JP6496398B2 - Dispersion composition, photosensitive composition, color filter and method for producing the same, and solid-state imaging device - Google Patents

Description

  The present invention relates to a dispersion composition, a photosensitive composition, a color filter and a method for producing the same, and a solid-state imaging device.

Conventionally, for the purpose of improving the resolution of image sensors (CCD, CMOS), pixel miniaturization has progressed with the increase in the number of pixels of the image sensor, but on the other hand, the aperture becomes smaller and the sensitivity is lowered. Yes. Thus, for the purpose of improving sensitivity, one color of a plurality of color filters may be white (transparent).
As a method for producing such a white pattern (white filter pixel) in a color filter, for example, a photosensitive transparent for color filter containing a photopolymerization initiator, a polymerizable compound, an alkali-soluble resin, inorganic fine particles, and the like. A technique using a composition is known (see Patent Document 1).

JP 2012-137564 A

In recent years, along with further improvement in performance of image sensors, further improvement in lithography performance when forming a white pattern (white filter pixel) is required, and further improvement in refractive index is required.
In order to improve such a refractive index, titanium oxide particles are used among the inorganic particles described in Patent Document 1 above, and a dispersion composition containing the titanium oxide particles is preferably used. However, when the present inventors use a photosensitive composition containing such a dispersion composition, other materials are damaged by the photocatalytic action of the titanium oxide particles, and the photosensitive composition can be obtained. It has been found that the light resistance of the resulting film is reduced.

  Moreover, the dispersibility of the inorganic particles contained in the dispersion composition may become unstable depending on the type of the dispersant and the like, and the dispersion composition may be thickened (decrease in dispersion stability). Furthermore, when a white pattern (white filter pixel) is formed using a photosensitive composition containing such a dispersion composition, the lithography performance may deteriorate.

Then, this invention makes it a subject to provide the dispersion composition excellent in the dispersion stability. Another object of the present invention is to provide a dispersion composition that is excellent in light resistance and lithography performance and can form a white pattern with a high refractive index when a photosensitive compound is added to form a photosensitive composition. And
Furthermore, this invention also makes it a subject to provide a photosensitive composition, a color filter, its manufacturing method, and a solid-state image sensor.

As a result of intensive studies on the above problems, the present inventor has found that a desired effect can be obtained by using a dispersion composition containing specific inorganic particles and a specific dispersant, leading to the present invention. It was.
That is, the present inventor has found that the above problem can be solved by the following configuration.

[1]
Inorganic particles formed by coating the surface of the particles with a coating material containing at least one metal element excluding alkali metal, alkaline earth metal and Ti atom;
A dispersant having an acid value of 70 mgKOH / g or more;
Containing
Of the metal elements contained in the particles, 95 atm% or more is Ti atoms,
A dispersion composition in which 80 atm% or more of the metal elements contained in the coating material is at least one atom selected from the group consisting of Zr atoms, Sn atoms, and Nb atoms.
[2]
The dispersion composition according to [1], wherein the dispersant has a weight average molecular weight of 5,000 to 12,500.
[3]
The dispersion composition according to [1] or [2], wherein the dispersant has a structural unit represented by any one of the following general formulas (1) to (4).
[4]
The dispersion composition according to any one of [1] to [3], wherein the average primary particle diameter of the inorganic particles is 10 to 30 nm.
[5]
The photosensitive composition containing the dispersion composition as described in any one of said [1]-[4], a polymeric compound, and a photoinitiator.
[6]
When a cured film having a thickness of 1 μm is formed from the photosensitive composition, the light transmittance in the thickness direction of the cured film is 90% or more in the entire wavelength region of 400 to 700 nm, as described in [5] above. Photosensitive composition.
[7]
The photosensitive composition according to the above [5] or [6], which is used for forming a color filter.
[8]
Applying the photosensitive composition for forming a color filter as described in [7] above to form a coating layer, exposing the coating layer to development and forming a pattern to obtain a cured film; The manufacturing method of a color filter.
[9]
The color filter obtained using the photosensitive composition as described in any one of said [5]-[7].
[10]
A solid-state imaging device comprising the color filter according to [9] above.

As shown below, according to the present invention, a dispersion composition having excellent dispersion stability can be provided. In addition, according to the present invention, when a polymerizable compound is added to form a photosensitive composition, a dispersion composition that is excellent in light resistance and lithography performance and that can form a white pattern with a high refractive index is provided. Can do.
Furthermore, according to this invention, the photosensitive composition containing the said dispersion composition, a color filter, its manufacturing method, and a solid-state image sensor can be provided.

The dispersion composition, photosensitive composition, color filter and method for producing the same, and solid-state imaging device of the present invention will be described below.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer, refers to a compound having a molecular weight of 2,000 or less, and has substantially no molecular weight distribution.
In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.
In the present invention, light means actinic rays or radiation. In this specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV (Extreme ultraviolet) light), X-rays, electron beams, etc. means. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Dispersion composition]
The residual composition of the present invention is a coating material containing at least one metal element excluding alkali metal, alkaline earth metal and Ti atom, and has inorganic particles formed by coating the surface of the particles, and an acid value of 70 mgKOH / g. And 95 atm% or more of the metal elements contained in the particles are Ti atoms, and 80 atm% or more of the metal elements contained in the coating material are Zr atoms, Sn. It is at least one atom selected from the group consisting of atoms and Nb atoms.
In the present specification, the inorganic particles having the above characteristics are also simply referred to as “specific inorganic particles”. The dispersant having the above characteristics is also simply referred to as “specific dispersant”.

By using the dispersion composition of the present invention, a photosensitive composition that is excellent in light resistance and lithography performance and can form a white pattern (film) having a high refractive index can be obtained. The dispersion composition of the present invention is also excellent in dispersion stability.
As a result, by using the obtained white pattern as a white color filter, it is possible to perform imaging with an image sensor with high quality.
Although the details of the mechanism for obtaining such an effect have not been clarified, it is presumed to be due to the following reason.

That is, the specific inorganic particles described above have high purity (at least one kind of atoms selected from the group consisting of Zr atoms, Sn atoms, and Nb atoms on the surface of particles containing Ti atoms with high purity (95 atm% or more) ( 80 atm% or more).
Thus, since the specific inorganic particles are obtained by coating the surfaces of particles containing Ti atoms, the photocatalytic activity of titanium oxide containing Ti atoms can be suppressed. As a result, the damage of the film formed by the photosensitive composition is reduced, so that the light resistance of the film is considered to be excellent.
Moreover, it is thought that the refractive index of the obtained film | membrane improved by using the specific inorganic particle which contains each component with a high refractive index with high purity.

Furthermore, in the present invention, by using the above specific dispersant having an acid value of 70 mgKOH / g or more, the specific dispersant is easily adsorbed on the surface of the specific particles, and the dispersibility stability of the resulting dispersion composition is improved. It is thought to have improved.
As a result of improving the dispersion stability of the dispersion composition in this way, that is, by improving the dispersion stability of the specific inorganic particles, the property of improving the refractive index of the specific inorganic particles is better exhibited, It is estimated that the resulting white pattern has an excellent refractive index.
Moreover, it is thought that by using a specific dispersant, developability is improved and lithography performance (resolution, development residue, etc.) is improved.

<Specific inorganic particles>
As described above, the specific inorganic particle is an inorganic particle formed by coating the surface of the particle with a coating material containing at least one metal element excluding alkali metal, alkaline earth metal, and Ti atom. Of the metal elements contained in the particles, 95 atm% or more is Ti atoms. Further, at least 80 atm% of the metal elements contained in the coating material is at least one atom selected from the group consisting of Zr atoms, Sn atoms, and Nb atoms.
In the present specification, particles having the above characteristics are also simply referred to as “specific particles”, and coating materials having the above characteristics are also simply referred to as “specific coating materials”.
The specific inorganic particles may be any particles as long as at least a part of the surface of the specific particles is covered with the specific coating material, and the entire surface of the specific particles may be covered with the specific coating material.

The average primary particle diameter of the specific inorganic particles is preferably 10 to 30 nm, more preferably 10 to 25 nm or less, and further preferably 10 to 20 nm or less.
Since the average primary particle diameter of the specific inorganic particles is 10 nm or more, aggregation of the specific inorganic particles can be suppressed, so that the dispersion stability of the dispersion composition is further improved. Moreover, it exists in the tendency for transparency to become more excellent because it is 30 nm or less.
In the present invention, the average primary particle diameter of specific inorganic particles refers to a photograph obtained by observing the particles with a transmission electron microscope (for example, a device according to JEM-2100F field emission transmission electron microscope manufactured by JEOL). It can be determined and refers to the number average particle size. Specifically, the projected area of the particles is obtained by the above apparatus, and the equivalent circle diameter is obtained therefrom to obtain the average particle diameter. More specifically, after measuring 100 particles to determine the average particle size, the particle size of 80 particles excluding the maximum 10 particles and the minimum 10 particles is obtained by arithmetic averaging. It is done.

The refractive index of the specific inorganic particles is not particularly limited, but is preferably 1.8 to 2.9 from the viewpoint of further improving the refractive index of the obtained film, and is 2.0 to 2.9. More preferably.
Moreover, there is no restriction | limiting in particular in the shape of a specific inorganic particle, For example, a rice grain shape, a spherical shape, a cube shape, a spindle shape, or an indefinite shape etc. are mentioned.

The content of the specific inorganic particles is preferably 3 to 50% by mass, more preferably 3 to 40% by mass, and 5 to 30% by mass with respect to 100% by mass of the total mass of the dispersion composition. More preferably it is. The refractive index of the obtained film can be further improved when the content of the specific inorganic particles is 3% by mass or more, and the dispersion stability of the dispersion composition can be further improved when the content of the specific inorganic particles is 50% by mass or less. There is a tendency to improve.
The content of the specific inorganic particles is preferably 50 to 95% by mass, more preferably 60 to 92% by mass, and 65 to 90% by mass with respect to the total solid content of the dispersion composition. Is still more preferable, and it is especially preferable that it is 70-90 mass%. The refractive index of the film obtained when the content of the specific inorganic particles is 50% by mass or more can be further improved, and the dispersion stability of the dispersion composition can be further improved when the content of the specific inorganic particles is 95% by mass or less. There is a tendency to improve.

  The specific inorganic particles may be subjected to the same treatment as the surface treatment described with the specific particles described later.

(Specific particles)
As described above, the specific particle refers to a particle in which 95 atm% or more of the metal elements contained therein is Ti atoms.
The content of Ti atoms is 95 atm% or more, preferably 97 atm% or more, and preferably 99 atm% or more with respect to 100 atm% of the total of the metal elements contained in the specific particles. Moreover, it is preferable that an upper limit is 100 atm% or less.
When the Ti atom content is 95 atm% or more, the refractive index of the resulting white pattern (film) is improved. On the other hand, when the content of Ti atoms is less than 95 atm%, the refractive index of the resulting film is lowered.

  Here, the content of Ti atoms in the specific particles is measured by quantitative analysis by fluorescent X-ray analysis. Specifically, a specific particle is measured by a fluorescent X-ray analyzer (for example, trade name “ZSX primus II” manufactured by Rigaku Corporation), and the total of all metal elements is obtained from the result of quantitative measurement of all detected elements. It is obtained by setting the amount to 100 atm% and calculating the content (atm%) of Ti atoms contained therein.

  The specific particles are preferably titanium oxide particles. The titanium oxide particles may have any crystal structure of anatase type, rutile type, or brookite type. However, the titanium oxide particles are more excellent in refractive index and more excellent in light resistance of the film obtained by suppressing the photocatalytic activity. It is preferable to use a rutile type from the point that it becomes a product.

As long as the content of Ti atoms is 95 atm% or more, the specific particles may be surface-treated. For example, aluminum oxide, silica, organic groups, etc. may be introduced on the surface. .
The said organic group can be introduce | transduced by surface-treating using organic materials, such as a polyol, an alkanolamine, a stearic acid, a silane coupling agent, a titanate coupling agent, for example.

  Commercially available products can be used for the specific particles, and examples include TTO-55N manufactured by Ishihara Sangyo Co., Ltd., MT-150A manufactured by Teika Co., Ltd., and SRD-M manufactured by Sakai Chemical Industry Co., Ltd. .

(Specific coating material)
As described above, the specific coating material includes at least one metal element excluding alkali metal, alkaline earth metal, and Ti atom, and 80 atm% or more of the metal elements included in the specific coating material is Zr. A coating material that is at least one atom selected from the group consisting of atoms, Sn atoms, and Nb atoms (hereinafter also referred to as “specific atoms”).
Thus, the specific coating material is substantially free of alkali metal, alkaline earth metal, and Ti atom. Substantially free means that it is not intentionally added during production.
Among the specific atoms, Zr atoms are preferably used from the viewpoint of high refractive index.
The specific coating material may include an oxide (metal oxide) or hydroxide of the metal element.

  Here, the “coating material” in the present invention does not indicate the material itself used for coating the surface of the specific particle, but a material (on the surface of the specific particle after coating the surface of the specific particle ( That is, it indicates a coating film or a coating layer).

The specific atom content is 80 atm% or more and 90 atm% or more with respect to a total of 100 atm% of metal elements (that is, metal elements excluding alkali metal, alkaline earth metal and Ti atoms) contained in the specific coating material. It is preferable that it is 95 atm% or more. Moreover, an upper limit is 100 atm% or less.
Thus, when the content of the specific atom is 80 atm% or more, the refractive index of the obtained film is improved. On the other hand, when the content of the specific atom is less than 80 atm%, the refractive index of the obtained film becomes insufficient.

  Here, the content of the specific atom is measured by quantitative analysis by fluorescent X-ray analysis. Specifically, specific inorganic particles are measured with a fluorescent X-ray analyzer (for example, trade name “ZSX primus II” manufactured by Rigaku Corporation), and from the results of quantitative measurement of all detected elements, alkali metal, alkaline earth The total amount of all metal elements excluding the similar metals and Ti atoms is set to 100 atm%, and the content (atm%) of the specific atom contained therein is obtained.

  The production method (coating method) of the specific inorganic particles is not particularly limited, and examples thereof include conventionally known production methods. For example, the methods described in JP-A-5-155748 and JP-A-2008-69193 are used. Can do.

<Specific dispersant>
The dispersion composition of the present invention contains a specific dispersant. The specific dispersant is a dispersant having an acid value of 70 mgKOH / g or more as described above.
The acid value of the specific dispersant is 70 mgKOH / g or more, preferably 70 to 150 mgKOH / g, more preferably 75 to 130 mgKOH / g, and further preferably 80 to 120 mgKOH / g.
Thus, when the acid value of the specific dispersant is 70 mgKOH / g or more, the dispersibility of the dispersion composition is improved and the lithography performance of the obtained film is excellent. Moreover, it exists in the tendency for the dispersibility of a dispersion composition to improve more because the acid value of a specific dispersing agent is 150 mgKOH / g or less.
On the other hand, when the acid value is less than 70 mgKOH / g, the dispersibility of the dispersion composition and the lithography performance of the resulting film are deteriorated.
In the present invention, the acid value of the specific dispersant can be calculated, for example, from the average content of acid groups in the specific dispersant. Moreover, the specific dispersing agent which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises a specific dispersing agent.

The content ratio of the specific dispersant to the specific inorganic particles (specific dispersant / specific inorganic particles) is preferably 0.15 to 0.40 on a mass basis in terms of solid content, and is preferably 0.20 to 0.35. It is more preferable that When the content ratio is within the above range, the dispersibility of the dispersion composition and the refractive index of the obtained film tend to be further improved.
The content of the specific dispersant (in terms of solid content) is preferably 0.5 to 20% by mass, and preferably 1 to 15% by mass with respect to 100% by mass of the total mass of the dispersion composition. . When the content is in the above range, the dispersibility of the dispersion composition and the refractive index of the resulting film tend to be further improved.
The content of the specific dispersant (in terms of solid content) is preferably 5 to 50% by mass and more preferably 8 to 40% by mass with respect to the total solid content of the dispersion composition. When the content is in the above range, the dispersibility of the dispersion composition and the refractive index of the resulting film tend to be further improved.

The weight average molecular weight of the specific dispersant of the present invention is preferably 5,000 to 12,500, more preferably 6,000 to 12,000, and further preferably 7,000 to 11,000. When the weight average molecular weight of the specific dispersant is within the above range, the dispersion stability of the dispersion composition is further improved.
In the present invention, the weight average molecular weight of each component is a value determined by gel permeation chromatography (GPC) measurement in terms of polystyrene.
More specifically, the weight average molecular weight is measured using GPC (gel permeation chromatography) under the following conditions.
Apparatus: Tosoh HLC-8220GPC
Column: Tosoh Corporation
TSK-GEL-SUPER HZM-M
TSK-GEL-SUPER HZ4000
TSK-GEL-SUPER HZ3000
TSK-GEL-SUPER HZ2000
Column temperature: 40 ° C
Flow rate: 0.35 mL / min
Calibration curve: POLY STYREN STANDARD made by Tosoh Corporation
Eluent: THF (tetrahydrofuran)

The specific dispersant of the present invention includes a polymer dispersant (for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, ( (Meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate), and surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and alkanol amine.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  Examples of the terminal-modified polymer having an anchor site to the surface include a polymer having a phosphate group at the terminal described in JP-A-3-112992, JP-T-2003-533455, and the like. A polymer having a sulfonic acid group at its terminal described in JP-A-273191, a polymer having a partial skeleton or a heterocyclic ring of an organic dye described in JP-A-9-77994, or the like in JP-A-2008-29901 Examples thereof include a polymer produced by modifying an oligomer or polymer having a hydroxyl group or an amino group at one end and an acid anhydride. In addition, a high molecular weight terminal in which two or more anchor portions (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) to the surface of the infrared shielding material are introduced at the polymer ends described in JP-A-2007-277514. Molecules are also preferred because of their excellent dispersion stability.

  Examples of the graft type polymer having an anchor site on the surface include poly (lower alkyleneimine) described in JP-A No. 54-37082, JP-A No. 8-507960, JP-A No. 2009-258668, and the like. ) And polyester reaction product, reaction product of polyallylamine and polyester described in JP-A-9-169821, etc., amphoteric dispersion resin having basic group and acidic group described in JP-A-2009-203462, Copolymers of macromonomer and nitrogen atom monomer described in JP-A-10-339949, JP-A-2004-37986, etc., JP-A-2003-238837, JP-A-2008-9426, JP-A-2008 JP-A-81732, etc., a graft type polymer having a partial skeleton or heterocyclic ring of an organic dye, They include copolymers of macromonomer and acid group-containing monomers described in 06268 JP like.

  As a macromonomer used when producing a graft polymer having an anchor site on the surface by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal group) manufactured by Toa Gosei Co., Ltd. Is a methacryloyl group polymethyl methacrylate), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (terminal Polybutyl acrylate whose group is a methacryloyl group), Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd. (2-hydroxyethyl methacrylate, ε-caprolactone 5 molar equivalent addition product), FA10L (ε of 2-hydroxyethyl acrylate) -Caprolactone 10 molar equivalent addition product), and JP-A-2-272009 Polyester macromonomer described in the publication No. and the like. Among these, a polyester-based macromonomer that is particularly flexible and excellent in solvophilicity is a dispersion stability of inorganic particles in the dispersion composition, and a viewpoint of developability exhibited by a film obtained from the photosensitive composition containing the dispersion composition. Particularly preferred are polyester macromonomers represented by polyester macromonomers described in JP-A-2-272009.

  As the block polymer having an anchor site to the surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

As the specific dispersant of the present invention, for example, a known dispersant or surfactant can be appropriately selected and used.
Specific examples thereof include Disperbyk-106, 111, 140, 142, and 180 manufactured by BYK Chemie, and EFKA 5220 and 6230 manufactured by EFKA.
In the present invention, the specific dispersant may be used alone or in combination of two or more.

Further, the specific dispersant of the present invention is preferably the following resin described in JP-A-2010-106268 from the viewpoint of further improving the dispersion stability of the dispersion composition and the lithography performance when a film is formed. .
In particular, the specific dispersant of the present invention is at least represented by the following general formulas (1) to (4) from the viewpoint of further improving the dispersion stability of the dispersion composition and the lithography performance when a film is formed. It is more preferable to have one structural unit and a structural unit having an acid group.

The specific dispersant of the present invention may have one or more structural units having the above acid group.
Preferred acid groups in the specific dispersant include, for example, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, and preferably at least one of carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. Particularly preferred are carboxylic acid groups having good adsorptivity to specific inorganic particles and high dispersibility.
The content in the case of including the structural unit having an acid group can be appropriately set to obtain a desired acid value, but is preferably 30 to 65% by mass with respect to the total mass of the specific dispersant. More preferably, it is 35-50 mass%.

  The structural units represented by the following formulas (1) to (4) are preferably included in an amount of 35 to 70% by mass, and included in an amount of 50 to 65% by mass with respect to the total mass of the specific dispersant. More preferred. Dispersion stability of a dispersion composition improves more because content is in the said range.

Below, the dispersing agent described in Unexamined-Japanese-Patent No. 2010-106268 preferably used in this invention is demonstrated.
A preferable dispersant preferably includes at least a structural unit represented by any one of the following general formulas (1) to (4), and includes at least the following general formula (1A), general formula (2A), It is more preferable that the structural unit represented by any one of the general formula (3A), the general formula (3B), and the general formula (4) is included, and the structural unit represented by the following formula (1A) is included. Further preferred.

In General Formula (1) to General Formula (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and particularly preferably an oxygen atom.
In General Formula (1) to General Formula (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ and X ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints, and are a hydrogen atom or a methyl group Are more preferable, and a methyl group is particularly preferable.
In the general formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a divalent linking group and are not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following (Y-1) to (Y-21) linking groups. A and B in the following structures represent bonds to the left terminal group and the right terminal group in the general formulas (1) to (4), respectively. Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In Formula (1) to Formula (4), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a hydrogen atom or a monovalent organic group, and the structure is not particularly limited. Includes an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group, and the like. Among these, the monovalent organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ preferably has a steric repulsion effect from the viewpoint of improving dispersibility. As the organic group represented by Z ^{1 to} Z ³ , an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms is preferable independently, and each independently a branched alkyl having 5 to 24 carbon atoms. An alkoxy group having a group or an alkoxy group having a cyclic alkyl group having 5 to 24 carbon atoms is preferred. The organic group represented by Z ^4, preferably an alkyl group having 5 to 24 carbon atoms, more preferably a branched alkyl group or a cyclic alkyl group having a carbon number of 5 to 24 5 to 24 carbon atoms.
In General formula (1)-General formula (4), n, m, p, and q represent the integer of 1-500 each independently.
Moreover, in General formula (1) and General formula (2), j and k represent the integer of 2-8 each independently. J and k in the general formula (1) and the general formula (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability, dispersion stability, and lithography performance.

R ³ in the general formula (3) represents a branched or straight chain alkylene group. R ³ in the general formula (3) is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
R ⁴ in the general formula (4) represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ in the general formula (4) is preferably a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ in Formula (4) is an alkyl group, the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or 5 to 20 carbon atoms. Are preferable, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. Further, as R ⁴ in the general formula (4), two or more types of R ⁴ having different structures may be mixed and used in the specific dispersant.

  The dispersion composition may contain one specific dispersant or two or more specific dispersants having different structures.

The structural unit represented by the general formula (1) is more preferably a structural unit represented by the following general formula (1A) from the viewpoint of dispersion stability and lithography performance.
Further, the structural unit represented by the general formula (2) is more preferably a structural unit represented by the following general formula (2A) from the viewpoint of dispersion stability and lithography performance.

In the general formula ^{(1A), X 1, Y} 1, Z 1 and n, ^X 1 in the general formula ^(1), Y ^1, have the same meaning as ^{Z 1} and n, preferred ranges are also the same.
In the general formula ^(2A), X ^2, Y 2, ^{Z 2} and m have the general formula (2) have the same meanings as ^{X 2,} Y 2, ^{Z 2} and m in the preferred range is also the same.
Further, the structural unit represented by the general formula (3) is a structural unit represented by the following general formula (3A) or the following general formula (3B) from the viewpoint of dispersion stability and lithography performance. preferable.

In formula (3A) and the general formula ^(3B), X ^3, Y 3, ^{Z 3} and p is ^{X 3,} Y 3, the same meaning as ^{Z 3} and p in the general formula (3), and their preferred ranges are also It is the same.

  The specific dispersant is more preferably one having a structural unit represented by the general formula (1A).

Specific examples include the following compounds.
In the following exemplified compounds, alphabets such as x, y, z, etc. written together with each structural unit (alphabetical written together with the main chain repeating unit) are the contents of the structural unit [described as mass%: (wt%)]. A dispersant having an acid value of 70 or more can be obtained by appropriately adjusting the ratio of x, y, and z. In addition, x, y, z in each formula shall be mutually independent, and the value is suitably adjusted for every formula so that it may become the acid value 70 or more.
The numerical value written together with the repeating part of the side chain indicates the number of repetitions of this repeating part.

<Other ingredients>
The dispersion composition of the present invention preferably contains an organic solvent from the viewpoints of dispersibility, solubility, handleability and the like of each component. The organic solvent is preferably selected from the viewpoints of solubility, applicability, and safety of the alkali-soluble resin in consideration of the case where it is used in the photosensitive composition described later.
Examples of the organic solvent include 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, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And as ethers For example, 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 acetate, propylene glycol monopropyl ether acetate, and ketones, for example, acetone, diacetone alcohol, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, etc. In addition, preferable examples of the aromatic hydrocarbons include toluene, xylene and the like.
Among these organic solvents, when the dispersion composition is applied to a photosensitive composition to be described later, it is composed of ethers and ketones from the viewpoint that the solubility of the alkali-soluble resin, the coated surface state, and the like become better. It is preferable to include at least one selected from the group, and it is more preferable to include at least one selected from propylene glycol monomethyl ether acetate, cyclohexanone and cyclopentanone.

  When the organic solvent is contained, the content is preferably 30 to 95% by mass and more preferably 50 to 90% by mass with respect to the total mass (100% by mass) of the dispersion composition.

[Photosensitive composition]
The photosensitive composition of this invention contains the said dispersion composition, a polymeric compound, and a photoinitiator. Since the photosensitive composition of this invention contains the said dispersion composition, it is excellent in light resistance and lithography performance, and can form a white pattern (film | membrane) with a high refractive index.
Hereinafter, the component contained in the photosensitive composition of this invention and the component which may be contained are explained in full detail.

<Dispersion composition>
Since the details of the dispersion composition contained in the photosensitive composition are as described above, the description thereof is omitted.
The content (solid content) of the dispersion composition contained in the photosensitive composition is preferably 50 to 95% by mass and preferably 60 to 90% by mass with respect to the total solid content of the photosensitive composition. Is more preferable.
The content of the specific inorganic particles is preferably 30 to 75% by mass, more preferably 40 to 70% by mass, and 45 to 65% by mass with respect to the total solid content of the photosensitive composition. More preferably. When the content of the specific inorganic particles is 30% by mass or more, the refractive index of the obtained film can be further improved, and when the content of the specific inorganic particles is 75% by mass or less, the lithography performance tends to be further improved. is there.

<Polymerizable compound>
The photosensitive composition contains a polymerizable compound. Here, the polymerizable compound is a compound that causes polymerization by an active species. Examples of the active species include radicals, acids, and bases.
When the radical is an active species, a compound having a terminal ethylenically unsaturated bond as a polymerizable group is usually used as the polymerizable compound.
On the other hand, when the active species is an acid such as sulfonic acid, phosphoric acid, sulfinic acid, carboxylic acid, sulfuric acid, and sulfuric monoester, examples of the polymerizable compound include cyclic groups such as an epoxy group, an oxetanyl group, and a tetrahydrofuranyl group. A compound having an ether group or a vinylbenzene group is used.
When the active species is a base such as an amino compound, the polymerizable compound is, for example, a compound having a cyclic ether group such as an epoxy group, oxetanyl group or tetrahydrofuranyl group or a vinylbenzene group. The
The polymerizable compound is preferably selected from compounds having at least one terminal ethylenically unsaturated bond, more preferably two or more. Such a compound group is widely known in the industrial field relevant to the present invention, and these can be used without any particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. A polymeric compound may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in JP-A-2009-288705, paragraphs 0095 to 0108 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
As other preferable polymerizable compounds, compounds having a fluorene ring and having two or more functional ethylenic polymerizable groups described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and cardo resins. Can also be used.
Further, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. It is.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an -OC (= O) C (CH 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. Can also be suitably used.
In addition, compounds described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a polymerizable compound.

  Among them, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

As a polymeric compound, it may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, for example, the ethylenically unsaturated compounds which have an acid group can be mentioned suitably. Ethylenically unsaturated compounds having an acid group can be obtained by (meth) acrylate partial hydroxyl groups of polyfunctional alcohols, and by adding an acid anhydride to the remaining hydroxyl groups to form carboxyl groups. It is done.
If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is essential.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymeric compound.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)) , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  In addition, the polymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) yCH} 2 O) -, or _{- ((CH 2) yCH (} CH 3) O) - represents, y is Each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (i), the sum total of an acryloyl group and a methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (ii), the sum total of an acryloyl group and a methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the terminal oxygen atom side X The form which couple | bonds with is preferable.
The compound represented by general formula (i) or (ii) may be used individually by 1 type, and may be used together 2 or more types. Particularly, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.
Moreover, as a total content in the polymeric compound of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable and 50 mass% or more is more preferable.

  The compound represented by the general formula (i) or (ii) has a ring-opening skeleton by a ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide, which is a conventionally known process. It can be synthesized from the step of bonding and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (i) or (ii), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  As a commercial item of the polymeric compound represented by general formula (i) or (ii), SR-494 which is tetrafunctional acrylate which has four ethyleneoxy chains made from Sartomer, for example, Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Examples of commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), U-4HA, U-6LPA, UA-32P, U-10HA, U-10PA, UA-122P, UA-1100H, 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 (Kyoeisha) Product), UA-9050, UA-9048 (manufactured by BASF) and the like.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of the photosensitive composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In addition, from the viewpoint of increasing the strength of the cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using them together is also effective. Furthermore, it is preferable to use a trifunctional or higher functional polymerizable compound having a different ethylene oxide chain length in that the developability of the photosensitive composition can be adjusted and an excellent pattern formation can be obtained. In addition, the selection and use method of the polymerizable compound is also an important factor for compatibility and dispersibility with other components (eg, photopolymerization initiator, alkali-soluble resin, etc.) contained in the photosensitive composition. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.
Hereinafter, although the specific example of a polymeric compound is given, it is not limited to this.

Further, the polymerizable compound may be a compound having a polymerizable group and a silyl group (hereinafter also referred to as a silyl compound). When the photosensitive composition containing the silyl compound is applied (for example, coated) on a support, the photosensitive composition and the support are caused by the interaction between the Si atoms of the silyl compound and the components constituting the support. Adhesiveness is improved.
The silyl compound is preferably a compound represented by the following general formula (a) (hereinafter also referred to as “specific silyl compound”) from the viewpoint of improving the interaction with the support and the compatibility.

In general formula (a), X is a hydrogen atom or an organic group, and preferably an organic group having at least one polymerizable group and having an amino group. Y ¹ , Y ² , and Y ³ are each independently an alkyl group, alkenyl group, alkynyl group, aryl group, hydroxyl group, alkoxy group, halogen atom, aryloxy group, amino group, silyl group, heterocyclic group, or hydrogen Represents an atom, and is preferably an alkyl group or an alkoxy group.
In general formula (a), X, Y ¹ , Y ² , and Y ³ have a polymerizable group (for example, (meth) acrylic acid ester group, (meth) acrylamide group, styryl group, etc.). Also good.
As said silyl compound, the silyl compound which has a polymeric group in paragraphs 0056-0066 of Unexamined-Japanese-Patent No. 2009-242604 is mentioned, for example.
As the polymerizable compound, the thio (meth) acrylate compounds described in Japanese Patent No. 4176717, paragraphs 0024 to 0031 (paragraphs 0027 to 0033 of US2005 / 0261406) can also be used, and the contents thereof can be incorporated and incorporated in the present specification. It is.

0.1-50 mass% is preferable with respect to the total solid in a photosensitive composition, and, as for content of the polymeric compound in a photosensitive composition, 0.5-30 mass% is more preferable.
A polymeric compound may be used by 1 type, or may be used in combination of 2 or more type.

<Photopolymerization initiator>
The photosensitive composition is provided with photosensitivity by containing a photopolymerization initiator, and is coated with the photosensitive composition by containing the polymerizable compound (and an alkali-soluble resin which is an optional component described later). After forming the layer (coating film), the pattern can be formed by exposing and developing the coating layer. The pattern thus obtained can be used as a white (transparent) filter in the color filter.
The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable, and photoexcited photopolymerization initiators are preferably used. It may be an activator that produces some action with the sensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within the range of about 300 to 800 nm (more preferably 330 to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Examples include oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by Ciba Japan) can be used.
As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by Ciba Japan) can be used.
As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by Ciba Japan) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of oxime compounds such as oxime derivatives that are suitably used as photopolymerization initiators include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyiminobutane-2. -One, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyl) And oxy) iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products.
As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP 2013-164471 A ( C-3). This content is incorporated herein.
Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904 in which oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and dyes A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced, a ketoxime compound described in International Publication No. 2009-131189, a triazine skeleton and an oxime skeleton are contained in the same molecule The compound described in US Pat. No. 7,556,910, the compound described in JP2009-221114A having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.

Further, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000 (corresponding US Patent Application Publication No. 2011/0123929) and JP2007-322744.
In addition, an oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-26979 (corresponding US Patent Application Publication No. 2010/0104976) and Japanese Patent Application Laid-Open No. 2009-191061 (corresponding US Patent Application Publication) No. 2009/023085) and oxime compounds having a thioaryl group.
It is represented by formula (OX-1), (OX-2) or (OX-3) after paragraph 0513 of JP2012-208494A (paragraph 0632 of the corresponding US Patent Application Publication No. 2012/235099). The description of the compound can be referred to and the contents thereof are incorporated herein.

  As oxime polymerization initiators, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) Commercial products such as can be used. In addition, the description of the polymerization initiator described in paragraphs 0092 to 0096 of JP2012-113104A can be referred to, and the contents thereof are incorporated in the present specification. By using such an oxime polymerization initiator, a photosensitive composition having high curing sensitivity and good developability can be provided. The oxime polymerization initiator is a compound described in paragraphs 0030 and after of JP2012-113104A. The general formula is represented by the general formula (I) described in claim 1 of JP2012-113104A, more preferably the general formula (IA) described in claim 3. These descriptions can be referred to, and the contents thereof are incorporated in the present specification.

  Hereinafter, specific examples of oxime compounds that can be suitably used include paragraphs 0090 to 0106 of JP-A-2009-191061 (paragraph 0393 of the corresponding US Patent Application Publication No. 2009/023085), JP-A-2012-032556. The description in Japanese Laid-Open Patent Publication No. 0054, Japanese Laid-Open Patent Publication No. 2012-122045, paragraph 0054, and the like can be referred to, and the contents thereof are incorporated in the present specification. (PIox-1) to (PIox-13) are shown below, but the present invention is not limited to these.

The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and has a high absorbance at 365 nm and 455 nm. Particularly preferred.
From the viewpoint of sensitivity, the oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm of 3,000 to 300,000, more preferably 5,000 to 300,000, and 10,000 to 200. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrphotometer) using an ethyl acetate solvent is used. It is preferable to measure at a concentration of / L.

You may use a photoinitiator in combination of 2 or more type as needed.
The content of the photopolymerization initiator with respect to the total solid content of the photosensitive composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and More preferably, it is 4-10 mass%.

The photosensitive composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the photoradical polymerization initiator, which is a photopolymerization initiator, and increasing the photosensitive wavelength. As the sensitizer, a photosensitizer that is sensitized by an electron transfer mechanism or an energy transfer mechanism is preferable.
Examples of the sensitizer used in the photosensitive composition include compounds described in paragraphs 0101 to 0154 of JP-A-2008-32803.
The content of the sensitizer in the photosensitive composition is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency into the deep part and initiation decomposition efficiency, and preferably 0.5 to 15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

<Alkali-soluble resin>
The photosensitive composition of the present invention preferably contains an alkali-soluble resin.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group.
From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins are preferred, and developability From the viewpoint of control, (meth) acrylic resins, (meth) acrylamide resins, and (meth) acryl / (meth) acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility include an acid group, an alcoholic hydroxyl group, a pyrrolidone group, and an alkylene oxide group, and an acid group is more preferable.
The acid group is not particularly limited, and examples thereof include a carboxyl group, an active methylene group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and a carboxylic acid anhydride group. Those that can be developed with an aqueous solution are preferred, and carboxyl groups are particularly preferred. These acid groups may be used alone or in combination of two or more.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as monomers and polymethylmethacrylate macromonomers include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  It is also preferable that the alkali-soluble resin has a repeating unit represented by the formula (X) or a resin that is soluble in an alkali solution and has a glass transition temperature (Tg) of 100 to 250 ° C. By using the resin, lithography performance such as resolution is further improved, and the refractive index of the formed cured film is improved.

In formula (X), R ¹ represents a hydrogen atom or an alkyl group. As an alkyl group, a C1-C3 alkyl group is preferable and a methyl group is preferable.
L ¹ represents a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), -O-, -S —, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (eg, alkyleneoxy group, alkylene Oxycarbonyl group, alkylenecarbonyloxy group, etc.).
Examples of the divalent aliphatic hydrocarbon group (for example, an alkylene group) include a methylene group, an ethylene group, a propylene group, or a butylene group.
Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group.
In addition, with a single bond, A in Formula (X) intends connecting with the carbon atom connected with R < ¹ > directly.
Hereinafter, specific examples of L ^1, L ¹ is not limited thereto. Note that * indicates a binding position.

A represents a substituted or unsubstituted condensed aromatic ring group. A fused aromatic group refers to a group having two or more aromatic ring structures, each ring having a structure sharing two or more atoms. Here, the condensed aromatic ring group includes both a condensed aromatic hydrocarbon group and a condensed aromatic heterocyclic group.
As the condensed aromatic hydrocarbon group, for example, naphthyl group, acenaphthylenyl group, anthryl group, phenanthryl group, pyrenyl group, acephenanthrenyl group, aceanthrylenyl group, chrysenyl group, dibenzochrysenyl group, benzoanthryl group Group, dibenzoanthryl group, naphthacenyl group, picenyl group, pentacenyl group, fluorenyl group, 9,9-dihydroanthryl group, triphenylenyl group, perylenyl group, fluoranthenyl group, benzo [k] fluoranthenyl group, etc. It is done.
Examples of the condensed aromatic heterocyclic group include indolyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, carbazolyl group (including both 3-carbazolyl group and 9-carbazolyl group), acridinyl group, Examples include a phenazinyl group, a benzofuryl group, an isothiazolyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzotriazolyl group, and a pyranyl group.
Among them, carbazolyl group, naphthyl group, benzothiazolyl group, benzoate are excellent in lithography performance and / or in the point that the refractive index of the obtained film is more excellent (hereinafter also referred to simply as “the excellent effect of the present invention”). An oxazolyl group or a benzotriazolyl group is preferable, and a carbazolyl group or a naphthyl group is more preferable.
In the above A, a substituent may be substituted. Examples of the substituent include an alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, alkylthioxy group, arylthioxy group, Acyloxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, amino group, phosphinoyl group, heterocyclic group, silyl ether group Thiol group, sulfonamide group, amide group, urea group, thiourea group, carboxyl group, urethane group, halogen atom, nitro group, and the like.

The content of the repeating unit represented by the formula (X) in the alkali-soluble resin is not particularly limited, but is preferably 40 to 95% by mass with respect to all the repeating units in terms of more excellent effects of the present invention. -90 mass% is more preferable.
The alkali-soluble resin contains a repeating unit represented by the above formula (X), and its structure is not particularly limited as long as it is soluble in an alkaline solution, but preferably has an acid group.
The acid group is not particularly limited, and examples thereof include a carboxyl group, an active methylene group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and a carboxylic acid anhydride group. Those that can be developed with an aqueous solution are preferred, and carboxyl groups are particularly preferred. These acid groups may be used alone or in combination of two or more.

  The alkali-soluble resin preferably further has a repeating unit represented by the formula (Y) in that the effect of the present invention is more excellent.

In the formula (Y), R ² represents a hydrogen atom or an alkyl group. As an alkyl group, a C1-C3 alkyl group is preferable, and a methyl group etc. are mentioned specifically ,.
L ² represents a single bond or a divalent linking group. Definition of the divalent linking group represented by L ² are the same as those defined divalent linking group represented by L ^1.
B represents an acid group. The definition of the acid group is as described above.
The content of the repeating unit represented by the formula (Y) in the alkali-soluble resin is not particularly limited, but is preferably 5 to 60% by mass with respect to all the repeating units in terms of more excellent effects of the present invention. -40 mass% is more preferable.

The alkali-soluble resin may have a repeating unit other than the repeating unit represented by the above formula (X) and the repeating unit represented by the formula (Y).
For example, the alkali-soluble resin preferably has a repeating unit having a hydrophilic group (excluding an acid group) (hereinafter also referred to as “hydrophilic repeating unit”) from the viewpoint of more excellent effects of the present invention.
Examples of the hydrophilic group include a hydroxy group, an alkylene oxide group, a pyrrolidone group, a morpholine group, a 1,3-diketone group, an amino group, and an ammonium group. Among these, a hydroxy group is preferable in that the effect of the present invention is more excellent. The hydrophilic group does not include the acid group described above.
The alkylene oxide group is preferably a group represented by the following formula (W). Note that * represents a bonding position.
Formula (W) *-(A-O) _n -R
In formula (W), A represents an alkylene group (preferably an alkylene group having 2 to 3 carbon atoms), R represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 2 carbon atoms), and n Represents an integer of 1 or more (preferably an integer of 1 to 25).
A pyrrolidone group, a morpholine group, and a 1,3-diketone group each represent the following groups. Note that * represents a bonding position.

The amino group is a concept including primary, secondary, and tertiary amino groups, and a group represented by the following formula (P) is preferable.
Formula (P) *-N (R) ₂
In formula (P), R represents a hydrogen atom or an alkyl group each independently.

  As the hydrophilic repeating unit, a repeating unit represented by the following formula (Z) is preferable in that the effect of the present invention is more excellent.

In formula (Z), R ³ represents a hydrogen atom or an alkyl group. The definition of an alkyl group is synonymous with the definition of the alkyl group represented by R < ¹ >.
L ³ represents a single bond or a divalent linking group. Definition of the divalent linking group represented by L ³ are the same as those defined divalent linking group represented by L ^1.
C represents a hydrophilic group (excluding an acid group).

The hydrophilic repeating unit is a repeating unit derived from a monomer having an SP value (calculated by the Okitsu method) of 20.2 to 35 MPa ^0.5 (preferably 21 to 33 MPa ^0.5 ) in that the effect of the present invention is more excellent. Preferably there is.
The SP value is calculated by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)).

The production method of the alkali-soluble resin is not particularly limited, and for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. It can also be done.
In order to produce an acrylic-soluble resin containing a repeating unit represented by the above formula (X), for example, the following monomer (hereinafter also referred to as monomer a) is used.

  In addition, in order to produce an acrylic soluble resin containing a repeating unit represented by the above formula (Y), for example, the following monomer (hereinafter also referred to as monomer b) is used.

  In order to produce an acrylic-soluble resin containing a repeating unit represented by the above formula (Z), for example, the following monomer (hereinafter also referred to as monomer c) is used.

  The combination of the monomer a and the monomer b and the mass ratio of the two are not particularly limited. For example, an alkali obtained by using the monomer a and the monomer b having the following combinations and the following quantitative relationships: Soluble resin is mentioned.

  Further, the combination and mass ratio of the monomer a, the monomer b, and the monomer c are not particularly limited. For example, the monomer a, the monomer b, and the monomer c having the following combinations and the following quantitative relationships are used. An alkali-soluble resin obtained by using

  The alkali-soluble resin is also preferably an alkali-soluble resin having a compound represented by the following general formula (ED) (hereinafter also referred to as “ether dimer”) as a monomer component.

In formula (ED), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group.
The hydrocarbon group as R ¹ and R ² is preferably a hydrocarbon group having 1 to 25 carbon atoms, and may further have a substituent.

Thereby, the photosensitive composition of this invention can form the cured coating film which was very excellent also in heat resistance and transparency. In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. A linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; an aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

  Moreover, in order to improve the crosslinking efficiency of the photosensitive composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-described polymer containing a polymerizable group include: Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UC Corporation), and the like. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, Japanese Patent Application Laid-Open No. 2002-229207 And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.

  Examples of the alkali-soluble resin include paragraphs [0015] to [0023] of JP-A-2008-273934, paragraphs [0015] to [0025] of JP-A-2008-274299, and paragraph [0015] of JP-A-2008-274234. 0015] to [0018], paragraphs [0012] to [0019] of JP 2009-67939 A, paragraphs [0014] to [0021] of JP 2009-126824 A, paragraphs of JP 2009-270009 A. [0014] to [0021], paragraphs [0018] to [0025] of JP 2009-270010 A, paragraphs [0071] to [0077] of JP 2011-2111179 A, and JP 2011-151164 A. The compounds described in paragraphs [0062] to [0081] may be used.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  As content when containing alkali-soluble resin, 0.01-50 mass% is preferable with respect to the total solid of a photosensitive composition, and 0.05-40 mass% is more preferable.

  Specific examples of the alkali-soluble resin include the following resins (E-1) to (E-8), but the present invention is not particularly limited thereto. The numerical value shown in each unit represents each unit molar fraction in the resin molecule.

<Other ingredients>
(Organic solvent)
The photosensitive composition of the present invention preferably contains an organic solvent from the viewpoint of improving coatability and handleability. Since the organic solvent is as described in the above dispersion composition, the description thereof is omitted.
When the organic solvent is contained, the content is preferably 30 to 95% by mass and more preferably 50 to 90% by mass with respect to the total mass (100% by mass) of the photosensitive composition. In addition, when the organic solvent is contained in the dispersion composition, the amount of the organic solvent derived from the dispersion composition is also included in the content of the organic solvent in the photosensitive composition.

(Adhesion promoter (silane coupling agent))
The photosensitive composition of the present invention may contain any adhesion promoter as long as the object of the present invention is not impaired. Examples of the adhesion promoter include 3-glycidyloxypropyltrimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- Examples include aminopropyltrimethoxysilane. In addition, the compounds described in paragraph 0048 of JP2008-243945A are used.
Although content in particular when containing an adhesion promoter is not restrict | limited, Usually, it is preferable that it is 10 mass% or less with respect to the total solid of a photosensitive composition, and especially 0.005-5 mass%.

(UV absorber)
The photosensitive composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a pattern can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples of these compounds, compounds described in paragraphs 0137 to 0142 of JP2012-068418A (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) can be used, and the contents thereof can be incorporated into the present specification. Incorporated.
In addition, a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) is also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP 2012-32556 A.

  The content in the case of containing an ultraviolet absorber is preferably 0.01 to 35% by mass and more preferably 1 to 20% by mass with respect to the total solid content of the photosensitive composition.

(Surfactant)
It is preferable that the photosensitive composition of this invention contains surfactant from a viewpoint of improving applicability | paintability more. As the surfactant, various surfactants such as a fluorosurfactant, nonionic surfactant, cationic surfactant, anionic surfactant, and silicone surfactant can be used. Is preferred.
The type of the surfactant used is not particularly limited, and examples thereof include surfactants exemplified in paragraphs 0240 to 0244 of JP2012-122045. More specifically, Megafuck F171, F172, F173, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F781 (above, manufactured by DIC Corporation) and the like.
Moreover, the compound represented by a following formula is also illustrated as a fluorine-type surfactant of this invention. The weight average molecular weight of the compound represented by the following formula is not limited to this.

  When the surfactant is contained, the content is preferably 0.01 to 5% by mass and more preferably 0.05 to 3% by mass with respect to the total solid content of the photosensitive composition. .

(Other ingredients)
The photosensitive composition of this invention may contain other components other than the component mentioned above. Specifically, a polymerization inhibitor, an antioxidant, an anti-aggregation agent, a base as long as the properties (heat resistance, mechanical strength, coatability, adhesion, etc.) of the film obtained using the photosensitive composition are not impaired. Additives such as sexual compounds may be added.

<Characteristics of photosensitive composition>
The photosensitive composition of the present invention is preferably a transparent composition. More specifically, when a cured film having a thickness of 1 μm is formed from the photosensitive composition, the light with respect to the thickness direction of the cured film is used. The transmittance is preferably 90% or more over the entire wavelength region of 400 to 700 nm.
Regarding the photosensitive composition of the present invention, the light transmittance of 90% or more in the entire wavelength region of 400 to 700 nm means that the white filter pixel included in the color filter functions sufficiently as a white filter pixel. (That is, it is necessary for imaging with an image sensor with high sensitivity).
The light transmittance is more preferably 95% or more, further preferably 99% or more, and most preferably 100% over the entire wavelength region of 400 to 700 nm.
The manufacturing method of a photosensitive composition is not specifically limited, When an organic solvent is included, each component of the photosensitive composition is added to the organic solvent, and is obtained by mixing and stirring. Moreover, after stirring each component, you may filter the photosensitive composition with a filter etc.

[Color filter and manufacturing method thereof]
The photosensitive composition of the present invention is preferably used for forming a color filter, more specifically, for white filter pixels in a color filter of a solid-state imaging device.
Hereinafter, as an example of the method for producing a color filter of the present invention, a method for producing a color filter of a solid-state imaging device will be described.
In the method for producing a color filter for a solid-state imaging device of the present invention (hereinafter also referred to as a color filter for a solid-state imaging device), the above-described photosensitive composition is applied to form a coating layer (photosensitive composition layer) ( Hereinafter, it is also referred to as “photosensitive composition layer forming step”, the coating layer is exposed (hereinafter also referred to as “exposure step”), and a pattern is formed by development to form a white filter in the color filter of the solid-state imaging device. Including obtaining a cured film as a pixel.
Moreover, the color filter for solid-state image sensors of this invention is manufactured by the manufacturing method of the color filter for solid-state image sensors of this invention.
The solid-state image sensor color filter of the present invention only needs to have at least a transparent (white) pattern (white filter pixel) manufactured by the method for manufacturing a solid-state image sensor color filter of the present invention. As a specific form of the color filter for a solid-state imaging device of the present invention, for example, a form of a multicolored color filter that combines a transparent pattern and another colored pattern (for example, a transparent pattern, a red pattern, a blue pattern, and a green color) A color filter having four or more colors having at least a pattern is preferable.
Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.
<Photosensitive composition layer forming step>
In the photosensitive composition layer forming step, the photosensitive composition of the present invention is applied on the support to form a photosensitive composition layer.
As a support that can be used in this step, for example, a solid-state imaging in which an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). An element substrate can be used.
The transparent pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate.
Further, if necessary, an undercoat layer may be provided on the support to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate surface.
As a method for applying the photosensitive composition layer of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied. .
As a film thickness of the photosensitive composition layer, 0.1-10 micrometers is preferable, 0.1-3 micrometers is more preferable, 0.1-2 micrometers is further more preferable.
Drying (prebaking) of the photosensitive composition layer coated on the support can be performed at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, an oven or the like.

<Exposure process>
In the exposure step, the photosensitive composition layer formed in the photosensitive composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper, for example.
The radiation (light) that can be used for the exposure means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like, and ultraviolet rays such as g rays and i rays are particularly preferred (particularly preferred). i line). Irradiation dose (exposure dose) is more preferably 50~1700mJ / cm ² is preferably 50~1000mJ / cm ^2, more preferably 75~500mJ / cm ^2.

<Development process>
Next, by performing an alkali development treatment, the photosensitive composition layer in the light-irradiated portion in the exposure step is eluted in the alkaline aqueous solution, and only the photocured portion remains.
The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 to 30 ° C., and the development time is conventionally 20 to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such as methylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, etc. Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used. Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkali developer is usually from 10.0 to 15.0. The alkali concentration and pH of the alkali developer can be appropriately adjusted and used. The alkali developer may be used after adding a surfactant or an organic solvent.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

Next, it is preferable to perform heat treatment (post-bake) after drying. If a multicolor pattern is formed, a cured film can be produced by sequentially repeating the process for each color. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as processes other than the above as needed. For example, after performing the photosensitive composition layer forming step, the exposure step, and the development step described above, a curing step of curing the formed transparent pattern by heating and / or exposure may be included as necessary.
In addition, when using the photosensitive composition according to the present invention, for example, clogging of nozzles and piping parts of the coating device discharge unit, contamination due to adhesion, sedimentation, and drying of the photosensitive composition and inorganic particles in the coating machine. May occur. JP-A-7-128867, JP-A-7-146562, JP-A-8-278637, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, JP-A The cleaning liquids described in JP 2007-2101, JP 2007-2102, JP 2007-281523, and the like can also be suitably used for cleaning and removing the photosensitive composition according to the present invention.
Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid with respect to contaminants, a surfactant related to the present composition described above may be added to the cleaning liquid.

The color filter for a solid-state imaging device of the present invention has an excellent pattern shape and high resolution because the white filter pixels contained in the color filter are obtained using the photosensitive composition of the present invention. And the development residue is reduced. The white filter pixel in the color filter preferably has a refractive index of 1.8 or more for light having a wavelength of 550 nm.
By mounting the color filter for a solid-state imaging device of the present invention on an image sensor, it is possible to perform imaging with the image sensor with high sensitivity and high quality.
The color filter for a solid-state image sensor according to the present invention can be suitably used for a solid-state image sensor such as a CCD (Charge Coupled Device), a CMOS (Complementary Metal Oxide Semiconductor), etc. It is suitable for CMOS and the like. The color filter for a solid-state image sensor of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixel or white filter pixel) in the color filter for the solid-state imaging device is preferably 2.0 μm or less, and more preferably 1.0 μm or less. Here, “coloring” of the coloring pattern (colored pixel) is a concept including transparency (white).
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.0 μm or less, more preferably 1.7 μm or less, and particularly preferably 1.1 μm or less. When the photosensitive composition of the present invention is used, since the lithography performance is good, it is suitable for use in such a small colored pattern.

[Solid-state imaging device]
The solid-state image sensor of the present invention includes the above-described color filter for a solid-state image sensor of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. A configuration is mentioned.

The support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.), and the photodiode and the transfer electrode are placed on the transfer electrodes. A light-shielding film made of tungsten or the like having an opening only in the light-receiving portion, and a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. In addition, the solid-state image sensor color filter of the present invention is included.
Further, a configuration having a light collecting means (for example, a micro lens, etc., the same applies hereinafter) on the device protective film and below the color filter (on the side close to the support), a structure having the light collecting means on the color filter, etc. It may be.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

[Preparation of dispersion composition]
<Production of inorganic particles A>
970 parts of titanium dioxide particles (Taika MT-150A, rutile type) are charged into 10000 parts of water, and while stirring, 1034 parts of an aqueous zirconium sulfate solution containing 15% of zirconium sulfate in terms of ZrO ₂ Then, 160 parts of an aluminum chloride aqueous solution containing 10% of aluminum chloride in terms of Al ₂ O ₃ was added and neutralized with 25% aqueous ammonia, whereby zirconium hydrated oxide and aluminum were formed on the surface of the titanium dioxide particles. After heating to 80 ° C. for 30 minutes, the mixture was filtered, washed, and then dried at 150 ° C. for 30 minutes.
The obtained dried product was calcined at 500 ° C. for 3 hours, and then pulverized with a dry media stirring type pulverizer (product name “Dry Attritor MA1D”, manufactured by Nippon Coke Co., Ltd.) to obtain inorganic particles A. At this time, 5 mm zirconia beads (YTZ manufactured by Nikkato Co., Ltd.) were used as media, and processing was performed at a peripheral speed of 5 m / s for 20 minutes.

Elemental analysis was performed on each of the titanium dioxide particles (MT-150A manufactured by Teica) and the inorganic particles A using a fluorescent X-ray analyzer (product name “scanning fluorescent X-ray analyzer ZSX primus II”, manufactured by Rigaku Corporation).
Specifically, for titanium dioxide particles (MT-150A manufactured by Teica), the Ti atom content was determined according to the method described in the above-mentioned “Content of Ti atom in specific particles”. As a result, the content of Ti atoms was 99 atm% with respect to a total of 100 atm% of all the metal elements contained in the titanium dioxide particles.
Moreover, about the inorganic particle A, content of the specific atom (Zr, Sn, Nb) was calculated | required according to the method demonstrated by "content of a specific atom" mentioned above. As a result, the Zr atom content was 80 atm%, the Sn atom content was 0 atm%, and the Nb atom content was 0 atm%.

Further, the average primary particle diameter of the inorganic particles A obtained as described above was measured in the same manner as described in the above-mentioned “average primary particle diameter of specific inorganic particles”.
As a result, the average primary particle diameter of the inorganic particles A was 15 nm.

<Manufacture of inorganic particles B to K>
In the manufacturing method of said inorganic particle A, the same manufacturing method was implemented except having changed the kind of titanium dioxide particle, and the addition amount of zirconium sulfate aqueous solution and aluminum chloride aqueous solution as shown in the following Table 1. Inorganic particles B to K were produced. In Table 1, the added amount of titanium dioxide particles represents a solid content conversion amount.
About each of obtained inorganic particle BK, the average primary particle diameter and content of the specific atom (Zr, Sn, Nb) were calculated | required by the measuring method similar to the inorganic particle A. The results are shown in Table 1 below.
The outline of each titanium dioxide particle in Table 1 is as follows. Moreover, about each titanium dioxide particle, content of Ti atom was measured with the measuring method similar to the titanium dioxide particle (Taika Co., Ltd. MT-150A) shown by the manufacturing method of an inorganic particle. The results are also shown in parentheses.
MT-150A (trade name, manufactured by Teika, rutile type, Ti atom content: 99 atm%)
SRD-M (trade name, manufactured by Sakai Chemical Industry Co., Ltd., rutile type, 15.2% by mass methanol solution, Ti atom content: 99 atm%)
・ TTO-55N (trade name, manufactured by Ishihara Sangyo Co., Ltd., rutile type, Ti atom content: 99 atm%)
-OPTOLAKE 6320Z (trade name, manufactured by JGC Catalysts & Chemicals Co., Ltd., 20.0 mass% MEK (methyl ethyl ketone) solution, Ti atom content: 93 atm%)

<Synthesis of inorganic particles L (Sn-coated TiO ₂ )>
970 parts of titanium dioxide particles (Taika MT-150A, rutile type) were put into 10,000 parts of water and heated to 80 ° C. while stirring. Into this, 1141 parts of a tin chloride ethanol solution containing 15% in terms of SnO ₂ was added, heated at 80 ° C. for 30 minutes, filtered, washed, and then dried at 150 ° C. for 30 minutes.
The obtained dried product was calcined at 500 ° C. for 3 hours, and then pulverized with a dry media stirring type pulverizer (product name “Dry Attritor MA1D”, manufactured by Nippon Coke Co., Ltd.) to obtain inorganic particles L. At this time, 5 mm zirconia beads (YTZ manufactured by Nikkato Co., Ltd.) were used as media, and processing was performed at a peripheral speed of 5 m / s for 20 minutes.
In Table 1, the added amount of titanium dioxide particles represents a solid content conversion amount.
About the obtained inorganic particle L, the average primary particle diameter and the content of specific atoms (Zr, Sn, Nb) were determined by the same measurement method as that for the inorganic particle A. The results are shown in Table 1 below.

<Synthesis of inorganic particles M (Nb-coated TiO ₂ )>
970 parts of titanium dioxide particles (Taika MT-150A, rutile type) were put into 10,000 parts of water and heated to 80 ° C. while stirring. Into this, 1141 parts of a niobium sulfate aqueous solution containing 15% in terms of NbO ₂ was added, heated at 80 ° C. for 30 minutes, filtered, washed, and then dried at 150 ° C. for 30 minutes.
The obtained dried product was calcined at 500 ° C. for 3 hours, and then pulverized with a dry media agitation type pulverizer (product name “Dry Attritor MA1D”, manufactured by Nippon Coke Co., Ltd.) to obtain inorganic particles M. At this time, 5 mm zirconia beads (YTZ manufactured by Nikkato Co., Ltd.) were used as media, and processing was performed at a peripheral speed of 5 m / s for 20 minutes.
In Table 1, the added amount of titanium dioxide particles represents a solid content conversion amount.
About the obtained inorganic particle M, the average primary particle diameter and the content of specific atoms (Zr, Sn, Nb) were determined by the same measurement method as that for the inorganic particle A. The results are shown in Table 1 below.

<Preparation of Dispersion Composition A-1>
A circulating dispersion device (for a mixed liquid in which the inorganic particles A, the dispersing agent D-1 (see the following formula D-1) and an organic solvent (propylene glycol monomethyl ether acetate (PGMEA)) are mixed at the following blending ratio ( Dispersion treatment was performed using an ultra apex mill (trade name) manufactured by Kotobuki Industries Co., Ltd. as a bead mill) to obtain a dispersion composition A (titanium oxide dispersion A).
(Composition of dispersion composition A-1)
Inorganic particles A: 2.36 parts by mass Dispersant D-1 (30% by mass PGMEA solution): 2.13 parts by mass (solid content: 0.64 parts)
・ Organic solvent: 5.51 parts by mass

<Preparation of dispersion compositions A-2 to A-23>
Dispersion compositions A-2 to A-23 were obtained in the same manner as the preparation of the dispersion composition A-1, except that the types of inorganic particles and the dispersant were changed to the combinations shown in Table 2. A summary of the composition of each dispersion composition is shown in Table 2 below.
In addition, the structure of each dispersing agent (D-1 to D-7) in Table 2 is shown in the following formula. Table 2 shows the acid value and weight average molecular weight (measured by the above method) of each dispersant.

In the above formulas representing the dispersants D-1 to D-7, x, y, and n are as follows.
Dispersant D-1: x = 27, y = 73, n = 10, weight average molecular weight (Mw) = 10000
Dispersant D-2: x = 19, y = 81, n = 10, weight average molecular weight (Mw) = 10000
Dispersant D-3: x = 13, y = 87, n = 10, weight average molecular weight (Mw) = 10000
Dispersant D-4: x = 27, y = 73, n = 10, weight average molecular weight (Mw) = 8000
Dispersant D-5: x = 27, y = 73, n = 10, weight average molecular weight (Mw) = 12000
Dispersant D-6: x = 27, y = 73, n = 10, weight average molecular weight (Mw) = 15000
Dispersant D-7: x = 38, y = 62, n = 10, weight average molecular weight (Mw) = 10000

[Preparation of photosensitive composition]
<Preparation of photosensitive composition C-1>
Using the dispersion composition A-1 obtained above, each component was mixed so as to have the following composition to obtain a photosensitive composition C-1.
(Composition of photosensitive composition C-1)
Organic solvent (PGMEA): 41.84 parts Alkali-soluble resin (44% by mass PGMEA solution) B-1: 0.18 parts (solid content 0.079 parts)
Polymerizable compound (trade name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 2.85 parts Surfactant (1% by mass PGMEA solution, fluorosurfactant, see structure below, weight average molecular weight 14000): 2 .50 parts (0.025 parts solids)
-Photopolymerization initiator (trade name "IRGACURE OXE-01" manufactured by BASF): 0.60 parts-UV absorber U-1: 1.20 parts-Silane coupling agent S-1: 0.02 parts-Polymerization Inhibitor (p-methoxyphenol): 0.01 part Dispersion composition A-1: 50.80 parts (solid content 15.24 parts)

  The structures of the alkali-soluble resin B-1, the ultraviolet absorber U-1, and the silane coupling agent S-1 are as follows. In addition, the weight average molecular weight (Mw) of B-1 was 5000.

<Preparation of photosensitive compositions C-2 to C-23>
Photosensitive compositions C-2 to C-23 were obtained in the same manner as in the preparation of the photosensitive composition C-1, except that the type of the dispersion composition was as shown in Table 3. Table 3 below shows the types of dispersion compositions contained in each photosensitive composition.
In Table 3, the “concentration of the coating material” refers to the sum of the “addition amount of titanium dioxide particles” and the “addition amount of material used for forming the coating material” when each inorganic particle is produced. It refers to the ratio of the “addition amount of material used for forming the coating material”. Ratio Specifically, in the inorganic particles A, the addition amount of the titanium dioxide particles, in terms of ZrO ₂ amount, and the to the sum of terms of Al ₂ O ₃ amount, the sum of ZrO ₂ in terms of quantity and in terms of Al ₂ O ₃ amount is occupied Point to.

<Preparation of photosensitive compositions C-24 to C-25>
Using the dispersion compositions A-4 and A-5 obtained above, photosensitive components C-24 and C-25 were obtained by mixing the components so as to have the following composition.
Organic solvent (PGMEA): 38.90 parts Alkali-soluble resin (44% by mass PGMEA solution) B-1: 0.14 parts (solid content 0.062 parts)
Polymerizable compound (trade name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 2.20 parts Surfactant (similar to the surfactant used in the preparation of photosensitive composition C-1): 2.50 parts (Solid content 0.025 parts)
-Photopolymerization initiator (trade name "IRGACURE OXE-01" manufactured by BASF): 0.60 part-UV absorber U-1: 0.60 part-Silane coupling agent S-1: 0.02 part-Polymerization Inhibitor (p-methoxyphenol): 0.01 parts Dispersion composition A-4 or A-5: 55.03 parts (solid content 16.51 parts)

<Preparation of photosensitive composition C-26>
Using the dispersion composition A-5 obtained above, the components were mixed so as to obtain the following composition, thereby obtaining a photosensitive composition C-26.
Organic solvent (PGMEA): 41.76 parts Alkali-soluble resin (30% by mass PGMEA solution) Exemplary resin 48 described above: 0.26 parts (solid content 0.079 parts)
Polymerizable compound (trade name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 2.85 parts Surfactant (similar to the surfactant used in the preparation of photosensitive composition C-1): 2.50 parts (Solid content 0.025 parts)
-Photopolymerization initiator (trade name "IRGACURE OXE-01" manufactured by BASF): 0.60 parts-UV absorber U-1: 1.20 parts-Silane coupling agent S-1: 0.02 parts-Polymerization Inhibitor (p-methoxyphenol): 0.01 parts Dispersion composition A-5: 50.80 parts (solid content 15.24 parts)

[Evaluation test]
<Evaluation test of dispersion stability>
Each dispersion composition prepared as described above was stored at 45 ° C. for 3 days, and the viscosity before and after storage was measured with a viscometer (product name “RE-85 type viscometer”, manufactured by Toki Sangyo Co., Ltd.). The increase rate (thickening rate) was calculated. The viscosity was measured under the conditions of a rotation speed of 20 rpm and a temperature of 25 ° C. Based on the obtained thickening rate, the dispersion stability was evaluated. The dispersion stability was evaluated according to the following criteria.
“5”: The thickening rate is 5% or less.
“4”: The thickening ratio exceeds 5% and is 7% or less.
“3”: The thickening ratio exceeds 7% and is 10% or less.
“2”: The viscosity increase rate exceeds 10% and is 20% or less.
“1”: The thickening rate exceeds 20%.

<Evaluation test of transmittance and refractive index>
Each photosensitive composition was applied to high refractive index glass (manufactured by Sumita Optical Glass Co., Ltd., SFLD-6 [trade name]) with a spin coater (H-360S [trade name], manufactured by Mikasa Corporation). . Subsequently, it prebaked at 100 degreeC using the hot plate for 2 minutes, and obtained the coating film.
About the obtained coating film, it exposed at 1000 mJ / cm < ² > with the ultra-high pressure mercury lamp ("USH-500BY" (brand name)) made by Ushio Electric. Subsequently, the coated film after exposure was heated on a hot plate in an air atmosphere at 200 ° C. for 5 minutes to obtain a cured film having a thickness of 1.0 μm.
About the obtained cured film, Otsuka Electronics Co., Ltd. product "MCPD-3000" (brand name) was used, The light transmittance (transmittance) of the range of 400 nm-700 nm was measured. As the transmittance, a minimum transmittance value in the range of 400 to 700 nm was adopted. The test was performed 5 times for each sample, and the average value of 3 results excluding the maximum and minimum values was adopted.
At this time, the refractive index at a wavelength of 550 nm at a room temperature of 25 ° C. was measured using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd.) with the same cured film.

<Light resistance evaluation test>
The cured film used in the transmittance and refractive index evaluation tests was irradiated with light of 5 million lxh for 50 hours using a light resistance tester (Xenon Weather Meter SX75 [trade name] manufactured by Suga Test Instruments Co., Ltd.). A light resistance test was conducted. The temperature of the cured film (temperature in the test apparatus) was set to 63 ° C. The relative humidity in the test apparatus was 50% RH. After the light resistance test, the light resistance was evaluated according to the following criteria based on the amount of change in the remaining film ratio and transmittance of the cured film. The test was performed 5 times for a cured film produced under the same conditions, and an average value of 3 results excluding the maximum value and the minimum value was adopted.
“5”: The remaining film rate is 90% or more, and the change in transmittance is ± 5% or less.
“4”: The remaining film rate is 90% or more, and the transmittance change amount exceeds ± 5%.
“3”: The remaining film ratio is 85% or more and less than 90%.
“2”: The remaining film rate is less than 85%, and the change in transmittance is ± 20% or less.
“1”: The remaining film rate is less than 85%, and the change in transmittance exceeds ± 20%.

<Evaluation test of lithography performance>
Each photosensitive composition obtained above was spin-coated using Acton [trade name] manufactured by Tokyo Electron on an 8-inch silicon wafer with an undercoat layer so that the film thickness after coating was 1.0 μm. And then heated at 100 ° C. for 2 minutes on a hot plate to obtain a cured film.
Next, the obtained cured film was exposed to a 1.1 μm square pattern through a mask using an i-line stepper exposure apparatus “FPA-3000i5 +” (trade name, manufactured by Canon Inc.) (exposure amount 50). ˜1700 mJ / cm ² ).
Next, the developability of the cured film after exposure was evaluated using a developing device (Act 8 [trade name] manufactured by Tokyo Electron). As a developer, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used, and shower development was performed at 23 ° C. for 60 seconds. Then, it rinsed with the spin shower using a pure water, and the pattern was obtained.
The obtained pattern was observed at a magnification of 20000 using a scanning electron microscope (SEM) (S-4800H [trade name], manufactured by Hitachi High-Technologies Corporation). And based on the observed image, the lithography performance was evaluated according to the following criteria. The evaluation test of lithography performance was performed three times for each sample, and the results were comprehensively determined.
“5”: The pattern is clear and there is no residue.
“4”: The pattern is clear and the residue is small.
“3”: The pattern is slightly tapered, but there is little residue.
“2”: The pattern is tapered, and there are many residues.
“1”: A pattern cannot be formed.

[Evaluation results]
The results of the above evaluation tests are also shown in Table 3.

As shown in the evaluation results in Table 3, the above-mentioned specific inorganic particles (Ti atom content is 95 atm% or more and the specific atom content is 80 atm% or more) and the above-mentioned specific dispersant (acid value). 70 mg KOH / g or more) and dispersion compositions (dispersion compositions A-1 to A-13, A-20 to A-23) were used. 1-20).
Further, photosensitive compositions C-1 to C-13 and C-20 to C-26 containing any one of such dispersion compositions A-1 to A-13 and A-20 to A-23 are used. Thus, it was shown that the formed film was excellent in refractive index, light resistance and lithography performance (Examples 1 to 20).
Further, in comparison with Examples 7 to 9, by using a dispersant having a weight average molecular weight in the range of 6000 to 12000 (Examples 7 and 8), dispersion stability and lithography performance can be improved to a higher level. I found it satisfactory.
From the comparison of Examples 4, 10, and 11, it is shown that the average primary particle diameter of the inorganic particles is in the range of 15 to 30 nm (Examples 4 and 11), and the dispersion stability of the dispersion composition is more excellent. It was.

On the other hand, when the dispersion compositions A-14 to A-16 containing inorganic particles having a specific atom content of less than 80 atm% in the coating material are used, the photosensitive compositions C-14 to C-16 containing this are used. It was shown that at least one of the refractive index and light resistance of the film formed by the above decreases (Comparative Examples 1 to 3).
Moreover, it was shown that the dispersion stability is lowered when the dispersion composition A-17 containing a dispersant having an acid value of less than 70 mgKOH / g is used. Moreover, it was shown that the lithography performance of the film | membrane formed with the photosensitive composition C-17 containing this falls (comparative example 4).
Further, when the dispersion compositions A-18 and A-19 containing inorganic particles having a Ti atom content of less than 95 atm% are used, films formed of the photosensitive compositions C-18 and C-19 containing the dispersion compositions A-18 and A-19 It has been shown that the refractive index of the film decreases (Comparative Examples 5 and 6).

Claims (16)

Inorganic particles formed by coating the surface of the particles with a coating material containing at least one metal element excluding alkali metal, alkaline earth metal and Ti atom;
A dispersant having an acid value of 70 mgKOH / g or more;
Containing
Of the metal elements contained in the particles, 95 atm% or more is Ti atoms,
The above 80 atm% of the metal element contained in the coating material is at least one atom selected from the group consisting of Zr atom Contact and Nb atoms, dispersion composition.   The dispersion composition of Claim 1 whose weight average molecular weights of the said dispersing agent are 5000-12500.   3. The dispersion composition according to claim 1, wherein 80 atm% or more of the metal elements contained in the coating material is a Zr atom.   The dispersion composition of any one of Claims 1-3 whose acid group which the said dispersing agent has is at least 1 sort (s) of a carboxylic acid group, a sulfonic acid group, and a phenolic hydroxyl group.   The dispersion composition according to any one of claims 1 to 4, wherein the content of the dispersant (in terms of solid content) is 5 to 50% by mass with respect to the total solid content of the dispersion composition. .   The content of the dispersant (in terms of solid content) is 0.5 to 20% by mass with respect to 100% by mass of the total mass of the dispersion composition, according to any one of claims 1 to 5. A dispersion composition.   Inorganic particles formed by coating the surface of the particles with a coating material containing at least one metal element excluding alkali metal, alkaline earth metal and Ti atom;
  A dispersant having an acid value of 70 mgKOH / g or more;
Containing
  Of the metal elements contained in the particles, 95 atm% or more is Ti atoms,
  80 atm% or more of the metal elements contained in the coating material is at least one atom selected from the group consisting of Zr atoms, Sn atoms, and Nb atoms,
  The dispersion composition whose weight average molecular weights of the said dispersing agent are 5000-12500. The dispersion composition according to any one of claims 1 to 7, wherein the dispersant has a structural unit represented by any one of the following general formulas (1) to (4).

In the general formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group. Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a hydrogen atom or a monovalent organic group. n, m, p and q each independently represent an integer of 1 to 500. j and k each independently represent an integer of 2 to 8.
R ³ in the general formula (3) represents a branched or straight chain alkylene group.
R ⁴ in the general formula (4) represents a hydrogen atom or a monovalent organic group. The dispersion composition according to any one of claims 1 to 8 , wherein an average primary particle diameter of the inorganic particles is 10 to 30 nm. The dispersion composition according to any one of claim 1 to 9 containing a polymerizable compound, a photopolymerization initiator and a photosensitive composition.   Containing a dispersion composition, a polymerizable compound, and a photopolymerization initiator,
  The dispersion composition comprises inorganic particles obtained by coating the surface of particles with a coating material containing at least one metal element excluding alkali metal, alkaline earth metal and Ti atom, and dispersion having an acid value of 70 mgKOH / g or more And 95 atm% or more of the metal elements contained in the particles are Ti atoms, and 80 atm% or more of the metal elements contained in the coating material are Zr atoms, Sn atoms, and Nb atoms. A photosensitive composition which is at least one atom selected from the group consisting of: When forming a cured film having a thickness of 1μm by the photosensitive composition, the light transmittance for the thickness direction of the cured film is 90% or more in the wavelength range the entire region of 400 to 700 nm, in claim 10 or 11 The photosensitive composition as described. The photosensitive composition of any one of Claims 10-12 used for color filter formation. Applying the photosensitive composition for forming a color filter according to claim 13 to form a coating layer, exposing and developing the coating layer to form a pattern, and obtaining a cured film; A method for producing a color filter. The color filter obtained using the photosensitive composition of any one of Claims 10-13 . A solid-state imaging device comprising the color filter according to claim 15 .