514 (Japanese Patent Application No. 2006-269707), the disclosure of which is incorporated herein by reference. .

. A ¹

The above A ¹ represents a monovalent substituent having at least one group selected from the group consisting of an acid group, a urea group, an urethane group, a group having a coordinating oxygen atom, and a group containing a basic nitrogen atom. a group in the group consisting of a heterocyclic group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group group. In the following, the portion (the functional group and the structure) having an adsorption ability for the high refractive index particles will be collectively referred to as an "adsorption site" as appropriate.

The adsorption site may contain at least one of A ¹ and may contain two or more types. The substituent is preferably a monovalent substituent bonded to the above-mentioned adsorption site and the above-mentioned linking group, wherein the linking group is composed of 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, and 0 to 100 oxygen atoms. An atom, one to 400 hydrogen atoms and 0 to 40 sulfur atoms are formed. Further, in the case where the adsorption site itself can constitute a monovalent substituent, the adsorption site itself can also be a monovalent substituent represented by A ¹ .

Examples of the above-mentioned "acid group" include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group, and a carboxylic acid group or a sulfonic acid group is more preferred. The group, the monosulfate group, the phosphoric acid group, the monophosphate group, and further preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and more preferably a carboxylic acid group.

Examples of the "ureido group" include -NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein, R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 or more carbon atoms). Or an aralkyl group having a carbon number of 7 or more is more preferably -NR ¹⁵ CONHR ¹⁷ (wherein, R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, carbon number 6 or more aryl groups and aralkyl groups having 7 or more carbon atoms are particularly preferably -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or carbon). Number 7 or more of aralkyl groups).

Examples of the above-mentioned "urethane group" include -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , and -OCONR ²² R ²³ (here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, and the like, and more preferably -NHCOOR ¹⁸ or -OCONHR ²¹ (this) Wherein R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like, and particularly preferably -NHCOOR ¹⁸ or -OCONHR ²¹ ( Here, R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

The above "coordinating oxygen atom-containing group" is exemplified by acetonitrile acetone. Base, crown ether group, etc.

Further, examples of the "basic group containing a basic nitrogen atom" include an amine group (-NH ₂ ) and a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ , here, R ⁸ , R ⁹ and R ¹⁰ Each of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 or more carbon atoms, and the aralkyl group having 7 or more carbon atoms, and the fluorenyl group represented by the following formula (a1), and the following formula (a2) A thiol group or the like is shown as a preferred example.

In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

More preferably, these groups are an amine group (-NH ₂ ) or a substituted amine group (-NHR ⁸ , -NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ and R ¹⁰ each independently represent a carbon number of 1~ 10 alkyl group, phenyl group, benzyl group), fluorenyl group represented by the above formula (a1). In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group, and Benzyl], a fluorenyl group represented by the above formula (a2): In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group, and the like.

In particular, an amine group (-NH ₂ ) or a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ may be preferably used, wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent a carbon number of 1 to 5; An alkyl group, a phenyl group, a benzyl group, and a fluorenyl group represented by the above formula (a1). In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, and a benzyl group. In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group, and the like.

The alkyl group in the above "alkoxycarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group and an ethyl group.

The alkyl group in the above "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.

The "carboxylate group" may, for example, be a group containing an ammonium salt of a carboxylic acid.

As the above "sulfonylamino group", a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (methyl group, etc.), a mercapto group (ethyl fluorenyl group, a trifluoroethenyl group or the like).

The above-mentioned "heterocyclic structure" is exemplified by the following structures: thiophene, furan, dibenzopyran, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyridyl Zolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane (trithiane), isoporphyrin, isoindolinone, benzimidazolone, benzothiazole, amber imine, phthalimide, naphthyl imine, etc. Hydantoin, guanidine, quinoline, carbazole, acridine, acridone, hydrazine.

Further, the above-mentioned "heterocyclic structure" may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon number of 6 to 16 such as a phenyl group or a naphthyl group. An aryl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonyl decylamino group, an ethoxy group, a methoxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. ~20 alkoxy group, halogen atom such as chlorine or bromine; alkoxycarbonyl group having a carbon number of 2 to 7 such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; a cyano group; a third butyl carbonate; carbon Acid ester group and the like.

The above "alkoxyalkylene group" may be any of a monoalkoxyalkyl group, a dialkoxyalkyl group or a trialkoxyalkyl group, and is preferably a trialkoxyalkyl group. For example, a trimethoxy group may be mentioned. A decyl group, a triethoxy decyl group, and the like.

The above "epoxy group" may, for example, be a substituted or unsubstituted oxiranyl group (oxiranyl group).

In the present specification, each of the technical matters such as the temperature and the thickness including the option of the substituent or the linking group of the compound may be combined with each other even if the list is independently described.

The linking group bonded to the above adsorption site is preferably a single bond or consists of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 a linking group formed by ~20 sulfur atoms, which may be unsubstituted or more substituted.

In the above, the above A ^{1 is} preferably a monovalent substituent having at least one selected from the group consisting of an acid group, a urea group, an urethane group, a sulfonamide group, a quinone group, and a coordination group. A group in a group consisting of groups of oxygen atoms.

In particular, from the viewpoint of well interacting with the high refractive index particles, increasing the refractive index, and lowering the viscosity of the composition, A ^{1 is more} preferably a monovalent substituent having at least one functional group having a pKa of 5 to 14.

Here, "pKa" is the same as that defined later.

The functional group having a pKa of 5 to 14 may, for example, be a ureido group, a urethane group, a sulfonylamino group, a quinone imine group or a group containing a coordinating oxygen atom.

Specific examples thereof include a urea group (pKa of about 12 to 14), a urethane group (pKa of about 11 to 13), and a COCO ₂ CO- (a pKa of 8 as a coordinating oxygen atom). ~10 or so), sulfonamide group (pKa is about 9 to 11) and the like.

The above A ^{1 is} preferably represented by a monovalent substituent represented by the following formula (A4).

In the above formula (A4), B ¹ represents the above-mentioned adsorption site (i.e., an acid group, a urea group, a urethane group, a group containing a coordinating oxygen atom, a group containing a basic nitrogen atom, an alkoxy group). Alkylcarbonyl, alkylaminocarbonyl, carboxylate, sulfonylamino, heterocyclyl, alkoxyalkyl, epoxy, isocyanate or hydroxy), R ²⁴ represents a single bond or (a+ 1) The linkage of the price. a represents an integer of 1 to 10, in the presence of a plurality of B in the formula (A4) ¹ may be identical or different.

The adsorption site represented by the above B ¹ may be the same adsorption site as the adsorption site of A ¹ constituting the above formula (A1), and preferred examples are also the same.

Among them, an acid group, a urea group, a urethane group, a sulfonylamino group, a quinone imine group or a group having a coordinating oxygen atom is preferred, and a functional group having a pKa of 5 to 14 is more preferred. From this point of view, a ureido group, a urethane group, a sulfonylamino group, a quinone imine group or a group containing a coordinating oxygen atom is more preferable.

R ²⁴ represents a single bond or a (a+1)-valent linking group, and a represents 1 to 10. Preferably, a is 1 to 7, more preferably a is 1 to 5, and particularly preferably a is 1 to 3.

The (a+1)-valent linking group includes from 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group formed may be unsubstituted or more substituted. Hereinafter, this linking group is defined as a linking group LA.

The linking group LA is preferably a single bond or from 1 to 50 carbon atoms, 0 to 8 (a+1)-valent linking group formed by a nitrogen atom, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms, more preferably a single bond or one by one (a+1) valence linkage formed by 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms. Preferably, it is a single bond or consists of 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. +1) the link of the price.

As the linking group LA, the (a+1)-valent linking group in the above group has In the case of a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amine group and a carboxyl group. Sulfhydryl group, N-sulfonyl decylamino group, ethoxycarbonyl group, etc. having 1 to 6 carbon atoms, alkoxy group such as methoxy group and ethoxy group, alkoxy group having 1 to 6 carbon atoms, chlorine and bromine Examples thereof include a halogen atom, a oxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group, and a carbonate group such as a cyano group or a tert-butyl carbonate.

. R ²

R ² represents a single bond or a divalent linking group. The n R ^{2 's} may be the same or different. Examples of the linking group include the above-described linking group LA (wherein the valence is divalent).

. R ¹

R ¹ represents a (m + n) valent linking group. m+n satisfies 3~10. The (m+n)-valent linking group represented by R ¹ above may be one to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 hydrogen atoms. A group formed by 0 to 20 sulfur atoms (referred to as a linking group LB). Among them, a group formed by 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms is preferred. . The linking group may have a substituent, and examples of the substituent include a substituent which the substituent LA may have. Specific examples of the (m+n)-valent linking group represented by the above R ¹ include specific examples disclosed in the columns [0082] and [0083] of JP-A-2007-277514 (Japanese Patent Application No. 2006-269707). Example (1) to specific example (17).

Specific examples of the (m+n)-valent linking group represented by the above R ¹ are shown below. However, the present invention is not limited to these specific examples.

[Chemical 6]

. m

m represents a positive number of 8 or less. m is preferably from 0.5 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3.

. n

n means 1~9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

. P ¹

P ¹ represents a polymer chain, and can be selected from known polymers or the like according to the purpose and the like. m P ¹ may be the same or different. In the polymer, when the polymer chain is formed, it is preferably a polymer or copolymer selected from a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, or a guanamine polymer. , an epoxy-based polymer, an anthrone-based polymer, and a modified or copolymer of the polymers [for example, copolymerization of a polymer including a polyether/polyurethane copolymer, a polyether/vinyl monomer) At least one of the group consisting of a substance (which may be any of a random copolymer, a block copolymer, and a graft copolymer) is more preferably selected from a polymer or copolymer of a vinyl monomer. At least one of a group consisting of an ester polymer, an ether polymer, a urethane polymer, and a modified or copolymer of the polymers, particularly preferably a polymer of a vinyl monomer or Copolymer.

The polymer chain P ¹ preferably contains at least one repeating unit. The number k of repetitions of the at least one repeating unit in the polymer chain P ¹ is preferably 3 or more, and more preferably 5 or more, from the viewpoint of exerting a steric repulsive force and improving dispersibility. Further, from the viewpoint of suppressing the large volume of the dispersant and causing the high refractive index particles to be densely present in the white cured film, the number k of repeating units of the at least one repeating unit is preferably 50 or less, more preferably 40 or less. Further, it is preferably 30 or less. Further, the above polymer chain is preferably soluble in an organic solvent. When the affinity with an organic solvent is low, affinity with a dispersion medium becomes weak, and the adsorption layer which is sufficient for dispersion stabilization may not be ensured.

Among the dispersants represented by the above formula (A1), a dispersant represented by the following formula (A2) is preferred.

A ² has the same meaning as A ¹ above.

R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. The n R ^{4 's} may be the same or different. In addition, m R ^{5 's} may be the same or different. The divalent linking group represented by R ⁴ and R ⁵ may be the same as those exemplified as the divalent linking group represented by R ^{2 of} the above formula (A1), and the preferred embodiment is also the same.

R ³ is a linking group having the same meaning as the above R ¹ .

m and n are the same as the above formula (A1).

P ² has the same meaning as the above P ¹ .

Among the dispersants represented by the above formula (A2), a dispersant which satisfies all of R ³ , R ⁴ , R ⁵ , P ² , m and n shown below is preferable.

R ³ : the above specific example (1), specific example (2), specific example (10), specific example (11), specific example (16) or specific example (17)

R ⁴ : a single bond, or the following structural unit or a combination of the structural units: "1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30" A divalent linking group formed by a hydrogen atom and 0 to 5 sulfur atoms (may also have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, and a phenyl group; a naphthyl group having 6 to 16 carbon atoms such as a aryl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonyl decylamino group, an ethoxy group, and the like, and a decyloxy group having 1 to 6 carbon atoms. Alkoxy group having 1 to 6 carbon atoms such as an oxy group or an ethoxy group; a halogen atom such as chlorine or bromine; and an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; , cyano group, carbonate ester such as tributyl carbonate, etc.)

R ⁵ : single bond, ethyl group, propyl group, the following group (a) or the following group (b)

Further, in the following groups, R ¹² represents a hydrogen atom or a methyl group, and 1 represents 1 or 2.

[化10]

P ² : a polymer or copolymer of a vinyl monomer, an ester polymer, an ether polymer, a urethane polymer, and a modified product of the polymers

m:1~3

n: 3~6

The acid value of the specific dispersion resin A is not particularly limited, and from the viewpoint of dispersibility, the acid value is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and particularly preferably 250 mgKOH/g or less. In addition, the lower limit of the acid value is not particularly limited, and is preferably 5 mgKOH/g or more, and more preferably 10 mgKOH/g or more from the viewpoint of dispersion stability of the high refractive index particles. Here, the acid value of the specific dispersion resin A is a solid component acid value. The acid value of the specific dispersion resin A can be calculated, for example, from the average content of the acid groups in the specific dispersion resin A described above.

The molecular weight of the specific dispersion resin A is preferably from 1,000 to 50,000, more preferably from 3,000 to 30,000, still more preferably from 3,000 to 20,000, based on the weight average molecular weight. When the weight average molecular weight is within the above range, the effect of introducing a plurality of the adsorption sites introduced into the terminal of the polymer can be sufficiently exhibited, and the property of exhibiting excellent adhesion to the surface of the titanium oxide particles can be exhibited. The method for measuring the molecular weight is based on the conditions of Gel Permeation Chromatography (GPC) as defined later.

The above specific dispersion resin A is not particularly limited and may be based on Japanese patents. The synthesis method described in paragraphs 0114 to 0140 and paragraphs 0266 to 0348 of No. 2007-277514 is synthesized.

. Specific dispersion resin B

The dispersing agent for dispersing the high refractive index particles is preferably an oligoimine-based dispersing agent containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine-based dispersant is preferably a dispersion resin (hereinafter referred to as "specific dispersion resin (B)" as appropriate), and the dispersion resin contains a repeat having a partial structure X (the partial structure X has a pKa of 14 or less) The unit and the side chain containing the side chain Y having an atomic number of 40 to 10,000 contain a basic nitrogen atom in at least one of the main chain and the side chain. Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

The specific resin (B) may have a partial structure W which is paired with the partial structure X or the like, and the partial structure W is preferably a structural portion having a nitrogen atom having a pKb of 14 or less, and more preferably a nitrogen having a pKb of 10 or less. The structure of the atom. The alkali strength pKb is one of the indexes for quantitatively indicating the strength of the alkali, and is the same as the basicity constant. The alkali strength pKb has a relationship of pKb = 1 - pKa with respect to the acid strength pKa described later. Further, when the partial structure X and the partial structure W are paired to form a salt structure, it is assumed that the respectively dissociated structure is bonded to the compound of the structures by proton (H ⁺ ) or hydroxide ion (OH ^- ) ions. Form to evaluate its pKa and pKb. The partial structure X will be further described in detail below.

Regarding the partial structure X, the details of its preferred range are as will be described below. Part of the structure X is the same meaning. Further, the details of the preferred range of the above-mentioned side chain Y are the same as those of the side chain Y which will be described later. The above W is preferably a structure in which the connecting portion of the side chain Y is dissociated to become an ion-bonding portion.

An example of the specific dispersion resin (B) is a resin represented by the following formula [B].

In the above formula, x, y and z respectively represent the polymerization molar ratio of the repeating unit, and preferably x is 5 to 50, y is 5 to 60, and z is 10 to 90. l represents the number of bonds of the polyester chain, and is an integer which can form a side chain having an atomic number of 40 to 10,000, and l is preferably 5 to 100,000, more preferably 20 to 20,000, and still more preferably 40 to 2,000. The repeating unit in which the copolymerization ratio is defined by x in the formula is a partial structure X, and the repeating unit in which the copolymerization ratio is defined by z in the formula is a partial structure Y.

The specific dispersion resin (B) is preferably a dispersion resin containing a repeating unit (i) and a side chain (ii) having a side chain Y having an atomic number of 40 to 10,000 (hereinafter referred to as "specific dispersion resin (B1)"). The above repeating unit (i) is (i) selected from a poly(lower alkylene imine) repeating unit, a polyallylamine repeating unit, a polydiallyl group At least one of an amine repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and a polyvinylamine repeating unit containing a basic nitrogen atom and having a bond to the basic nitrogen A partial structure X having an atom and having a functional group having a pKa of 14 or less.

The specific dispersion resin (B1) contains the above repeating unit (i). Thereby, the adsorption force of the dispersion resin on the particle surface is improved, and the interaction between the particles can be reduced. The poly(lower alkylene imide) may be in the form of a chain or a network. Here, the lower alkylene imine refers to an alkyleneimine having an alkylene chain having 1 to 5 carbon atoms. The above repeating unit (i) is preferably a main chain portion forming a specific dispersion resin. The number average molecular weight of the main chain portion, that is, the portion obtained by removing the side chain containing the side chain Y moiety from the specific dispersion resin (B1), preferably has a number average molecular weight of 100 to 10,000, more preferably 200 to 5,000, most Good for 300~2,000. The number average molecular weight of the main chain portion can be measured by a polystyrene equivalent value by a GPC method.

The specific dispersion resin (B1) preferably contains a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), or a repeating unit represented by the formula (I-1). The dispersion resin of the repeating unit represented by (I-2a).

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group (preferably, carbon number 1 to 6). a independently represents an integer from 1 to 5, respectively. * indicates the connection between the repeating units.

R ⁸ and R ⁹ are the same meaning as R ¹ .

L is a single bond, an alkyl group (preferably having a carbon number of 1 to 6), an alkenyl group (preferably having a carbon number of 2 to 6), an extended aryl group (preferably having a carbon number of 6 to 24), and an extension of the aromatic group. A linking group (preferably having a carbon number of 1 to 6), an imido group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group or a combination of such groups. Among them, a single bond or -CR ⁵ R ⁶ -NR ⁷ - (imino group becomes X or Y) is preferred. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group (preferably, carbon number 1 to 6). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

L ^a is a structural moiety which forms a ring structure together with CR ⁸ CR ⁹ and N, and preferably forms a structural part of a non-aromatic heterocyclic ring having 3 to 7 carbon atoms together with the carbon atom of CR ⁸ CR ⁹ . Further, it is preferable to form a structural part of a non-aromatic heterocyclic ring of 5 to 7 members together with a carbon atom of CR ⁸ CR ⁹ and N (a nitrogen atom), and it is more preferable to form a structural part of a non-aromatic heterocyclic ring of 5 members. It is especially preferred to form a structural moiety of pyrrolidine. Among them, the structural moiety may further have a substituent such as an alkyl group.

X represents a group having a functional group having a pKa of 14 or less.

Y represents a side chain having an atomic number of 40 to 10,000.

The specific dispersion resin (B1) preferably further contains a repeating unit represented by the formula (I-3), the formula (I-4) or the formula (I-5) as a copolymerization component. The dispersion property can be further improved by including such a repeating unit in the specific dispersion resin (B1).

[Chemistry 13]

R ¹ , R ² , R ⁸ , R ⁹ , L, La and a have the same meanings as defined in the formula (I-1), the formula (I-2) and the formula (I-2a).

Ya represents a side chain having an anion group of 40 to 10,000 atoms. The repeating unit represented by the formula (I-3) can be formed by adding an oligomer having a group which reacts with an amine to form a salt in a resin having a primary amino group or a secondary amine group in the main chain portion. The reaction is carried out with a substance or a polymer. Ya is preferably a formula (III-2) described later.

In the formula (I-1) to the formula (I-5), R ¹ and R ^{2 are} particularly preferably a hydrogen atom. From the viewpoint of raw material acquisition, a is preferably 2.

The specific dispersion resin (B1) may further contain a lower alkyleneimine having a primary amino group or a tertiary amino group as a repeating unit. Further, the group represented by the above X, Y or Ya may be further bonded to the nitrogen atom of the lower alkyleneimine repeating unit. Further, a resin containing both a repeating unit to which a group represented by X is bonded and a repeating unit to which Y is bonded in such a main chain structure is also contained in the specific dispersion resin (B1).

From the viewpoint of storage stability and developability, among all the repeating units contained in the specific dispersion resin (B1), the repeating unit represented by the formula (I-1) preferably contains 1 mol% to 80 mol%. %, preferably contains 3 mol% to 50 mol%. on From the viewpoint of storage stability, among all the repeating units contained in the specific dispersion resin (B1), the repeating unit represented by the formula (I-2) preferably contains 10 mol% to 90 mol%, which is the best. It contains 30% by mole to 70% by mole. From the viewpoint of the balance of dispersion stability and hydrophilicity and hydrophobicity, the content ratio of the repeating unit (I-1) and the repeating unit (I-2) is preferably [(I-1): (I-2)] The ear ratio is in the range of 10:1 to 1:100, more preferably in the range of 1:1 to 1:10. From the viewpoint of the effect, among all the repeating units contained in the specific dispersion resin (B1), the repeating unit represented by the formula (I-3) which is used in combination as needed preferably contains 0.5 mol% to 20 mol%. %, preferably contains 1 mol% to 10 mol%. Further, the case where the polymer chain Ya is ion-bonded can be confirmed by infrared spectroscopy or alkali titration.

In addition, the description of the copolymerization ratio of the above formula (I-2) also has the same meaning for the repeating unit represented by the formula (I-2a), the formula (I-4), and the formula (I-5). When both are included, it refers to the total amount.

. Partial structure X

The partial structure X in each of the above formulas has a functional group having a pKa of 14 or less at a water temperature of 25 °C. The term "pKa" as used herein refers to the definitions described in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). "The functional group having a pKa of 14 or less" is not particularly limited as long as the physical properties satisfy the above conditions, and examples thereof include a group having a pKa satisfying the above range in a known functional group, and particularly preferably a functional group having a pKa of 12 or less. Particularly preferred is a functional group having a pKa of 11 or less. The lower limit does not particularly exist, and is actually -5 or more. The partial structure X is preferably a carbon number of 1 to 12, more preferably 1 to 6. Specifically, for example, it has a carboxylic acid group (pKa: about 3 to 5), a sulfonic acid group (pKa: about 3 to 2), -COCH ₂ CO- (pKa: about 8 to 10), and COCH ₂ CN (pKa: about 8 to 11), -CONHCO-, phenolic hydroxyl group, -R _F CH ₂ OH or -(R _F ) ₂ CHOH (R _F represents a perfluoroalkylene group or a perfluoroalkyl group. pKa A group such as a sulfonamide group (pKa: about 9 to 11), preferably a carboxylic acid group (pKa: about 3 to 5) or a sulfonic acid group (pKa: -3~-) 2 or so), -COCH ₂ CO- (pKa: about 8 to 10).

The interaction with the high refractive index particles can be achieved by the pKa of the functional group of the partial structure X being 14 or less. The partial structure X is preferably a direct bond to the basic nitrogen atom of the above repeating unit containing a basic nitrogen atom. The partial structure X may be linked not only by a covalent bond but also by a state in which an ion bond is formed to form a salt. The partial structure X is particularly preferably a structure represented by the following formula (V-1), formula (V-2) or formula (V-3).

U represents a single bond or a divalent linking group.

d and e each independently represent 0 or 1.

Q represents a mercapto or alkoxycarbonyl group.

The divalent linking group represented by U may, for example, be an alkylene group (more specifically, for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CHMe- (Me is a methyl group), -(CH) ₂ ) _5- , -CH ₂ CH(nC ₁₀ H ₂₁ )-, etc.), an alkyl group containing oxygen (more specifically, for example, -CH ₂ OCH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ - Etc.), an alkenyl group (preferably having a carbon number of 2 to 12, more preferably 2 to 6, more preferably 2 to 3), or an aryl group (for example, a phenyl group, a tolylene group, and a biphenyl group). a base, an anthranyl group, a furfuryl group, a pyrrolyl group, etc., an alkoxy group (e.g., an ethoxy group, a propenoxy group, a phenoxy group, etc.) or a combination thereof, particularly preferably a carbon number of 1 to 30. The alkyl group or the aryl group having a carbon number of 6 to 20 is preferably an alkyl group having 1 to 20 carbon atoms or an extended aryl group having 6 to 15 carbon atoms.

Further, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents a mercapto or alkoxycarbonyl group. The fluorenyl group of Q is preferably a fluorenyl group having 1 to 30 carbon atoms (e.g., a fluorenyl group, an ethyl fluorenyl group, a n-propyl fluorenyl group, a benzamidine group, etc.), and particularly preferably an acetamino group. The Q alkoxycarbonyl group, acyl Q particularly preferably, it is ease of manufacture, the viewpoint of obtaining a raw material (X precursors X ^a) is concerned, is preferably acetyl group.

The partial structure X is preferably bonded to the basic nitrogen atom of a repeating unit containing a basic nitrogen atom. Thereby, the dispersibility and dispersion stability of the titanium dioxide particles are drastically improved. It is considered that the partial structure X also imparts solvent solubility and suppresses precipitation of the resin over time, thereby contributing to dispersion stability. Further, since the partial structure X contains a functional group having a pKa of 14 or less, it also functions as an alkali-soluble group. It is considered that the developability is improved by this, and dispersibility, dispersion stability, and developability can be simultaneously achieved.

The content of the functional group having a pKa of 14 or less in the partial structure X is not particularly limited, and is preferably 0.01 mmol to 5 mmol, particularly preferably 0.05 mmol to 1 mmol, per 1 g of the specific dispersion resin (B1). In addition, from the viewpoint of acid value, From the viewpoint of the developability, it is preferable that the acid value of the specific dispersion resin (B1) is about 5 mgKOH/g to 50 mgKOH/g, and the functional group having a pKa of 14 or less is contained.

. Side chain Y

Y is a known polymer chain such as polyester, polyamine, polyimide or poly(meth)acrylate which can be bonded to the main chain portion of the specific dispersion resin (B1). The bonding site of Y with the specific dispersion resin (B1) is preferably the terminal of the side chain Y.

Y is preferably a polycondensation with a poly(lower alkylene imine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, and m-xylenediamine-epichlorohydrin. The above nitrogen atom is bonded to at least one of the repeating unit of the system and the repeating unit of the polyvinylamine-based repeating unit containing a nitrogen atom. a poly(lower alkylene imine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate repeating unit, and The bonding method of the main chain portion and the Y of the repeating unit containing at least one of the polyvinylamine-based repeating units and the like is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the bonding mode of Y to the main chain portion is a covalent bond: ion bond = 100:0 to 0:100, preferably 95:5 to 5:95, and particularly preferably 90:10 to 10:90.

Y preferably forms a guanamine bond with the above nitrogen atom of the above-mentioned repeating unit containing a basic nitrogen atom, or forms an ionic bond as a carboxylate.

The number of atoms of the side chain Y is preferably from 50 to 5,000, more preferably from 60 to 3,000, from the viewpoint of dispersibility, dispersion stability, and developability.

Further, the number average molecular weight of Y can be measured by a polystyrene equivalent value by a GPC method. At this time, Y is actually measured in a state before being incorporated into the resin. Its molecular weight. The number average molecular weight of Y is particularly preferably from 1,000 to 50,000, and from the viewpoint of dispersibility, dispersion stability, and developability, it is preferably from 1,000 to 30,000. The molecular weight of Y can be determined based on the polymer compound which is a raw material of Y, and the measurement method is based on the measurement conditions of GPC which will be described later.

The side chain structure represented by Y is preferably two or more in one molecule of the resin with respect to the main chain, and more preferably five or more.

More preferably, Y has a structure represented by the formula (III-1).

In the formula (III-1), Z is a polymer having a polyester chain as a partial structure Or an oligomer, which represents a residue obtained by removing a carboxyl group from a polyester having a free carboxylic acid represented by HO-CO-Z. When the specific dispersion resin (B1) contains a repeating unit represented by the formula (I-3) to the formula (I-5), it is preferred that Ya is a formula (III-2).

In the formula (III-2), Z has the same meaning as Z in the formula (III-1). In the above partial structure Y, the polyester having a carboxyl group at a single terminal can be obtained by a carboxylic acid and a lactone. It is obtained by polycondensation, polycondensation of a hydroxyl group-containing carboxylic acid, polycondensation of a glycol with a dicarboxylic acid (or a cyclic acid anhydride), and the like.

Z is preferably -(L ^B ) _nB -Z ^B .

Z ^B represents a hydrogen atom or a monovalent organic group. When Z ^B is an organic group, an alkyl group (preferably having 1 to 30 carbon atoms), an aryl group or a heterocyclic group is preferable. Further, Z ^B may have a substituent. Examples of the substituent include an aryl group having 6 to 24 carbon atoms and a heterocyclic group having 3 to 24 carbon atoms.

L ^B is an alkylene group (preferably having a carbon number of 1 to 6), an alkenyl group (preferably having 2 to 6 carbon atoms), an aryl group (preferably having a carbon number of 6 to 24), and a heteroaryl group ( A linking group having a carbon number of 1 to 6), an imido group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group or a combination of these groups is preferred. Among them, a linking group having an alkyl group (preferably having a carbon number of 1 to 6), an ether group, a carbonyl group or a combination of these groups is preferred. The alkyl group may be a branch or a straight chain. The alkylene group may have a substituent, and a preferred substituent is an alkyl group (preferably having 1 to 6 carbon atoms), a mercapto group (preferably having 2 to 6 carbon atoms), and an alkoxy group (preferably having a carbon number). 1~6), or an alkoxycarbonyl group (preferably having a carbon number of 2-8). L ^B preferably has a structure of -CO-R ^B -O- together with CO attached thereto (that is, in the form of CO-L ^B ). R ^{B is} particularly preferably an alkylene group which may have a substituent (preferably having a carbon number of 1 to 12, more preferably 1 to 6, more preferably 1 to 3). nB is an integer of 5 to 100,000, preferably an integer of 5 to 1000, more preferably an integer of 5 to 100. nB L ^Bs may also have different structures.

Specific examples of the specific dispersion resin (B) are shown below by the specific structure of the repeating unit of the resin and a combination thereof, but the present invention is not limited thereto. In the following formula, k, l, m and n respectively represent the polymerization molar ratio of the repeating unit, k is 1 to 80, l is 10 to 90, m is 0 to 80, n is 0 to 70, and k + l +m+n=100. The one defined by k, l, m and only defined by k and l respectively mean k+l+m=100 and k+l=100. p and q represent the number of linkages of the polyester chains, and each independently represents 5 to 100,000. R ^a represents a hydrogen atom or an alkoxycarbonyl group.

[化18]

[Chemistry 19]

[Chemistry 20]

[Chem. 21]

[化22]

[化23]

[Chem. 24]

[化25]

[Chem. 26]

When the specific dispersion resin (B1) is synthesized, it can be produced by the following method: (1) a method of reacting a resin having a primary amine group or a secondary amine group with a precursor y of a partial structure X precursor x and Y (2) A method of polymerizing a monomer having a structure corresponding to a part of the structure X and a macromonomer containing Y, and the like. Preferably, it is produced by first synthesizing a resin having a primary amine group or a secondary amine group in the main chain, and then reacting the precursor x of X and the precursor y of Y with the resin, by polymer The reaction introduces a part of the structures X and Y onto the nitrogen atom present in the main chain. The details of the manufacturing method can be referred to Japanese Patent Laid-Open No. 2009-203462 and the like.

The specific molecular weight of the specific dispersion resin B is preferably 3,000 to 100,000, more preferably 5,000 to 55,000, and the weight average molecular weight is within the above range, and the plurality of adsorptions introduced to the end of the polymer can be sufficiently exhibited. The effect of the part is excellent in the adsorptivity to the surface of the titanium dioxide particle. In addition, in this specification, GPC is set to TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (made by Tosoh Corporation) using HLC-8020GPC (made by Tosoh Co., Ltd.) unless otherwise specified. To determine. The carrier may be appropriately selected, and if it is soluble, it is set to use tetrahydrofuran.

In the photosensitive composition of the present invention, the dispersing agent for the high refractive index particles may be used alone or in combination of two or more.

The content of the dispersant for the high refractive index particles relative to the total solid content of the composition of the present invention is preferably 0.05% by mass or more, more preferably 1% by mass or more, and further preferably from the viewpoint of dispersibility and dispersion stability. It is 5% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 10% by mass or less. In the case of the high refractive index particles, the dispersing agent for the high refractive index particles is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, based on 100 parts by mass of the high refractive index particles. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

(dispersant for black pigment)

Specific examples of the commercially available product which can be used as a dispersing agent for a black pigment include, for example, an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a (meth)acrylic (co)polymer polise. Polyflow No.75, Polyflow No.90, Polyflow No.95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (Yushang Co., Ltd.) Manufactured) Active agent; polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl phenyl benzene Nonionic surfactants such as ethyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yushang Co., Ltd.) Anionic surfactants; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all Ciba Speciality Chemicals) ))), Disperse-aid 6, Disperse-aid 8, Disperse-aid 15, Disperse-aid 9100 (all manufactured by Sannopco) polymer dispersant; Solsperse 3000, Solsperse 5000, Solsperse 9000, Sonour Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 24000, Solsperse 26000 , Solsperse 28000, Solsperse 32000, Solsperse 36000 and other Solsperse dispersants (Lubrizol) Manufacturing); Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Eddie Popular Science Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Eddie Pronknik Adeka Pluronic) P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Ai Adeka Pluronic P-123 (made by Adeco (ADEKA)) and Eonet S-20 (made by Sanyo Chemicals Co., Ltd.), Disperbyk 101, Disperbyk 103, Disperbyk 106, Disperbyk 108, Disperbyk 109, Disperbyk 111, Disperbyk 112, Disperbyk 116, Disperbyk 130, Disperbyk 140, Disperbyk 142, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Di Disperbyk 167, Disperbyk 170, Disperbyk 171, Disperbyk 174, Disperbyk 176, Diss Disperbyk 180, Disperbyk 182, Disperbyk 2000, Disperbyk 2001, Disperbyk 2050, Diss Disperbyk 2150 (manufactured by BYK Chemie Co., Ltd.). In addition, it can also be manufactured by Kawaken Fine Chemicals Co., Ltd. An amphoteric dispersant such as Hinoact T-8000E.

In addition, an oligomer or a polymer having a polar group at a molecular terminal or a side chain such as an acrylic copolymer or the like can be preferably used as a dispersing agent. Further, an amine-based resin obtained by adding a polyester chain to an amine group of a polyethylenimine or a polyallylamine having a weight average molecular weight of 300 to 20,000 can also be used as a dispersing agent.

From the viewpoint of dispersibility, developability, and sedimentation property, it is preferred to use a resin as described below, and in particular, from the viewpoint of dispersibility, it is preferred to disperse a polymer having a polyester chain in a side chain. Agent. Further, from the viewpoint of dispersibility and resolution of a pattern formed by photolithography, a resin having an acid group and a polyester chain is preferable. From the viewpoint of adsorptivity, a preferred acid group in the pigment dispersant is preferably an acid group having a pKa of 6 or less, and more preferably a carboxylic acid, a sulfonic acid or a phosphoric acid.

Preferred examples of the dispersing resin include graft copolymers having the following graft chains in the molecule, and the number of atoms of the graft chain other than a hydrogen atom is in the range of 40 to 10,000, and is selected from a polyester structure and a polyether. Structure and polyacrylate structure. More preferably, it is a graft copolymer containing a structural unit represented by the following formula (A), and more preferably a graft copolymer containing a structural unit represented by any one of the formulas (1) to (5) (specific dispersion) Resin C).

In the formula, X ^A represents a hydrogen atom, a halogen atom or a monovalent organic group, Y ^A represents a single bond or a divalent linking group, and Z ^A represents a hydrogen atom or a monovalent organic group. When Z ^A is an organic group, it is preferably an alkyl group (preferably having a carbon number of 1 to 30, more preferably 1 to 12) or an alkenyl group (preferably having a carbon number of 2 to 30, more preferably 2 to 12). An aryl group (preferably having a carbon number of 6 to 30, more preferably 6 to 10) or a heteroaryl group (preferably having a carbon number of 1 to 30, more preferably 1 to 6). The alkyl group may be a branch or a straight chain. The aryl group and the heteroaryl group may be a single ring or a polycyclic ring. The groups may have more substituents, and the substituents may have a hydroxyl group, a halogen atom, a mercapto group (preferably having a carbon number of 2 to 6), an amine group (preferably having a carbon number of 0 to 6), and an alkane. An oxy group (preferably having a carbon number of 1 to 6), an alkoxycarbonyl group (preferably having 2 to 8 carbon atoms), an aryl group (preferably having a carbon number of 6 to 24), and a heterocyclic group (preferably carbon). Number 1~12). In the presence of a plurality of L ^A, may vary. Z ^A may further have a substituent, and examples of the substituent include an aryl group having 6 to 24 carbon atoms and a heteroaryl group having 3 to 24 carbon atoms. nA represents an integer of 1 to 500, preferably an integer of 5 to 100.

L ^A is an alkylene group (preferably having a carbon number of 1 to 6), an alkenyl group (preferably having 2 to 6 carbon atoms), an aryl group (preferably having a carbon number of 6 to 24), and a heteroaryl group ( A linking group having a carbon number of 1 to 6), an imido group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group or a combination of these groups is preferred. Among them, a linking group having an alkyl group (preferably having a carbon number of 1 to 6), an ether group, a carbonyl group or a combination of these groups is preferred. The alkyl group may be a branch or a straight chain. The alkylene group may have a substituent. Preferred substituents are a hydroxyl group, a halogen atom, a fluorenyl group (preferably having a carbon number of 2 to 6), an amine group (preferably having a carbon number of 0 to 6), and an alkoxy group ( It is preferably a carbon number of 1 to 6), an alkoxycarbonyl group (preferably having 2 to 8 carbon atoms), an aryl group (preferably having a carbon number of 6 to 24), and a heterocyclic group (preferably having a carbon number of 1 to 6). 12). In the presence of a plurality of L ^A, may vary.

In the formula, X ¹ to X ⁶ have the same meanings as X ^A above. Y ¹ to Y ⁵ have the same meanings as the above Y ^A . Z ¹ to Z ⁵ have the same meaning as the above Z ^A . R represents a hydrogen atom or a monovalent organic group, and R may have a structural difference in the copolymer. n, m, p, q, and r respectively represent integers having the same meaning as nA. j and k are each independently an integer of 2-8.

Y ¹ to Y ^{5 are} preferably an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, more preferably 1 to 3) or an alkenyl group (preferably having a carbon number of 6 to 22, more preferably 6 to 14), an imido group (NR ^N : R ^N is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), an ether group (O), a carbonyl group (CO), a thioether group (S) or the groups The combination. When X ¹ to X ⁶ are an organic group, an alkyl group is preferred (preferably, the carbon number is from 1 to 12, more preferably from 1 to 6, more preferably from 1 to 3).

When n, m, p, q, and r are 2 or more, the structure of each linking group may also differ. The alkylene group represented by C _j H _2j and C _k H _2k may be a straight chain or a branched chain. Further, H may be appropriately substituted with an arbitrary substituent.

Among them, a compound having a polyester chain in a side chain represented by the above formula (1) is preferred. Representative examples of these compounds are preferably exemplified by the exemplified compound 1 to the exemplified compound 71 described in Paragraph No. [0046] to Paragraph No. [0078] of JP-A-2010-106268.

Further, the exemplified compounds which are preferred dispersants are described below, but the present invention is not limited to the exemplified compounds. In the following exemplified compounds, the numerical values described in the respective structural units indicate the content of the structural unit [% by mass, suitably described as (wt%)].

[化29]

[化30]

[化31]

[化32]

[化33]

[化34]

[化35]

[化36]

[化37]

[化38]

The specific molecular weight of the specific dispersion resin B is preferably 3,000 to 100,000, more preferably 4,000 to 55,000, and the weight average molecular weight is within the above range, and the plurality of adsorptions introduced to the end of the polymer can be sufficiently exhibited. The effect of the part is excellent in the adsorptivity to the surface of the titanium dioxide particle. The method for determining the molecular weight is set to be measured by GPC and utilize the conditions described above. Wait.

Dispersing agent for black pigments from the viewpoint of dispersibility and dispersion stability The content of the total solid content of the composition of the present invention is preferably 0.05% by mass or more, more preferably 1% by mass or more, and still more preferably 5% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, and particularly preferably 10% by mass or less. In the case of the relationship with the black pigment, the dispersing agent for the black pigment is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, based on 100 parts by mass of the black pigment. The upper limit is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

In the composition of the present invention, the total amount of the dispersing agent is preferably in the solid content. It is 0.05% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. By using a dispersing agent in such a range, dispersibility and dispersion stability can be effectively imparted, and good optical characteristics or photosensitivity can be achieved, which is preferable in this respect.

[Polymerization initiator]

The polymerization initiator is preferably a compound which is decomposed by light or heat to initiate and accelerate polymerization of a polymerizable compound described later. In the case where polymerization is initiated by light, it is preferred to have absorption in a wavelength range of 300 nm to 500 nm. In the case of using heat to initiate polymerization, an initiator which decomposes at 150 ° C to 250 ° C is preferred.

The polymerization initiator is preferably a compound having at least an aromatic group, and examples thereof include (bis)decylphosphine oxide or an ester thereof, an acetophenone-based compound, and an α-aminoketone. a compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound, a thioxanthone compound, an oxime ester compound, a hexaarylbiimidazole compound, a halomethyl compound, an azo compound An organic peroxide, a diazonium compound, an anthraquinone compound, an anthraquinone compound, a sulfonium compound, a metallocene compound or the like, an onium salt compound, an organic boron salt compound, a diterpene compound, and the like.

From the viewpoint of sensitivity, an oxime ester compound, a mercaptophosphine oxide compound, an acetophenone compound, an α-amino ketone compound, a trihalogenated methyl compound, a hexaarylbiimidazole compound, and sulfur are preferred. Alcohol compound.

Examples of preferred polymerization initiators are listed below, but the invention is not limited to the examples.

Specific examples of the acetophenone-based compound include 2,2-diethoxy group. Acetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4'-isopropyl -2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)- Butanone-1, 2-tolyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinylacetone-1, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4 -(4-morpholinyl)phenyl]-1-butanone and 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one. Among them, a compound which can be preferably used as a commercially available product is exemplified by 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one [trade name] "Irgacure-907" (manufactured by Ciba Speciality Chemicals).

Further, an α-alkylaminobenzophenone [Irgacure-379 (manufactured by Ciba Speciality Chemicals)] is also preferably exemplified as the initiator which can be obtained as a commercial product. Wait.

More preferably, the trihalogenated methyl compound may be substituted with at least one monohalogen substituted group A. a s-triazine derivative obtained by binding a dihalo-substituted methyl group or a trihalogen-substituted methyl group to a s-triazine ring, and specifically, for example, 2,4,6-tris(monochloromethyl) -s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6- Bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4 ,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6 - bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl) -4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethane) -s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethane) -s-triazine, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis ( Trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis ( Trichloromethyl)- Triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tri (tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)- Is a triazine or the like.

Examples of the hexaarylbiimidazole compound include various compounds described in the respective specifications of Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5 '-Tetraphenylbiimidazole, 2,2'-bis(o-, p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorobenzene) Base)-4,4',5,5'-tetra(m-methoxyphenyl) , 2,2'-bis(o-o-o-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4 , 4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'- Bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole and the like.

About fluorenylphosphine oxide compounds, such as [2,4,6-trimethylbenzhydramidine The bis-diphenyl-phosphine oxide can be obtained under the trade name of Darocur TPO (manufactured by Ciba Japan Co., Ltd.) [bis(2,4,6-trimethylbenzhydrazide) The base)-phenylphosphine oxide can be obtained under the trade name of Irgacure 819 (manufactured by Ciba Japan Co., Ltd.).

The oxime ester compound can be listed as: "Journal of the Chemical Society, JCS) Perkin II (1979) 1653-1660, "Journal of the Chemical Society (JCS) Perkin II (1979) 156-162 , "The Journal of Photopolymer Science and Technology" (1995) 202-232, the compound described in Japanese Patent Laid-Open Publication No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent In the case of the compound described in JP-A-2004-534797, commercially available products include IRGACURE OXE 01 (1,2-octanedione, 1-[4-) manufactured by Ciba Speciality Chemicals. (phenylthio)-, 2-(o-benzylidene hydrazide)]), IRGACURE OXE 02 (ethyl ketone, 1-[9- Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-,1-(o-ethylindenyl), TR-PBG-304 (Changzhou Power Electronic New Material Co., Ltd.) The company manufactures and the like as a preferred compound.

Further, a cyclic ruthenium compound described in JP-A-2007-231000 and JP-A-2007-322744 can be preferably used.

The ruthenium compound having a specific substituent disclosed in Japanese Laid-Open Patent Publication No. 2007-269779, or the ruthenium compound having a thioaryl group disclosed in Japanese Laid-Open Patent Publication No. 2009-191061, is exemplified.

Further, the ruthenium compound shown below can also be preferably used.

[39]

Bismuth compounds have maximum absorption in the wavelength range of 350nm~500nm The absorption wavelength preferably has an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably a high absorbance at 365 nm and 455 nm.

From the viewpoint of sensitivity, the cerium compound is at 365 nm or 405 nm. The molar absorption coefficient is preferably from 3,000 to 300,000, more preferably from 5,000 to 300,000, and particularly preferably from 10,000 to 200,000.

The molar absorption coefficient of the compound can be determined by a known method, specifically For example, it is preferably measured by using an ultraviolet-visible spectrophotometer (carry-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

The photopolymerization initiator may be used alone or in combination of two or more. In the solid content, the content of the photopolymerization initiator in the photosensitive composition is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, even more preferably from 0.1% by mass to 15% by mass. .

[Polymerizable compound]

The polymerizable compound is preferably a compound having at least one ethylenically unsaturated group capable of undergoing addition polymerization. Further, the polymerizable compound is preferably a compound having a boiling point of 100 ° C or higher at normal pressure. The polymerizable compound is more preferably a carbon number of 14 to 70.

Examples of the compound having at least one ethylenically unsaturated group capable of undergoing addition polymerization and having a boiling point of 100 ° C or more at normal pressure include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (methyl). a monofunctional acrylate or methacrylate such as acrylate or phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylic acid Ester, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylic acid Ester, trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene oxy)ethyl isocyanate, addition to polyfunctional alcohols such as glycerol or trimethylolethane Ethylene oxide or propylene oxide followed by (meth) acrylated, pentaerythritol or dipentaerythritol poly (meth) acrylate, Japanese Patent Special Publication No. 48-41708, Japanese Patent The urethane urethanes described in Japanese Laid-Open Patent Publication No. SHO-51-37193, Japanese Patent Laid-Open No. Sho-48-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52 The polyester acrylate described in the publication No. -30490 is a polyfunctional acrylate or methacrylate such as an epoxy acrylate which is a reaction product of an epoxy resin and (meth)acrylic acid.

Further, a compound which is described as a photocurable monomer and an oligomer in the Japanese Society of Associations Vol. 20, No. 7, and pages 300 to 308 can also be used.

In addition, it is also possible to add ethylene oxide or propylene oxide to the above polyfunctional alcohol as described in the above formulas (1) and (2) in Japanese Patent Publication No. Hei 10-62986. (Methyl) acrylated compound.

Among them, preferred are dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure of propylene sulfonate-based ethylene glycol or propylene glycol residues of these compounds. These oligomer types can also be used.

Further, an amine acrylate group as described in JP-A-48-41708, JP-A-53-37193, JP-A-2-32293, and JP-A No. 2-16765 is also preferred. An acid ester, or an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. Sho 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 Carbamate compounds. Further, an addition having an amine structure or a thioether structure in the molecule described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A polymerizable compound can obtain a photopolymerizable composition having a very excellent photospeed. city The products sold include: urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by Shanyang Guoce Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H ( Manufactured by Nippon Kayaku Co., Ltd., UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha).

Further, an ethylenically unsaturated compound having an acid group is also preferable, and commercially available products include, for example, a carboxyl group-containing trifunctional acrylate TO-756 manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. TO-1382 and so on.

Further, preferred are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate succinic acid monomer, and dipentaerythritol triacrylate.

The polymerizable compound is more preferably a tetrafunctional or higher acrylate compound.

The polymerizable compound may be used alone or in combination of two or more.

The content of the photosensitive composition is not particularly limited as long as a sufficient curing reaction can be carried out. For example, it is preferably 3 parts to 55 parts, more preferably 10 parts by mass based on 100 parts by total solid content. ~50 servings. When the content of the polymerizable compound is within the above range, the hardening reaction proceeds sufficiently.

[bonded polymer]

In the composition of the present invention, in order to improve the film properties and the like, other binder polymers having a structure different from the above components may be further used as long as the effects of the present invention are not impaired. The binder is preferably a linear organic polymer. A well-known polymer can be used arbitrarily for such a "linear organic polymer". Preferably, it is a linear or organic polymer which is soluble or swellable in water or weakly alkaline water for water development or weak alkalinity. Water development. The linear organic polymer is selected for use not only as a film forming agent but also as a developer of water, weakly alkaline water or an organic solvent.

For example, if a water-soluble organic polymer is used, water development can be performed. Examples of such a linear organic polymer include a radical polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho 58-12577 The polymer described in Japanese Patent Laid-Open Publication No. Sho 54-25957, Japanese Patent Laid-Open Publication No. Sho 54-92723, Japanese Patent Laid-Open Publication No. Sho 59-53836, No. 59-71048, a resin obtained by homopolymerization or copolymerization of a monomer of a carboxyl group, a resin obtained by homopolymerizing or copolymerizing a monomer having an acid anhydride, and hydrolyzing or semi-esterifying or semi-aminating an acid anhydride unit, using an unsaturated single An epoxidized acrylate obtained by modifying an epoxy resin with a carboxylic acid or an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include maleic anhydride.

Further, there is an acidic cellulose derivative having a carboxylic acid group in the side chain as well. In addition to this, a compound obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group or the like is useful.

In addition, Japanese Patent Laid-Open No. 7-12004, Japanese Patent Special Publication No. 7-120041, Japanese Patent Special Publication No. 7-120042, Japanese Patent Special Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent The acid group-containing urethane-based adhesive polymer described in JP-A-63-287947, JP-A No. 1-271741, and Japanese Patent Application No. Hei 10-116232, etc. It is excellent in strength and is therefore advantageous in terms of low exposure suitability.

In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in the above-mentioned European Patent No. 993966, the European Patent No. 2001-318463, and the like has an excellent balance between film strength and developability, and thus is preferable. . Further, in addition to this, polyvinylpyrrolidone or polyethylene oxide is useful as a water-soluble linear organic polymer. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin or the like is also useful.

In the case of using another binder polymer which can coexist, the content in the total solid content of the composition is preferably from 0.1% by mass to 10.0% by mass, and it is more preferable from the viewpoint of suppressing pattern peeling while suppressing development residue. It is 0.3% by mass to 6.0% by mass, and more preferably 1.0% by mass to 5.0% by mass.

[other colorants]

For the coloring agent which can be used in combination, for example, a pigment described in Paragraph No. [0030] to Paragraph No. [0044] of JP-A-2008-224982, or a color index (Color Index, CI) pigment can be mentioned. The pigments obtained by changing the Cl substituent of the Pigment Green 58 and the Pigment Blue 79 are changed to OH, and the pigments which can be preferably used among the pigments include the following pigments. However, the present invention is not limited to these pigments.

CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Orange 36, CI Pigment Red 122, CI Pigment Red 150, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Blue (Pigment Blue) 15:1, CI Pigment Blue 15:3, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 66, CI Pigment Green 7, Pig Pigment Green 36, CI Pigment Green 37 , CI Pigment Green 58

C.I. Pigment Black 1

The dye which can be used as the colorant is not particularly limited, and a known dye can be appropriately selected and used. For example, Japanese Patent Laid-Open No. Sho 64-90403, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, U.S. Patent No. 5,333,500, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Gazette, Japanese Patent Special Open Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. Hei. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A pigment described in, for example, Japanese Laid-Open Patent Publication No. Hei 8- No. Hei 8- No. Hei. .

As the chemical structure, a pyrazole azo type, an anilino azo type, a triphenylmethane type, an anthraquinone type, an anthrapyridone type, a benzylidene type, an oxonol type, and a pyrazolotriazole couple can be used. Nitrogen, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, dibenzopyran, phthalocyanine, benzopyran, indigo a dye such as a system.

[Organic solvents]

In the composition of the present invention, an organic solvent is used. The organic solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the polymerizable composition, and it is particularly preferable to consider the solubility of the ultraviolet absorber and the binder, the coatability, and the safety. The type and amount are selected in a manner suitable for the concentration of the solid component of the viscosity. Further, in the preparation of the photosensitive composition, it is preferred to contain at least two kinds of organic solvents.

The organic solvent is preferably exemplified by esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, oxygen) Butyl acetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-oxypropionic acid Alkyl esters (eg methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy) Methyl propyl propionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxypropionate (eg methyl 2-oxypropionate, ethyl 2-oxypropionate, 2 -propyl oxypropionate or the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2-methyl) Methyl propyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 2-oxobutyl Methyl ester, ethyl 2-oxobutanoate, etc.; and as ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate Ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether An acid ester, propylene glycol monopropyl ether acetate, etc.; and as a ketone such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; and as an aromatic hydrocarbon such as toluene, Toluene, etc.

From the viewpoints of improving the solubility of the alkali-soluble resin and coating the surface, These organic solvents are also preferably mixed in two or more kinds. In this case, a mixed solution composed of two or more selected from the group consisting of the above 3-ethoxypropionic acid is preferred. Methyl ester, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2- Heptone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

From the viewpoint of coatability, the content of the organic solvent is preferably set to be a group The total solid content concentration of the product is from 5% by mass to 80% by mass, more preferably from 5% by mass to 60% by mass, even more preferably from 10% by mass to 50% by mass.

[sensitizer]

In the composition of the present invention, the sensitizer may be contained for the purpose of improving the radical generating efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength. The sensitizer is preferably sensitized by a combined polymerization initiator by an electron transfer mechanism or an energy transfer mechanism. Preferable examples of the sensitizer include the compounds described in Paragraph No. [0085] to Paragraph No. [0098] of JP-A-2008-214395. The content of the sensitizer is preferably in the range of 0.1% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, based on the mass of the total solid content of the composition, from the viewpoint of sensitivity and storage stability. The range is preferably in the range of 2% by mass to 15% by mass.

[Polymerization inhibitor]

In the manufacturing process or during the storage of the composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor to prevent unnecessary thermal polymerization of the polymerizable compound. A known thermal polymerization inhibitor can be used as the polymerization inhibitor, and specific examples thereof include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, biphenyltriol, and tert-butyl catechol. , benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4- Methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine sulfonium salt, and the like.

The amount of the thermal polymerization inhibitor added is preferably from about 0.01% by mass to about 5% by mass based on the total solid content of the composition.

Further, in order to prevent polymerization from being inhibited by oxygen, a higher fatty acid derivative such as maslinic acid or decyl amide may be added, and the drying process after coating may be applied to the surface of the coating film. . The amount of the higher fatty acid derivative added is preferably from about 0.5% by mass to about 10% by mass based on the total composition.

[Close Connection Improver]

In the composition of the present invention, in order to improve the adhesion to the hard surface of the support or the like, an adhesion improving agent may be added. Examples of the adhesion improving agent include a decane coupling agent and a titanium coupling agent.

The decane coupling agent is preferably γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, γ-propyleneoxypropyltrimethoxydecane. , γ-acryloxypropyltriethoxydecane, γ-mercaptopropyltrimethoxydecane, 3-methylpropenyloxypropyldimethoxymethylnonane, γ-aminopropyltri As the ethoxy decane or phenyltrimethoxy decane, γ-methacryloxypropyltrimethoxydecane and 3-methylpropenyloxypropyldimethoxymethylnonane are preferable.

The amount of the adhesion improving agent added is preferably from 0.5% by mass to 30% by mass, and more preferably from 0.7% by mass to 20% by mass, based on the total solid content of the composition.

[Surfactant]

In the composition of the present invention, various surfactants may be added from the viewpoint of further improving coatability. Surfactants can use fluorine-based surfactants, non- Various surfactants such as an ion-based surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant.

In particular, the composition of the preferred embodiment of the present invention contains a fluorine-based boundary The surface active agent has a further improved solution property (particularly fluidity) when it is prepared as a coating liquid, so that the uniformity of the coating thickness or the liquid-saving property can be further improved.

In other words, when a film is formed by using a coating liquid containing a composition containing a fluorine-based surfactant, the wettability of the surface to be coated is obtained by lowering the interfacial tension between the surface to be coated and the coating liquid. The coating property of the coated surface is improved. Therefore, even when a film having a thickness of about several micrometers (μm) is formed with a small amount of liquid, it is possible to more preferably form a film having a uniform thickness and a small thickness, which is effective in this respect.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass. % is more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. When the fluorine content is within this range, the fluorine-based surfactant is effective in thickness uniformity and liquid-saving property of the coating film, and solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171. Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Meijia Method (Megafac) F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Meijiafa (Megafac) F780, Meijia Method (Megafac) F781 (above is made by Di Aisheng (DIC)), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M) Manufacturing), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC -105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above) Manufactured by Asahi Glass Co., Ltd., Solsperse 20000 (made by Lubrizol Co., Ltd.).

Specific examples of the nonionic surfactant include glycerin and trimethylolpropane. Alkanes, trimethylolethane, and such ethoxylates and propoxylates (e.g., propoxylated glycerol, ethoxylated glycerol, etc.), polyoxyethylene ethyl lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Distearate, sorbitan fatty acid ester (Pluronic L10, Pluronic L31, Pluronic L61, Pluronic L62, Pro, manufactured by BASF) Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1, and the like.

Specific examples of the cationic surfactant include phthalocyanine derivatives (products). Name: EFKA-745, manufactured by Morishita Industry Co., Ltd.), organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. .75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

Specific examples of the anionic surfactants include W004, W005, and W017. (Manufactured by Yushang Co., Ltd.), etc.

Examples of the fluorenone-based surfactants include: Toray Dow Corning (Toray) "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Torayone" manufactured by Dow-corning) (Toray Silicone) SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Torayone (Toray) Silicone) SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials, Inc. "KP341", "KF6001", "KF6002" manufactured by the company, "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie.

The surfactant may be used alone or in combination of two or more. The amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass based on the total solid content of the composition.

[Other additives]

Furthermore, the composition of the present invention can further contain a co-sensitizer for the purpose of further improving the sensitivity of the sensitizing dye or the initiator to the active radiation or suppressing the polymerization of the photopolymerizable compound by oxygen. Further, in order to improve the physical properties of the cured film, a known additive such as a surfactant, a diluent, a plasticizer or a fat-sensitive agent may be added as needed.

[Gray hardened film]

The gray cured film of the preferred embodiment of the present invention can be formed by curing the photosensitive composition. Here, the term "gray" is defined as the amount of change in transmittance (25 ° C) when light having a wavelength of 400 nm to 700 nm (visible range) is taken out for transmitted light when a predetermined film is transmitted ( λ ^400-700 ) is 30% or less. In order to supplement the description of the above-described variation amount for the sake of caution, the transmittance spectrum is first obtained in the range of wavelengths of 400 nm to 700 nm. The maximum value (Tmax) and the minimum value (Tmin) of the transmittance are taken out, and the difference (Tmax - Tmin) is set as the amount of change in the above transmittance. The amount of variation is preferably 20% or less. There is no particular lower limit for this amount of variation, but it is actually 0.1% or more. In other words, it is preferable to have no excessive absorption peak at a specific wavelength in the visible light range, and it is preferable to exhibit a flat transmission spectrum as a whole in the range. The transmittance and the amount of fluctuation thereof are set to values measured in Examples described later unless otherwise specified. As described above, by setting a good gray cured film which does not exhibit excessive absorption at a specific wavelength, for example, it can be used as a gray pixel of a photographic element to achieve good performance without variation in transmittance.

The minimum value of the transmittance of the gray cured film at 400nm~700nm Preferably, it is 50% or more, more preferably 60% or more. Further, the maximum value of the transmittance at 400 nm to 700 nm is preferably 90% or less, more preferably 85% or less. By setting the transmittance to such a range, particularly when used as a gray pixel for a photographic element, it is possible to achieve good performance in response to an increase in sensitivity or an increase in dynamic range.

In the present invention, the gray cured film preferably has a predetermined refractive index. By In such a manner, for example, when used as a gray pixel of an imaging element, interference with light adjacent to the coloring pixels (R pixel, G pixel, B pixel) is not caused, and the gray pixel is preferably used. Required performance. From the above viewpoints, the refractive index (25 ° C) of the gray pixel is preferably more than 1.60, more preferably 1.65 or more, and still more preferably 1.70 or more. The upper limit is preferably 2.00 or less, more preferably 1.95 or less. In the present invention, the refractive index of the film is set to a value at 633 nm measured in Examples described later unless otherwise specified.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the following examples.

<Example 1 and Comparative Example 1>

(Preparation of titanium dioxide dispersion)

An ultrafine pulverizing mill (Ultra Apex Mill) (trade name) manufactured by Shou Industrial Co., Ltd. was used as a circulating type dispersing device (bead mill), and a mixed liquid having the following composition was subjected to dispersion treatment as follows to obtain dispersion. A titanium dioxide dispersion of the composition.

<composition>

. Titanium dioxide (Ishihara Industry Co., Ltd., trade name: TTO-51 (C)): 212.5 parts

. The following specific dispersion resin (A) (20% propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") solution): 286.9 parts

. PGMEA: 350.6 parts

In the specific dispersion resin (A), k:l:m:n=25:40:5:30 (polymerized molar ratio), p=60, q=60, and the weight average molecular weight was 10,000.

Further, the dispersion device was operated under the following conditions.

. Bead size: φ 0.05mm

. Bead filling rate: 75% by volume

. Weekly speed: 8m/sec

. Pump supply: 10Kg/hour

. Cooling water: tap water

. Bead mill annular passage internal volume: 0.15L

. The amount of the mixed solution for dispersion treatment: 0.44Kg

The two dispersions contained in the obtained dispersion liquid were obtained by a dynamic light scattering method described later. The average particle diameter of the titanium oxide particles was 30 nm.

(Synthesis of Dispersant 1)

600.0 g of ε-caprolactone and 22.8 g of 2-ethyl-1-hexanol were introduced into a 500 mL three-necked flask, and the mixture was stirred and dissolved while blowing nitrogen gas. 0.1 g of monobutyltin oxide was added and heated to 100 °C. After 8 hours, it was confirmed by gas chromatography that the raw material disappeared and then cooled to 80 °C. After 0.1 g of 2,6-di-tert-butyl-4-methylphenol was added, 27.2 g of 2-methylpropenyloxyethyl isocyanate was added. After 5 hours, it was confirmed by ¹ H-NMR (Nuclear Magnetic Resonance, NMR) that the disappearance of the starting material was carried out, and after cooling to room temperature, 200 g of a solid precursor M1 [the following structure] was obtained. It was confirmed by ¹ H-NMR, infrared (IR), mass spectrometry that the obtained compound was M1.

30.0 g of the above precursor M1, NK ester CB-1 (β-Methacryloyl Oxyethyl Hydrogen Phthalate) 70.0 g, dodecyl sulfur 2.3 g of alcohol and 233.3 g of propylene glycol monomethyl ether acetate were introduced into a three-necked flask substituted with nitrogen, and stirred by a stirrer (New One Science) to circulate in the flask. Nitrogen gas was simultaneously heated and heated to 75 °C. 0.2 g of 2,2-azobis(2-methylpropionic acid) dimethyl ester ("V-601" manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred under heating at 75 ° C for 2 hours. After 2 hours, 0.2 g of V-601 was further added and heated and stirred for 3 hours, and a 30% solution of Dispersant 1 having the following structure was obtained.

x:y=90:10

The composition ratio, acid value, and weight average molecular weight (Mw) of the dispersing agent 1 are as follows.

Further, the weight average molecular weight is measured by the measurement conditions defined above.

. Composition ratio: x = 33 (% by mass), y = 67 (% by mass)

. Acid value: 85 mgKOH/g, Mw: 35,000

(Preparation of titanium black dispersion)

The components shown in the following composition 1 were mixed for 15 minutes using a stirrer (Eurostar (IKOSTAR) manufactured by IKK) to obtain a dispersion mixture.

(composition 1)

. (A) Titanium black (13M-T (powder) manufactured by Mitsubishi Materials)...24 parts

. (B) 30% by mass PGMEA solution of Dispersant 1 ... 25 parts

. (C) Organic solvent: PGMEA...25 parts

. (D) Organic solvent: butyl acetate...26 parts

Using the bead mill NPM manufactured by Shinmaru Enterprises Co., Ltd., and the circulating piping and the input tank, the obtained dispersion mixture was subjected to dispersion treatment under the following conditions to obtain 2000 g of a titanium black dispersion.

<dispersion conditions>

. Bead size: φ 0.05mm

. Bead filling rate: 60% by volume

. Mill peripheral speed: 10m/sec

. The amount of the mixture to be dispersed: 5000 g

. Circulating flow (pump supply): 30kg/hour

. Treatment liquid temperature: 25 ° C ~ 30 ° C

. Cooling water: tap water

. Processing time: 30 cycles (pass)

(Preparation of photosensitive composition 101)

Using the titanium dioxide dispersion liquid (dispersion composition) obtained above, the components were mixed so as to have the following composition, and a photosensitive composition was obtained.

<Composition of photosensitive composition>

. The titanium dioxide dispersion (dispersion composition) prepared above: 22.9 parts

. The titanium black dispersion (dispersion composition) prepared above: 3.3 parts

. Polymeric compound (A) having the following structure: 4.5 parts

. Photopolymerization initiator (肟 compound of the following structure, trade name: Iruka

(IRGACURE) OXE-02, manufactured by BASF): 0.8 parts

. Adhesive polymer (A) of the following structure (20% PGMEA solution): 19.1 parts

. Ultraviolet absorber (A) of the following structure: 0.6 parts

. Surfactant (fluorine-based surfactant, 1% PGMEA solution, manufactured by Di Aisheng (DIC) Co., Ltd., trade name: Megafac F-781): 2.5 parts

. Cyclohexanone / PGMEA: 46.3 parts

(Preparation of other photosensitive compositions)

A carbon black dispersion and a red pigment dispersion were separately prepared. The examples 102 to 108 and Comparative Example C01 were prepared in the same manner as in Example 101 except that the obtained carbon black dispersion and the red pigment dispersion were used, and the amounts of the respective dispersions were changed in accordance with the following Table 1. The photosensitive composition of Comparative Example C02.

(Preparation of carbon black dispersion)

The components shown in the following composition 1 were mixed for 15 minutes using a stirrer (Eurostar (IKOSTAR) manufactured by IKA) to obtain a dispersion mixture.

(composition 1)

. (A) Carbon black (carbon black MA-100R (manufactured by Mitsubishi Chemical Industries Co., Ltd.))...19 parts

. (B) 45 mass% PGMEA solution of dispersant 2...18 parts

. (C) Organic solvent: PGMEA...63 parts

Using the bead mill NPM manufactured by Shinmaru Enterprises Co., Ltd., and the circulating piping and the input tank, the obtained dispersion mixture was subjected to dispersion treatment under the following conditions to obtain 2000 g of a carbon black dispersion composition.

<dispersion conditions>

. Bead size: φ 0.05mm

. Bead filling rate: 60% by volume

. Mill peripheral speed: 10m/sec

. The amount of the mixture to be dispersed: 5000 g

. Circulating flow (pump supply): 30kg/hour

. Treatment liquid temperature: 25 ° C ~ 30 ° C

. Cooling water: tap water

. Processing time: 30 cycles

(Preparation of red pigment dispersion)

(Red (Red) pigment dispersion: dispersion containing PR254/PY139)

By using a bead mill (zirconia beads, particle size 0.3 mm), it will contain 9.6 parts of Pigment Red 254, 4.3 parts of Pigment Yellow 139, 6.8 parts of pigment dispersant BYK-161 (Bicker A mixed liquid of 79.3 parts of propylene glycol methyl ether acetate (hereinafter referred to as "PGMEA") was mixed and dispersed for 3 hours to prepare a pigment dispersion liquid. Thereafter, a high-pressure disperser NANO-3000-10 (manufactured by BEE Co., Ltd.) equipped with a pressure reducing mechanism was further used, and the flow rate was set to 500 g/min under a pressure of 2000 kg/cm ³ to carry out dispersion treatment.

This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

<Method for Measuring Weight Average Particle Diameter of High Refractive Index Particles>

The weight average particle diameter of the particles was obtained by diluting the mixed liquid or dispersion containing particles with propylene glycol monomethyl ether acetate to 80 times, and measuring the obtained diluted solution by dynamic light scattering. The weight average particle diameter of the particles was set to a weight average particle diameter obtained by performing the measurement using Microtrac (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd.

<Method for Measuring Refractive Index of High Refractive Index Particles>

The method of measuring the refractive index of a substance constituting the high refractive index particles is based on the Japanese Industrial Standard (JIS K 0062: 1992).

<Method for Measuring Average Primary Particle Size of Black Pigment>

The average primary particle diameter of the pigment particles can be observed by a transmission electron microscope to observe the dispersed pigment particles, and based on the obtained photograph. Specifically, the projected area of the pigment particles is determined, and the average value of the circular approximate diameter corresponding thereto is set as the average primary particle diameter of the pigment particles. Further, the average primary particle diameter in the present invention is an arithmetic mean value set as a circular approximate diameter obtained for 300 pigment particles.

<Transmittance, transmittance variation λ ^400-700 >

Each of the photosensitive compositions of the examples and the comparative examples obtained above was applied onto a glass wafer by a spin coating method so as to have a film thickness of 0.6 μm after coating, and then dried at 100 ° C on a hot plate. Heat for 2 minutes. Further, the film was heated at 200 ° C for 8 minutes on a hot plate to form a photosensitive composition layer. The spectral transmittance of the substrate on which the photosensitive composition layer was formed was measured using a spectroscope UV3600 manufactured by Shimadzu Corporation. The measurement temperature was set to room temperature (25 ° C).

The transmittance spectra of the film test body 101 and the film test body 102 produced above are shown in Fig. 1 .

<Refractive index of film>

Each of the photosensitive compositions of the examples and the comparative examples obtained above was applied onto a ruthenium wafer so as to have a film thickness of 0.6 μm after application, and then heated at 100 ° C for 2 minutes on a hot plate. Further, the film was heated at 200 ° C for 8 minutes on a hot plate to form a photosensitive composition layer. The refractive index of the substrate on which the photosensitive composition layer was formed was measured using an ellipsometry VUV-VASE (manufactured by J.A. Woollam Japan Co., Ltd.). The measurement temperature was set to room temperature (25 ° C), and the measurement wavelength was set to 633 nm.

<pattern formation>

Each of the photosensitive compositions of the examples and the comparative examples obtained above was applied to a ruthenium wafer with an undercoat layer by a spin coating method so as to have a film thickness of 0.6 μm after coating, followed by heat. The plate was heated at 100 ° C for 2 minutes to obtain a photosensitive composition layer.

Then, the obtained photosensitive composition layer was irradiated with an i-ray stepwise exposure apparatus FPA-3000i5+ (manufactured by Canon), and exposed to a mask to expose a size of 0.9 μm square to 3.0 μm. A dot array pattern or a bayer pattern. Then, a 40% aqueous solution of tetramethylammonium hydroxide (TMAH) was used for the photosensitive composition layer after the exposure, and the mixture was immersed and developed at 23 ° C for 60 seconds. Thereafter, the mixture was rinsed with a spin shower, and further washed with pure water to obtain a transparent pattern.

Using a scanning electron microscope (Scanning Electron Microscope, SEM) (trade name: S-7800H, manufactured by Hitachi, Ltd.), and the shape of the obtained transparent pattern was observed at 30,000 times on the wafer.

The resolvable pattern size (μm square) is shown in Table 1.

Further, the results shown by "C" indicate that the pattern cannot be formed in a square shape of 0.9 μm to 3.0 μm, and the result shown by "B" indicates that the surface roughness was observed in the formed pattern. The result shown by "A" indicates that the pattern was preferably formed, and no surface roughness was observed by visual observation.

The appearance micrographs of the film test body 101 and the film test body C01 of the comparative example are shown in Fig. 2 (a) and Fig. 2 (b), respectively. As in the film test body 101 of the example, the surface is not rough and homogeneous, and thus it is preferable to use it as a gray pixel to achieve good optical characteristics without unevenness.

<矽 wafer with undercoat>

The undercoated silicon wafer used in the evaluation was fabricated as follows.

(Preparation of composition for undercoat layer)

(Production of tantalum wafer with undercoat)

The undercoated silicon wafer used in the evaluation was fabricated as follows.

The composition for the undercoat layer was uniformly applied by spin coating on a 8 Å wafer to form a coating film, and the formed coating film was subjected to heat treatment on a hot plate at 120 ° C for 120 seconds. Further, the application rotation speed of the spin coating was adjusted so that the film thickness of the coating film after the heat treatment was about 0.5 μm.

Further, the coating film after the heat treatment was treated in an oven at 220 ° C for 1 hour to cure the coating film to obtain an undercoat layer.

An undercoat layer was formed on the 8 Å wafer as described above to obtain a ruthenium wafer with an undercoat layer.

(note to the table)

( ) is the blending amount (parts by mass)... It means that the total amount is set to 100 parts, and the other is a surfactant (2.5 parts) and a solvent (the remainder).

* As a dispersing composition

The test at the beginning of C is a comparative example.

TiO ₂ : titanium dioxide particles

(Ishihara Industry Co., Ltd., trade name: TTO-51(C))

The weight average particle size is 30 nm and the refractive index is 2.71.

TB: Titanium black (13M-T made by Mitsubishi Materials)

The number average particle size is 75nm

CB: carbon black (MA-100R of Mitsubishi Chemical Industry Co., Ltd.)

The number average particle size is 24nm

OXE01: lanthanide polymerization initiator

(Manufactured by BASF, Irgacure OXE01 (trade name))

OXE02: lanthanide polymerization initiator

(Manufactured by BASF, Irgacure OXE02 (trade name))

IRG369: α-amino ketone polymerization initiator

(Manufactured by BASF, Irgacure 369 (trade name))

XAN: cyclohexanone

PGMEA: propylene glycol 1-monomethyl ether 2-acetate

When two kinds of solvents are used in combination, they are added in equal amounts and set in a quantitative manner.

BP-A: Adhesive Polymer A

BP-B: Adhesive polymer B

UV-A: UV absorber A

RPD: red pigment dispersion

Resin A: specific dispersion resin A

MA: polymerizable compound MA

According to the composition of the present invention, it is known that a cured film of gray having a good light transmittance and refractive index can be produced. Further, it has been found that the photosensitive composition of the present invention is particularly excellent in photo lithiativity, and can form a cured film which can form a good gray pixel which has no surface roughness and is not uniform in optical characteristics.

<Example 2>

A photosensitive composition was prepared in the same manner as in Sample 101 except that the TiO ₂ particles used in the above Example 1 were changed to the respective high refractive index particles described below to form a cured film. The cured film had a refractive index change rate (λ ^400-700 ) of about 10%, and the pattern formability was "A", and showed good performance.

. Zirconia particles (refractive index of 2.4, manufactured by the first dilute element chemical industry, USP-100)

. Zirconium oxide particles ("ZRDMA30WT%-M22" by CIK Nanotech Co., Ltd.)

. ITO particles / tin-doped indium oxide powder (Mitsubishi Materials Co., Ltd., P4-ITO)

In addition, the photosensitive composition was prepared in the same manner as the sample 101 except that the TiO ₂ particles used in the above Example 1 were changed to the respective high refractive index particles described below to form a cured film.

. Zinc oxide particles (manufactured by Ishihara Sangyo Co., Ltd., FZO-50 [trade name])

. Antimony dioxide particles (made by EVONIK, AEROSIL (R) RX300 [trade name])

. Alumina particles (made by EVONIK, AEROXIDE (R) Alu130 [trade name])

. Magnesium oxide particles (manufactured by Horizon Chemical Co., Ltd., SMO (1m) [trade name])

. Tin oxide particles (manufactured by Mitsubishi Materials Electronics Co., Ltd., S-1 [trade name])

. Vanadium oxide particles (manufactured by Wako Pure Chemical Industries, Vanadium Oxide)

. Cerium oxide particles (manufactured by Wako Pure Chemical Industries, Inc., yttrium oxide)

<Example 3>

A photosensitive composition was prepared in the same manner as in the above except that the dispersing agent used in the following Table was used instead of the dispersing agent used in the test 101 to form a cured film. The cured film had a refractive index change rate (λ ^400-700 ) of about 10%, and the pattern formability was "A", and showed good performance.

The present invention has been described in connection with the embodiments thereof, and the present invention should not be construed as limited to the details of the details. The spirit and scope of the invention as illustrated is widely explained.

The present application claims priority to Japanese Patent Application No. 2012-242230, filed on Jan. 1, 2011, the entire disclosure of which is hereby .

Claims (17)

A composition comprising high refractive index particles, a black pigment, a dispersing agent, and an organic solvent. The composition according to claim 1 further contains a polymerizable compound, a photopolymerization initiator, and an organic solvent. The composition according to claim 1, wherein the high refractive index particles are particles of titanium dioxide or zirconium oxide. The composition according to claim 1, wherein the content of the high refractive index particles in the total solid content of the composition is 5 mass% to 30 mass%. The composition of claim 1, wherein the black pigment is titanium black. The composition according to claim 1, wherein the content of the black pigment in the total solid content of the composition is from 0.5% by mass to 20% by mass. The composition according to claim 1, wherein the dispersing agent is an oligoimide dispersing agent or an acrylic dispersing agent. The composition described in claim 1 further contains a red pigment. The composition according to claim 1 further contains an ultraviolet absorber. The composition according to claim 1, wherein the content of the dispersing agent in the total solid content is 0.05% by mass to 10% by mass. The composition according to claim 1, wherein the dispersing agent is a dispersion resin, and the dispersing resin contains a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2) Or a repeating unit represented by the formula (I-1) and a repeating unit represented by the formula (I-2a), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group; a each independently represents an integer of 1 to 5; * represents a linking moiety between repeating units; and R ⁸ and R ^{9 have the} same meaning as R ¹ a group; L is a single bond, an alkyl group, an alkylene group, an aryl group, a heteroaryl group, an imido group, an ether group, a thioether group, a carbonyl group or a combination of such groups; ^a is a structural moiety which forms a ring structure together with CR ⁸ CR ⁹ and N; X represents a group having a functional group having a pKa of 14 or less; and Y represents a side chain having an atomic number of 40 to 10,000. The composition according to claim 1, wherein the dispersing agent contains any repeating unit of the following formulas (1) to (5), [Chemical 2] In the formula, X ¹ to X ⁶ represent a hydrogen atom, a halogen atom or a monovalent organic group; Y ¹ to Y ⁵ represent a single bond or a divalent linking group; Z ¹ to Z ⁵ represent a hydrogen atom or a monovalent organic group; and R represents A hydrogen atom or a monovalent organic group may have a structurally different R in the copolymer; n, m, p, q, and r each represent an integer of 1 to 500; and j and k are each independently an integer of 2 to 8. The composition according to claim 1, which is for forming a pixel of a solid-state imaging device. A gray cured film obtained by hardening the composition according to any one of claims 1 to 13. The gray cured film according to claim 14, wherein the cured film is gray, and the gray is defined as a difference between a maximum value and a minimum value of a transmittance in a visible light range of a wavelength of 400 nm to 700 nm of 0.1%. Less than 30% of the color. A gray pixel of a solid-state imaging element, which is a pixel of a solid-state imaging element comprising a cured film according to claim 14 or 15, and comprising the above-mentioned high refractive index particles, the above black pigment, and the above dispersion Agent. A solid-state imaging element comprising the gray pixel as described in claim 16 of the patent application.