TW201514237A - Photosensitive composition, dispersion composition, method for producing color filter with same, color filter, solid state image sensor - Google Patents

Abstract

A photosensitive composition, a dispersion composition, a method for producing color filter using the same, a color filter, and a solid state image sensor are provided, wherein the photosensitive composition is excellent in lithography performance, and a formed film exhibits an excellent refractive index. The photosensitive composition at least includes: a alkali-soluble resin, an inorganic particle, a dispersing agent, a photopolymerization initiator, and a polymerizable compound, wherein the alkali-soluble resin has a repeating unit represented by formula (X), or a glass transition temperature (Tg) of the alkali-soluble resin is 100 to 250 DEG C. In the formula (X), R1 represents a hydrogen atom or an alkyl group. L1 represents a single bond or a two-valent linkage group. A represents a substituted or non-substituted condensed aromatic ring group.

Description

Photosensitive composition, dispersed composition, color using the composition Filter manufacturing method, color filter, and solid-state imaging element

The present invention relates to a photosensitive composition, a dispersion composition, a method of producing a color filter using the composition, a color filter, and a solid-state imaging element.

Recently, in order to improve the resolution of image sensor (Charge Coupled Device (CCD), Complementary Metal Oxide Semiconductor (CMOS)), the pixel number of image sensor is being expanded. With the miniaturization of the pixels, on the other hand, the opening portion becomes small, resulting in a decrease in sensitivity. Therefore, in order to improve the sensitivity, one color of a color filter of a plurality of colors may be set to white (transparent).

In the color filter, as a method of producing such a white pattern (white filter pixel), for example, a color containing a photopolymerization initiator, a polymerizable compound, an alkali-soluble resin, and inorganic fine particles is known. A technique of using a photosensitive transparent composition for a filter (refer to Patent Document 1).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-137564

On the other hand, in recent years, with the further performance improvement of the image sensor, further improvement of the lithography performance when forming a white pattern (white filter pixel) is required, and further improvement of the refractive index is required.

The inventors of the present invention have studied the properties described above with reference to the invention described in Patent Document 1, and although the lithographic performance of the obtained pattern and the refractive index of the pattern satisfy the previous requirements, they are not satisfied recently. The higher level required, and further improvements are needed.

In view of the above circumstances, an object of the present invention is to provide a photosensitive composition which is excellent in lithography performance and which exhibits an excellent refractive index.

Further, it is an object of the invention to provide a color filter using the composition, a method of manufacturing the same, a solid-state imaging element, and a dispersion composition.

As a result of intensive studies on the subject, the present inventors have found that a desired effect can be obtained by using the following specific alkali-soluble resin.

More specifically, it has been found that the object can be achieved by the following constitution.

(1) A photosensitive composition comprising at least an alkali-soluble resin having a repeating unit represented by the formula (X), inorganic particles, a dispersing agent, a photopolymerization initiator, and a polymerizable compound.

(2) A photosensitive composition comprising at least an alkali-soluble resin having a glass transition temperature (Tg) of from 100 ° C to 250 ° C, inorganic particles, a dispersant, a photopolymerization initiator, and a polymerizable compound.

(3) The photosensitive composition according to (1), wherein the alkali-soluble resin has a glass transition temperature (Tg) of from 100 ° C to 250 ° C.

(4) The photosensitive composition according to (1) or (3), wherein A is selected from the group consisting of carbazolyl, naphthyl, benzothiazolyl, benzoxazolyl, and benzotriazole Group.

(5) The photosensitive composition according to any one of (1), wherein A is an oxazolyl group or a naphthyl group.

(6) The photosensitive composition according to any one of (1) to (5), wherein the alkali-soluble resin further has a repeating unit containing a hydrophilic group (excluding an acid group).

(7) The photosensitive composition according to (6), wherein the hydrophilic group is a hydroxyl group.

The photosensitive composition according to any one of the above aspects, wherein the dispersing agent is an oligoimide-based dispersing agent or contains any of the formulae (1) to (4) described below. The resin of the structural unit represented by one.

The photosensitive composition according to any one of (1) to (8) wherein the inorganic particles comprise titanium oxide or zirconium oxide.

(10) The photosensitive composition according to any one of (1) to (9) further comprising a low molecular compound having a carbazole structure.

The photosensitive composition according to any one of (1) to (10), wherein Also includes NaCl.

(12) The photosensitive composition according to any one of (1) to (11) which is used as a photosensitive composition for forming a color filter.

(13) A method of producing a color filter of a solid-state image sensor, comprising: applying a photosensitive composition for forming a color filter according to (12) to form a coating layer, and performing a coating layer on the coating layer The film is exposed and developed, thereby forming a pattern to obtain a cured film.

(14) A color filter obtained by using the photosensitive composition according to any one of (1) to (12).

(15) A solid-state photographic element comprising the color filter of (14).

(16) A dispersion composition comprising at least a glass transition temperature (Tg) of 100 ° C or higher, a repeating unit represented by the formula (X) and a hydrophilic group (excluding an acid group) A repeating unit of an alkali soluble resin, inorganic particles, and a dispersing agent.

According to the present invention, it is possible to provide a photosensitive composition which is excellent in lithography performance and which exhibits an excellent refractive index.

Further, according to the present invention, it is also possible to provide a color filter using the composition, a method for producing the same, a solid-state image sensor, and a dispersion composition.

Hereinafter, the photosensitive composition (photosensitive transparent composition) of the present invention will be described in detail.

In addition, in the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). 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).

Further, in the present invention, light means actinic rays or radiation. In the present specification, the term "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, and an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light). X-rays, electron beams, etc. The "exposure" in the present specification includes exposure using a mercury lamp, a far-ultraviolet light represented by a pseudo-molecular laser, X-rays, EUV light, or the like, and is performed by a particle beam such as an electron beam or an ion beam, unless otherwise specified. The depiction is also included in the exposure.

The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene. Mercapto and methacrylonitrile. In addition, in this specification, "Single volume" has the same meaning as "monomer". The monomer in the present invention is different from the oligomer and the polymer, and means a compound having a mass average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a single amount or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

The photosensitive composition of the present invention is a composition containing at least an alkali-soluble resin, inorganic particles, a dispersing agent, a photopolymerization initiator, and a polymerizable compound. Further, the photosensitive composition of the present invention is preferably a negative type composition (a composition forming a negative pattern).

By using the photosensitive composition of the present invention, a pattern having an excellent pattern shape and exhibiting a high refractive index can be obtained in a state of high resolution and a reduction in development residue, and as a result, the obtained pattern can be set. It is a white color filter, and it is possible to perform photography in an image sensor with high quality. As a reason for the improvement in performance, it is presumed that the refractive index is increased by the condensed aromatic ring group in the alkali-soluble resin or the alkali-soluble resin having a high glass transition temperature, and the condensed aromatic ring group interacts with the surface of the inorganic particles. On the other hand, the dispersibility of the particles is improved, and as a result, the lithography performance (the resolution, development residue, and the like) is also improved.

Hereinafter, each component (alkali-soluble resin, inorganic particles, dispersant, photopolymerization initiator, polymerizable compound, and the like) contained in the photosensitive composition will be described in detail, and then the use of the composition will be described in detail. .

In addition, the component contained in the dispersion composition of the present invention is the same as the component in the photosensitive composition except that the polymerizable compound is not contained.

<alkali soluble resin>

The alkali-soluble resin is an alkali-soluble resin having a repeating unit represented by the formula (X) or a glass transition temperature (Tg) of from 100 ° C to 250 ° C. By using this resin, the lithographic performance such as resolution is further improved, and the refractive index of the formed cured film is improved.

In the formula (X), R ¹ represents a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.

L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8), a divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12), and -O-. -S-, -SO ₂ -, -N(R)-(R:alkyl), -CO-, -NH-, -COO-, -CONH-, or a combination of these groups (for example, An alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, etc.).

The divalent aliphatic hydrocarbon group (for example, an alkylene group) may, for example, be a methylene group, an ethylidene group, a propyl group or a butyl group.

Examples of the divalent aromatic hydrocarbon group include a stretching phenyl group and a stretching naphthyl group. In addition, the single bond means that A in the formula (X) is directly bonded to a carbon atom which is bonded to R ¹ .

The following shows specific examples of L ^1, L ^1, but is not limited to this particular embodiment these. Furthermore, * indicates the bonding position.

A represents a substituted or unsubstituted condensed aromatic ring group. The condensed aromatic group refers to a group having a structure of two or more aromatic ring structures, and each ring has two or more atoms. Here, the condensed aromatic ring group includes either a condensed aromatic hydrocarbon group or a condensed aromatic heterocyclic group.

Examples of the condensed aromatic hydrocarbon group include a naphthyl group, an anthracenyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, an acephenanthrylenyl group, and an ethylene fluorenyl group. Base, dibenzo Benzo, benzofluorenyl, dibenzofluorenyl, fused tetraphenyl, fluorenyl, fused pentaphenyl, fluorenyl, 9,9-dihydroindenyl, triphenylene, fluorenyl, propyl [di]ene A fluorenyl group, a benzo[k]propyl[di]ene fluorenyl group, and the like.

Examples of the condensed aromatic heterocyclic group include an anthracenyl group, a quinolyl group, an isoquinolyl group, a pyridazinyl group, a quinoxalinyl group, a quinazolinyl group, and an oxazolyl group (including a 3-carbazolyl group, 9-carbazolyl), acridinyl, cyanozinyl, benzofuranyl, isothiazolyl, isoxazolyl, furazyl, phenoxazinyl, benzothiazolyl, benzoxazolyl , benzimidazolyl, benzotriazolyl, pyranyl and the like.

In view of the fact that the lithographic performance is excellent and/or the refractive index of the obtained film is more excellent (hereinafter, also referred to simply as "the viewpoint of the effect of the present invention is excellent"), carbazolyl or naphthyl is preferred. Or a benzothiazolyl group, a benzoxazolyl group or a benzotriazolyl group, more preferably an oxazolyl group or a naphthyl group.

The substituent may be substituted on the A, and examples of the substituent include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an anthracene. Oxyl, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, fluorenyl, decyloxy , alkoxycarbonyl, amine, phosphinium, heterocyclyl, decyl ether, thiol, sulfonylamino, guanylamino, ureido, thiourea, carboxyl, urethane Base, 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 from the viewpoint that the effect of the present invention is more excellent, it is preferably 40% by mass to 95% by mass based on all the repeating units. %, more preferably 50% by mass to 90% The mass%, and more preferably 60% by mass to 90% by mass.

The alkali-soluble resin contains a repeating unit represented by the above formula (X), and the structure thereof 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. Preferably, it is soluble in an organic solvent and can be weakly alkaline. A developer is used as an aqueous solution, and a carboxyl group is mentioned as a particularly preferable one. 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) from the viewpoint that the effect of the present invention is more excellent.

In the formula (Y), R ² represents a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and specific examples thereof include a methyl group and the like.

L ² represents a single bond or a divalent linking group. The definition of the divalent linking group represented by L ² is the same as the definition of the 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 It is not limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 20% by mass based on all the repeating units. %~40% by mass.

The alkali-soluble resin may have a repeating unit represented by the above formula (X) and a repeating unit other than the repeating unit represented by the formula (Y).

For example, in view of the fact that the effect of the present invention is more excellent, the alkali-soluble resin preferably has a repeating unit (hereinafter, also referred to as "hydrophilic repeating unit") containing a hydrophilic group (excluding an acid group).

Examples of the hydrophilic group include a hydroxyl group, an alkylene oxide group, a pyrrolidinone group, a morpholinyl group, a 1,3-diketo group, an amine group, and an ammonium group. Among them, from the viewpoint that the effect of the present invention is more excellent, a hydroxyl group is preferred. Further, the acid group is not contained in the hydrophilic group.

Further, as the alkylene oxide group, the group represented by the following formula (W) is preferred. Furthermore, * indicates the bonding position.

Formula (W)*-(AO) _n -R

In the formula (W), A represents an alkylene group (preferably an alkylene group having 2 to 3 carbon atoms), and R represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 2 carbon atoms), n An integer of 1 or more (preferably an integer of 1 to 25) is indicated. Further, when n is 2 or more, it is also called a polyalkylene oxide group.

The pyrrolidinyl group, the morpholinyl group, and the 1,3-diketyl group respectively represent the following groups. Furthermore, * indicates the bonding position.

Further, the amine group is a concept including a primary amino group, a secondary amino group, and a tertiary amine group, and is preferably a group represented by the following formula (P).

Formula (P)*-N(R) ₂

In the formula (P), R each independently represents a hydrogen atom or an alkyl group.

The hydrophilic repeating unit is preferably a repeating unit represented by the following formula (Z) from the viewpoint that the effect of the present invention is more excellent.

In the formula (Z), R ³ represents a hydrogen atom or an alkyl group. The definition of the alkyl group is the same as the definition of the alkyl group represented by R ¹ .

L ³ represents a single bond or a divalent linking group. The definition of the divalent linking group represented by L ³ is the same as the definition of the divalent linking group represented by L ¹ .

C represents a hydrophilic group (excluding an acid group). The definition of the hydrophilic group is as described above.

The content of the repeating unit represented by the formula (Z) in the alkali-soluble resin is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 5 mass% to 40 mass with respect to all the repeating units. %, more preferably 10% by mass to 30% by mass.

Further, it is more excellent effect of the present invention, the viewpoint of the hydrophilic repeating unit is preferably derived from the solubility parameter (Solubility Parameter, SP) value (calculated by the Okitsu method) of 20.2MPa ^0.5 ~ 35MPa ^0.5 (more best of 21MPa ^0.5 ~ 33MPa ^0.5) monomer repeating units.

The SP value is a value calculated by Okinawa (Okinawa Jun, "Japan Next Learning Society" 29 (3) (1993)).

The method for producing the alkali-soluble resin is not particularly limited, and for example, a method using a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the type of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by a person skilled in the art, and experimental conditions can be specified.

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

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

[Chemistry 7]

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

[化8]

The combination of the monomer a and the monomer b and the mass ratio of the two are not particularly limited, and examples thereof include an alkali-soluble resin obtained by using the following combination of the monomer a and the monomer b in the following relationship. .

In addition, the combination and the mass ratio of the monomer a, the monomer b, and the monomer c are not particularly limited, and examples thereof include a monomer a, a monomer b, and the following amounts. The alkali-soluble resin obtained by the monomer c. A preferred mass ratio of the monomer a, the monomer b, and the monomer c is 40% by mass to 80% by mass: 10% by mass to 30% by mass: 10% by mass to 30% by mass. By containing in such a ratio, the high refractive index of the alkali-soluble resin and the workability of the pattern can coexist.

Further, when an alkali-soluble resin is produced, other monomers may be used in addition to the monomers.

An alkali-soluble resin which is a repeating unit of a compound represented by the following formula (ED) (hereinafter sometimes referred to as "ether dimer") may be used as the alkali-soluble resin.

In the general formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ may, for example, be an alkyl group substituted with an alkoxy group or an alkyl group substituted with an aryl group such as a benzyl group. Among these, from the viewpoint of heat resistance, a substituent of a primary carbon or a secondary carbon which is not easily removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is particularly preferable.

Specific examples of the ether dimers include the specific examples of the ether dimers described in paragraph 0565 of the Japanese Patent Application Laid-Open No. 2012-208494 (paragraph 0694 of the specification of the corresponding US Patent Application Publication No. 2012/235099). For example, such content can be incorporated into the specification of the present application. Among them, dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxo-double (sub- Base]] bis-2-acrylate, dicyclohexyl-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxo double ( Methylene)] bis-2-acrylate. The ether II The polymer may be used alone or in combination of two or more. The structure of the compound represented by the free radical formula (ED) may also be copolymerized with other monoliths.

The acid value of the alkali-soluble resin is not particularly limited, but is preferably from 30 mgKOH/g to 200 mgKOH/g, more preferably from 50 mgKOH/g to 150 mgKOH/g, still more preferably from 100 mgKOH/g to 150 mgKOH/g.

Further, the weight average molecular weight (Mw) of the alkali-soluble resin is not particularly limited, but is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and still more preferably 7,000 to 20,000.

As the alkali-soluble resin, polylysine as described in paragraphs 0014 to 0025 of JP-A-2010-103171, Japanese Patent Laid-Open No. 2005-189399 (Japanese Patent No. 4292985), paragraph 0014 to paragraph 0029, may be used in combination. The copolymers described in paragraphs 0063 to 0069 (paragraph 0033 to paragraph 0060 of US2005/0157399, paragraph 0149 to paragraph 0162) can be cited, and the contents can be incorporated into the specification of the present application. .

The glass transition temperature (Tg) of the acrylic acid-soluble resin is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably 100 ° C or higher, more preferably 100 ° C to 250 ° C, and still more preferably 130 ° C. ~250 ° C, especially good 150 ° C ~ 250 ° C.

Further, the glass transition temperature (Tg) of the acrylic-soluble resin is a glass transition temperature (theoretical value) represented by the following formula.

1/Tg=(W ₁ /Tg ₁ )+(W ₂ /Tg ₂ )+...+(W _n /Tg _n )

In the formula, Tg represents the glass transition temperature (unit: K) of the acrylic-soluble resin, Tg _i represents the glass transition temperature (unit: K) of the homopolymer of monomer i, and W _i represents the monomer i in all monomers. The weight fraction (i = 1, 2, ..., n) in the composition. Furthermore, the acrylic soluble resin comprises monomer 1, monomer 2. . . . The calculation formula for the n kinds of monomer components of the monomer n.

The content of the alkali-soluble resin in the photosensitive composition (or dispersion composition) is preferably from 1% by mass to 60% by mass, and more preferably from 2% by mass to 50% by mass based on the total solid content of the composition. Further, it is more preferably from 3% by mass to 40% by mass, particularly preferably from 3% by mass to 20% by mass.

In addition, the solid component refers to a component constituting a cured film to be described later, and does not contain a solvent (such as an organic solvent).

In addition, when the sodium component is contained in the photosensitive composition as described later, the content of the sodium element derived from the alkali-soluble resin in the photosensitive composition is preferably 10 ppm by mass or less, more preferably 1 or less. The mass is ppm or less, and more preferably 0.1 mass ppm or less. The content of the sodium element can be adjusted by a refining operation such as distillation or filtration.

By the decrease in the amount of the sodium element, the surface defect or the like of the coating film or the cured film (color filter) obtained from the photosensitive composition is further suppressed, and as a result, the yield of the product is improved. Although the detailed reason is not clear, it is presumed that the sodium element forms a salt with other anions after ionization, and thus it is visually recognized as a surface defect. However, by reducing the amount thereof, salt formation is suppressed, and as a result, the amount of defects is reduced.

As a method of measuring the amount of the sodium element, a known method can be employed, and for example, an Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) can be used.

In addition, the sodium element derived from the alkali-soluble resin refers to a sodium element contained in the resin raw material when the alkali-soluble resin is synthesized, and when the alkali-soluble resin is mixed with other components to prepare a photosensitive composition, it means The sodium element mixed into the photosensitive composition.

<Inorganic Particles>

The inorganic particles are preferably inorganic particles having a high refractive index and being colorless, white or transparent, and more preferably metal oxide particles, and examples thereof include titanium (Ti), zirconium (Zr), aluminum (Al), and bismuth (Si). The oxide particles of zinc (Zn) or magnesium (Mg) are more preferably titanium dioxide (TiO ₂ ) particles, zirconium oxide (ZrO ₂ ) particles or cerium oxide (SiO ₂ ) particles.

The primary particle diameter of the inorganic particles is not particularly limited, but is preferably 1 nm to 100 nm, more preferably 1 nm to 80 nm, and particularly preferably 1 nm to 50 nm. When the primary particle diameter of the inorganic particles is within the above range, the dispersibility is excellent, and the refractive index and the transmittance are improved.

The refractive index of the inorganic particles is not particularly limited, but from the viewpoint of obtaining a high refractive index, it is preferably from 1.75 to 2.70, more preferably from 1.90 to 2.70.

The specific surface area of the inorganic particles is not particularly limited, but is preferably ^{10m 2 / g ~ 400m 2 /} g, more preferably ^{20m 2 / g ~ 200m 2 /} g, and further more preferably ^{30m 2 / g ~ 150m 2 /} g .

Further, the shape of the inorganic particles is not particularly limited, and examples thereof include a rice grain shape, a spherical shape, a cubic shape, a spindle shape, and an indefinite shape.

The inorganic particles may also be formed by surface treatment with an organic compound. Used for Examples of the surface-treated organic compound include a polyhydric alcohol, an alkanolamine, a stearic acid, a decane coupling agent, or a titanate coupling agent. Among them, a stearic acid or a decane coupling agent is preferred.

Further, from the viewpoint of further improvement in weather resistance, the surface of the inorganic particles is preferably treated by an oxide such as aluminum, lanthanum or zirconia.

As the inorganic particles, a commercially available one can be preferably used.

The inorganic particles may be used alone or in combination of two or more.

In addition, the content of the inorganic particles in the photosensitive composition (or the dispersion composition) of the present invention is more preferably 65% by mass or more based on the total solid content of the dispersion composition from the viewpoint of obtaining a high refractive index. Further, it is more preferably 70% by mass or more.

The upper limit of the content is not particularly limited, but is preferably 90% by mass or less, and more preferably 85% by mass or less based on the total solid content of the dispersion composition.

The content of the inorganic particles in the photosensitive composition of the present invention is preferably from 10% by mass to 90% by mass, more preferably from 10% by mass to 90% by mass, based on the total solid content of the photosensitive composition from the viewpoint of obtaining a high refractive index. 20% by mass to 85% by mass, and more preferably 30% by mass to 80% by mass.

Hereinafter, titanium oxide (TiO ₂ ) particles, cerium oxide (SiO ₂ ) particles, and zirconium oxide (ZrO ₂ ), which are suitable forms of inorganic particles, will be described in detail.

(titanium dioxide particles and cerium oxide particles)

The titanium dioxide particles may be represented by the chemical formula TiO ₂ , and preferably have a purity of 70% or more, more preferably 80% or more, and still more preferably 85% or more. The low-valent titanium oxide, titanium oxynitride, etc. represented by the general formula Ti _n O _2n-1 (n represents the number of 2 to 4) is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. Further, as the titanium dioxide particles, those of rutile crystal are preferable.

As a commercially available product of the titanium dioxide particles, for example, TTO series (TTO-51 (A), TTO-51 (C), TTO-55 (C), etc.) manufactured by Ishihara Industry Co., Ltd., TTO-S, V, Series (TTO-S-1, TTO-S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by Tayca (share).

As a commercial item of the cerium oxide particle, OG502-31 by Clariant Co., etc. are mentioned, for example.

(Zirconium oxide particles (zirconia particles))

The zirconia particles are inorganic particles containing a zirconium atom and an oxygen atom. By containing the particles, a film (cured film) exhibiting a high refractive index can be obtained.

The average particle diameter of the zirconia particles is not particularly limited, but is preferably from 1 nm to 200 nm, more preferably from 10 nm to 100 nm, still more preferably from 10 nm to 50 nm.

The specific surface area is preferably from 80 m ² /g to 120 m ² /g.

The average particle diameter of the zirconia particles can be observed by a transmission electron microscope and determined based on the obtained photograph. The projected area of the particles is determined, and the projected area diameter is obtained as the average particle diameter (generally, 300 or more particles are measured in order to obtain an average particle diameter).

For example, UEP, UEP-100 (manufactured by the first rare element chemical industry (share)), PCS (manufactured by Nippon Electric Co., Ltd.), JS-01, JS-03, JS are mentioned as a commercially available product of the zirconia particles. -04 (made by Nippon Electric Co., Ltd.).

As the content of the zirconia particles in the photosensitive composition, relative to the composition The total solid content is preferably from 10% by mass to 80% by mass, more preferably from 20% by mass to 70% by mass, even more preferably from 35% by mass to 55% by mass.

<dispersant>

The dispersant enhances the dispersion stability of the inorganic particles in the composition.

Examples of the dispersing agent include polymer dispersing agents [for example, polyamidoamine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, and a modified polycondensation. (Meth) acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], and surfactants such as polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and alkanolamine.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure.

The terminal-modified polymer having a fixed portion on the surface of the inorganic particles, for example, has a phosphate group at the terminal as described in JP-A-3-112992, JP-A-2003-533455, and the like. A polymer having a sulfonic acid group at the terminal, as described in JP-A-2002-273191, and a partial skeleton or a hetero group having an organic dye described in JP-A-H09-77994. A polymer produced by modifying a polymer having a hydroxyl group or an amine group at one terminal and modifying it with an oligomer or a polymer and an acid anhydride, as described in JP-A-2008-29901, and the like. In addition, two or more fixing sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic rings, etc.) to the surface of the infrared shielding agent are introduced into the polymer terminal as described in JP-A-2007-277514. The dispersion stability of the polymer is also excellent, and good.

Examples of the graft-type polymer having a fixed portion on the surface of the inorganic particles include, for example, JP-A-54-37082, JP-A-8-507960, and JP-A-2009-258668. The reaction product of the polyallylamine and the polyester described in JP-A-9-169821, and the like, Japanese Patent No. 9-169821, etc. The amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462, and the macromolecular singles described in JP-A-H05-339949, JP-A-2004-37986, and the like. Copolymer of a macromonomer and a nitrogen atom monomer, and an organic pigment described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like. A copolymer of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268, and the like.

A known macromonomer can be used as the macromonomer used in the production of the graft polymer having a fixed portion on the surface of the inorganic particles by radical polymerization, and examples thereof include the production of East Asia Synthetic (Stock). Macromonomer AA-6 (polymethyl methacrylate with terminal group of methacryl fluorenyl), AS-6 (polystyrene with terminal methacryloyl group), AN-6S (end group is a copolymer of styrene and acrylonitrile of methacryl oxime), AB-6 (polybutyl acrylate of methacryl fluorenyl group), PLACCEL FM5 manufactured by DAICEL Chemical Industry Co., Ltd. Ε-caprolactone 5 molar equivalent adduct of 2-hydroxyethyl methacrylate), FA10L (A ε-caprolactone 10 molar equivalent of 2-hydroxyethyl acrylate), and a polyester-based macromonomer described in Japanese Laid-Open Patent Publication No. Hei 2-272009. Among these, a polyester macromonomer which is excellent in flexibility and solvophilicity is particularly preferable from the viewpoint of dispersion stability of the inorganic particles in the photosensitive composition, and further preferably from Japan. A polyester-based macromonomer represented by a polyester-based macromonomer described in Japanese Laid-Open Patent Publication No. Hei.

The block type polymer described in the above-mentioned Japanese Patent Publication No. 2003-49110, and the like.

As the dispersing agent, for example, a known dispersing agent or a surfactant can be appropriately selected and used.

As such a specific example, "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylate), 110 (acid group-containing copolymer), 130 (by BYK Chemie) can be cited. Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA Manufactured "EFKA4047, 4050~4010~4165 (polyurethane type), EFKA4330~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), "AJISPER PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno Co., Ltd. "FLOWLEN TG-710 (urethane oligomer)" and "POLYFLOW" manufactured by Kyoeisha Chemical Co., Ltd. No. 50E, No. 300 (acrylic copolymer), "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA- manufactured by Kusumoto Kasei Co., Ltd. 703-50, DA-705, DA-725", "DEMOL RN, N (formalin naphthalenesulfonate polycondensate), MS, C, SN-B (aromatic sulfonic acid fumarin polycondensate) manufactured by Kao Corporation" "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearylamine acetate)", "SOLSPERSE 5000 (phthalocyanine derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer with functional part at the end) manufactured by Lubrizol (shares), 24000, 28000, 32000 , 38500, 71000 (grafted polymer), "Nikko Chemicals" company "NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemicals HINOACT T-8000E manufactured by the company, KP341, an organic siloxane polymer manufactured by Shin-Etsu Chemical Co., Ltd., "W001: Cationic surfactant", polyoxyethylene lauryl ether, manufactured by Yushang Co., Ltd. Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Non-ionic surfactants such as sorbitan fatty acid esters, and anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA-47, EFKA-47EA, manufactured by Morishita Industrial Co., Ltd." EFKA Polymer100, EFKA Polymer400, EFKA Polymer401, EFKA Polymer450", a polymer dispersant such as "DISPERSE AID6, DISPERSE AID8, DISPERSE AID15, DISPERSE AID9100" manufactured by San Nopco (shares), "ADEKA PLURONIC L31" manufactured by ADEKA (Stock) , F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and "IONET S-" manufactured by Sanyo Chemical (share) 20" and so on.

These dispersing agents may be used singly or in combination of two or more. Further, the dispersing agent may be used by using a terminal modified polymer having a fixed portion, a graft polymer, or a block polymer and an alkali-soluble resin. Examples of the alkali-soluble resin include a (meth)acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and a side chain. A resin having an acid cellulose derivative having a carboxylic acid and a modified acid anhydride in a polymer having a hydroxyl group is particularly preferably a (meth)acrylic copolymer. In addition, the N-substituted maleimide monomer copolymer described in Japanese Patent Laid-Open Publication No. Hei 10-300922, and the ether dimer copolymer described in JP-A-2004-300204, The alkali-soluble resin containing a polymerizable group described in Japanese Laid-Open Patent Publication No. Hei 7-319161 is also preferable.

From the viewpoint of the dispersibility and the deposition property, the oligoimide-based dispersant or the resin described below in JP-A-2010-106268 is preferred.

The oligoimine-based dispersant is particularly preferably a graft copolymer of a graft chain having a poly(lower alkyleneimine)-based repeating unit and having a polyester structure. Further, it is preferred that the oligoimine-based dispersant contains an acid group. Further, as a preferred acid group, adsorption From the viewpoint of the above, an acid group having a pKa of 6 or less is preferable, and a carboxylic acid group is particularly preferable. The acid value of the oligoimine-based dispersant is preferably 1 mg/KOH to 100 mg/KOH, more preferably 3 mg/KOH to 50 mg/KOH, still more preferably 5 mg/KOH to 35 mg/KOH.

Further, the weight average molecular weight of the oligoimine-based dispersant measured by a gel permeation chromatography (GPC) method is preferably from 2,000 to 100,000, more preferably from 3,000 to 50,000, and even more preferably from 4,000 to 4,000. 10000.

On the other hand, among the resins described in Japanese Laid-Open Patent Publication No. 2010-106268, in particular, from the viewpoint of dispersibility, a polymer dispersant having a polyester chain in a side chain is also preferable. A resin having an acid group and a polyester chain can be suitably cited. A preferred acid group in the dispersant is preferably an acid group having a pKa of 6 or less from the viewpoint of adsorptivity, and particularly preferably a carboxylic acid group, a sulfonic acid group or a phosphoric acid group.

In the following, the dispersion resin described in column 0173 of JP-A-2012-122045, which is preferably used in the present invention, will be described.

The preferred dispersant (dispersion resin) is preferably in the range of 40 to 10,000 atoms other than a hydrogen atom in the molecule, and has a structure selected from a polyester structure, a polyether structure, and a polyacrylate structure. A graft copolymer of a graft chain. Moreover, as another preferable aspect of the dispersing agent, it is preferable to contain at least the structural unit represented by any one of the following formulas (1) to (4), and more preferably at least the following formula (1A) A structural unit represented by any one of the following formula (2A), the following formula (3A), the following formula (3B), and the following formula (4).

[化10]

In the formulae (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of the limitation of the synthesis, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

In the formulae (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a divalent linking group, and the structure is not particularly limited. The definition of the divalent linking group is as described above. Specifically, the following (Y-1) to (Y-21) linking groups and the like are exemplified. In the following structures, A and B respectively represent a bond to the left terminal group and the right terminal group in the formulae (1) to (4). Among the structures shown below, (Y-2) and (Y-13) are more preferable in terms of ease of synthesis.

[11]

In the formulae (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a hydrogen atom or a monovalent organic group, and the structure of the organic group is not particularly limited, specifically, Listed are: an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, a heteroaryl sulfide group, an amine group and the like. Among them, in particular, from the viewpoint of enhancing dispersibility, it is preferred to have a steric repellency effect, and as the monovalent substituent represented by Z ¹ to Z ³ , it is preferably independently a carbon number of 5 to 24, respectively. The alkyl group or the alkoxy group having a carbon number of 5 to 24, and particularly preferably an alkoxy group each independently having a branched alkyl group having 5 to 24 carbon atoms or a ring having a carbon number of 5 to 24 Alkoxy group of an alkyl group. Further, as the monovalent substituent represented by Z ⁴ , an alkyl group having a carbon number of 5 to 24 is preferable, and among them, a branched alkyl group having a carbon number of 5 to 24 or a carbon number is preferably used independently. It is a cyclic alkyl group of 5 to 24.

In the formulae (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.

In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoint of dispersion stability, j and k in the formulae (1) and (2) are preferably an integer of 4 to 6, and most preferably 5.

In the formula (3), R' represents a branched or linear alkylene group. R' in the formula (3) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms.

Further, as R' in the formula (3), two or more kinds of R' having different structures may be used in combination.

In the formula (4), R represents a hydrogen atom or a monovalent organic group, and is not particularly limited in structure, but is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a ring having 5 to 20 carbon atoms. The alkyl group is more preferably a linear alkyl group having 1 to 20 carbon atoms, particularly preferably a linear alkyl group having 1 to 6 carbon atoms.

Further, as R in the formula (4), two or more kinds of R having different structures may be used in combination.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability.

In addition, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability.

In the formula ^{(1A), 1, Y 1} , Z 1 , and the same ^{n X 1, Y 1, Z} 1 and n have the meanings of formula X (1) is, preferred ranges are also the same.

In formula ^{(2A), X 2, Y} 2, Z 2 and m are as defined for the formula X (2) is ^2, Y ^2, Z ² and the same as m, the preferred ranges are also the same.

In addition, the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or the following formula (3B) from the viewpoint of dispersion stability.

[Chemistry 13]

Formula (3A) or (3B) in, ^3, Y ^3, Z ³ and same ^{p X 3, Y 3, Z} 3 and p are defined for the formula X (3) of the, preferred ranges are also the same.

As a specific example, the exemplified compound 1 to the exemplified compound 71 after the paragraph 0079 of the Japanese Patent Application Laid-Open No. 2010-106268 (paragraph 0121 of the corresponding US Patent Application Publication No. 2011/0124824) can be referred to, the contents of which are described. It can be incorporated into the specification of this application. Preferred examples of the compound include the compounds shown below. In addition, among the following exemplified compounds, the numerical value (the numerical value collectively described in the main chain repeating unit) which is described in each structural unit together shows the content [mass%: (wt%)] of the structural unit. The numerical value described in the repeated portion of the side chain together indicates the number of repetitions of the repeated portion.

[Chemistry 14]

[化15]

[Chemistry 16]

[化17]

[化18]

When a dispersing agent is used, from the viewpoint of improving dispersibility, it is preferred to first prepare a dispersion composition by using inorganic particles and a dispersing agent, and a suitable solvent, and then to prepare a photosensitive composition.

The content of the dispersant in the photosensitive composition is preferably from 3% by mass to 80% by mass, and more preferably from 15% by mass to 40% by mass based on the total solid content of the inorganic particles in the photosensitive composition. .

<Photopolymerization initiator>

The photosensitive composition is imparted with photosensitivity by containing a photopolymerization initiator, and After the coating layer is formed using the photosensitive composition by containing the polymerizable compound described later and the alkali-soluble resin, the coating layer is exposed and developed, whereby a pattern can be formed. Moreover, the pattern obtained in the manner described can be set as a white (transparent) filter in the color filter.

The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, it is preferably a photo-excited sensitizer for photosensitivity from an ultraviolet region to visible light. The active agent which generates a certain action and generates a living radical may also be an initiator which starts cationic polymerization as the type corresponding to the monomer.

Further, the photopolymerization initiator preferably contains at least one component having a molecular absorption coefficient of at least about 50 in a range of from about 300 nm to 800 nm (more preferably from 330 nm to 500 nm).

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, etc.), a mercaptophosphine compound such as a mercaptophosphine oxide, a hexaarylbiimidazole, or an anthracene derivative. An hydrazine compound, an organic peroxide, a sulfur compound, a ketone compound, an aromatic sulfonium salt, a ketoxime ether, an aminoacetophenone compound, a hydroxyacetophenone or the like. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a sulfhydryl phosphine oxide-based initiator described in Japanese Patent No. 42258899 can be used. .

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by Ciba Japan Co., Ltd.) can be used.

As the amino acetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by Nippon Ciba) can be used as a commercial product.

As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which is a wavelength of a long-wavelength source such as 365 nm or 405 nm, can be used.

As the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by Nippon Ciba) can be used as a commercial product.

More preferably, the photopolymerization initiator is an anthraquinone compound. As a specific example of the oxime-based initiator, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and JP-A-2006-342166 can be used. The compound described.

Examples of the ruthenium compound such as an anthracene derivative which can be suitably used as a photopolymerization initiator include 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyiminobutane. Alkan-2-one, 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1- Phenylpropan-1-one, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

As the oxime ester compound, "British Chemical Society, JC Perkin II" (1979) pp. 1653-1660, "JCS Perkin II" (1979) pp. 156-162, "Journal of Photopolymer Science and Technology" (1995) pp. 202-232, day The compound described in Japanese Laid-Open Patent Publication No. 2000-66385, the Japanese Patent Publication No. 2000-80068, the Japanese Patent Publication No. 2004-534797, and the Japanese Patent Publication No. 2006-342166 Compounds, etc.

Commercially available products such as IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF Corporation) can be suitably used.

In addition, as the oxime ester compound other than the above-mentioned, the compound described in Japanese Patent Laid-Open Publication No. 2009-519904, in which the oxime is bonded to the N-position of the carbazole, and the heterobenzoic acid introduced into the benzophenone moiety may be used. The compound described in Japanese Patent No. 7,626,957, the compound described in Japanese Patent Laid-Open Publication No. 2010-15025, and the Japanese Patent Publication No. 2009-292039, the International Patent Publication No. 2009-131189 The ketone-based compound described in the publication, the compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption at 405 nm, and has a good sensitivity to a g-ray source. A compound or the like described in JP-A-2009-221114.

In addition, the cyclic ruthenium compound described in Japanese Patent Laid-Open Publication No. 2007-23744 (Japanese Patent Application Laid-Open No. 2011/0123929), and the Japanese Patent Publication No. 2007-322744 .

In addition, an antimony compound having a specific substituent as shown in Japanese Patent Laid-Open Publication No. Hei. No. 2007-269779 (the corresponding U.S. Patent Application Publication No. 2010/0104976), or Japanese Patent Laid-Open No. 2009- No. 191061 (corresponding to the specification of US Patent Application Publication No. 2009/023085) An anthracene compound having a thioaryl group.

Reference may be made to the formula (OX-1), the formula (OX-2) or the formula after the paragraph 0513 of the Japanese Patent Laid-Open Publication No. 2012-208494 (paragraph 0632 of the corresponding US Patent Application Publication No. 2012/235099). Description of the compounds represented by (OX-3), the contents of which can be incorporated into the specification of the present application.

As a lanthanide polymerization initiator, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) can be used. ) and other commercial products. Further, the description of the polymerization initiator described in paragraphs 0092 to 0096 of JP-A-2012-113104 can be referred to, and the contents can be incorporated into the specification of the present application. By using such an oxime polymerization initiator, it is possible to provide a photosensitive composition having high curing sensitivity and good developability. The oxime polymerization initiator is a compound described in paragraph 0030 of JP-A-2012-113104. The general formula is represented by the general formula (I) described in the first paragraph of the patent application of Japanese Laid-Open Patent Publication No. 2012-113104, and is more preferably the general formula (IA) described in the third paragraph of the patent application. For those indicated, reference may be made to the descriptions, and the contents of the contents may be incorporated into the specification of the present application.

In the following, as a specific example of the ruthenium compound which can be suitably used, reference is made to paragraph 0090 to paragraph 0106 of the Japanese Patent Laid-Open Publication No. 2009-191061 (paragraph 0039 of the specification of the corresponding US Patent Application Publication No. 2009/023085), Japanese Patent Laid-Open No. 2012-032556, paragraph 0054, Japanese Patent Laid-Open The contents of paragraphs 0054 and the like in the Japanese Patent Publication No. 2012-122045, the contents of which are incorporated herein by reference. (PIox-1)~(PIox-13) is shown below, but the present invention is not limited to these specific examples.

The ruthenium compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a ruthenium compound having a high absorbance at 365 nm and 455 nm.

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

The molar absorption coefficient of the compound can be measured by a known method. Specifically, for example, an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) is preferably used. The measurement was carried out at a concentration of 0.01 g/L using an ethyl acetate solvent.

The photopolymerization initiator may be used in combination of two or more kinds as needed.

The content of the photopolymerization initiator relative to the total solid content of the photosensitive composition of the present invention is preferably from 0.1% by mass to 20% by mass, more preferably from 0.3% by mass to 15% by mass, even more preferably 0.4% by mass. ~10% by mass.

The photosensitive composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the photoradical polymerization initiator as a photopolymerization initiator and the long wavelength of the photosensitive wavelength. As the sensitizer, it is preferred to sensitize the photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

The sensitizer used in the photosensitive composition is, for example, a compound described in paragraphs 0101 to 0154 of JP-A-2008-32803.

The content of the sensitizer in the photosensitive composition is preferably from 0.1% by mass to 20% by mass, and more preferably 0.5% by mass, in terms of solid content, from the viewpoint of the light absorption efficiency in the deep portion and the initial decomposition efficiency. ~15% by mass.

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

<Polymerizable compound>

The photosensitive composition contains a polymerizable compound. Here, the polymerizable compound is a compound which causes polymerization by an active species. Examples of the active species include a radical, an acid, a base, and the like.

When the radical is an active species, as the polymerizable compound, a compound having a terminal ethylenically unsaturated bond as a polymerizable group is usually used.

On the other hand, when the active species is an acid such as a sulfonic acid, a phosphoric acid, a sulfinic acid, a carboxylic acid, a sulfuric acid or a sulfuric acid monoester, as the polymerizable compound, for example, an epoxy group, an oxetanyl group, a tetrahydrofuranyl group or the like is used. A cyclic ether group or a compound of a vinyl phenyl group.

In addition, when the active species is a base such as an amine compound, a compound having a cyclic ether group such as an epoxy group, an oxetanyl group or a tetrahydrofuranyl group or a vinylphenyl group is used as the polymerizable compound.

The polymerizable compound is preferably selected from compounds having at least one, more preferably two or more terminal ethylenically unsaturated bonds. Such a group of compounds is widely known in the industrial field, and these compounds can be used without particular limitation in the present invention. These compounds may be, for example, any of the chemical forms such as monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and multimers thereof. The polymerizable compound may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or Esters, guanamines, and multimers thereof, preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and guanamines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and Multimer. Further, an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, an addition reaction with a monofunctional or polyfunctional isocyanate or an epoxy group, or A dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid or the like. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol, A substituted carboxylic acid ester such as a halogen group or a toluenesulfonyloxy group or a decylamine and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable. Further, as another example, a group of compounds substituted with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether or allyl ether may be used instead of the unsaturated carboxylic acid.

As the specific compound, in the present invention, the compound described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used.

In addition, as the polymerizable compound, a compound having an ethylenically unsaturated group having at least one ethyl group which can undergo addition polymerization and having a boiling point of 100 ° C or higher at normal pressure is also preferable as the polymerizable monomer. . As an example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) propylene Monofunctional acrylate or methacrylate such as phenoxyethyl acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol (Meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (A) Acrylate, trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene methoxyethyl) isocyanurate, glycerol or trimethylolethane, etc. in polyfunctional alcohols For the addition of ethylene oxide or propylene oxide, the (meth) acrylate is obtained, for example, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho-50-6034, and Japanese Patent Laid-Open No. 51 The urethane (meth) acrylates described in each of the above-mentioned publications, Japanese Patent Laid-Open Publication No. SHO-48-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-30490 The polyester acrylates described in each of the publications are used as a reaction product of an epoxy resin and (meth)acrylic acid. A polyfunctional acrylate or methacrylate such as an epoxy acrylate or a mixture thereof.

A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate may, for example, be mentioned.

In addition, as another preferable polymerizable compound, an anthracene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, No. 4,436,216, and the like can be used. A compound having a functional or higher ethylenic polymerizable group, a cardo resin.

In addition, it has a boiling point of 100 ° C or more at normal pressure and has at least 1 A compound which can be subjected to addition polymerization of an ethylenically unsaturated group is also suitable as described in paragraphs 0254 to 0257 of JP-A-2008-292970.

In addition to the above, a radical polymerizable monomer represented by the following formula (MO-1) to formula (MO-5) can be suitably used. Further, in the formula, when T is an alkyloxy group, the terminal on the carbon atom side is bonded to R.

In the formula, n is 0 to 14, and m is 1 to 8. There are multiple molecules in one molecule R and T can be the same or different.

In each of the radical polymerizable monomers represented by the above formula (MO-1) to formula (MO-5), at least one of the plurality of R represents -OC(=O)CH=CH ₂ or a group represented by -OC(=O)C(CH ₃ )=CH ₂ .

Specific examples of the radical polymerizable monomer represented by the above formula (MO-1) to (MO-5) may be suitably used in the present invention. Japanese Patent Laid-Open Publication No. 2007-269779 The compound described in paragraphs 0248 to 0251.

The following compounds which are described in the general formula (1) and the general formula (2) together with the specific examples thereof can also be used as a polymerizable compound in a polyfunctional alcohol, as disclosed in Japanese Laid-Open Patent Publication No. Hei 10-62986. A compound obtained by (meth)acrylation after addition of ethylene oxide or propylene oxide.

Among them, as the polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Japan) are preferred. Chemical Pharmaceutical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available) KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and a structure in which the (meth)acryl fluorenyl group is interposed between an ethylene glycol residue and a propylene glycol residue. These oligomer types can also be used.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group, and examples thereof include an ethylenically unsaturated compound having an acid group. The ethylenically unsaturated compound having an acid group can be obtained by the following methods: A hydroxyl group of a part of the functional alcohol is (meth)acrylated, and the remaining hydroxyl group is subjected to an addition reaction with an acid anhydride to become a carboxyl group.

As described above, when the ethylenic compound is a compound having an unreacted carboxyl group as in the case of a mixture, the ethylenic compound can be directly used, and if necessary, the hydroxyl group and the non-aromatic carboxyl group of the ethylenic compound can also be used. The acid anhydride is reacted to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylation. Hexahydrophthalic anhydride, succinic anhydride, maleic anhydride.

The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably a polyfunctional single having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. Particularly preferred in the ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are polyacid-acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned, for example.

One type of these monomers may be used alone. However, since it is difficult to use a single compound in terms of production, two or more types may be used in combination. Further, as the monomer, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as needed.

A preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered, and if it is too high, the production or handling becomes difficult, and the photopolymerization performance is lowered, and the curability such as surface smoothness of the pixel is deteriorated. Therefore, when When two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is necessary to adjust the acid group of the entire polyfunctional monomer in the above range.

Further, as the polymerizable compound, a polyfunctional monomeric body having a caprolactone structure is preferable.

The polyfunctional monolith having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trishydroxymethylethane and di-trimethylol. Polyols such as ethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylol melamine, and (meth)acrylic acid and ε-caprolactone The ε-caprolactone obtained by esterification is modified with a polyfunctional (meth) acrylate. Among them, a polyfunctional mono-weight having a caprolactone structure represented by the following formula (1) is preferred.

(In the formula, all of the six R's are represented by the following formula (2), or one to five of the six R's are represented by the following formula (2), and the remainder is as follows The base represented by the formula (3)

[化22]

(wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond)

(wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond)

For example, the DPCA-20 (hereinafter referred to as Formula (1) to Formula (3)) which is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series is exemplified as the polyfunctional single component having such a caprolactone structure. , m = 1, a compound represented by the formula (2) = 2, a compound in which R ¹ is a hydrogen atom), DPCA-30 (in the formula, m = 1, represented by the formula (2) The number of groups = 3, a compound in which R ¹ is a hydrogen atom), DPCA-60 (in the formula, m = 1, the number of groups represented by the formula (2) = 6, and R ¹ is a hydrogen atom Compound), DPCA-120 (wherein m = 2, the number of groups represented by formula (2) = 6, and R ¹ is a compound of a hydrogen atom).

In the present invention, the polyfunctional monolith having a caprolactone structure may be used singly or in combination of two or more.

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

In the general formula (i) and the general formula (ii), E independently represents -((CH ₂ )yCH ₂ O)-, or -((CH ₂ )yCH(CH ₃ )O)-, y, respectively, independently An integer of 0 to 10 is represented, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (i), the total of the acryl fluorenyl group and the methacryl fluorenyl group is three or four, and m each independently represents an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group.

In the general formula (ii), the total of the acryloyl group and the methacryl fluorenyl group is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably 2 to 16 The number is particularly good for an integer from 4 to 8.

In the formula (ii), n is preferably an integer of 0 to 6, 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.

Further, -((CH ₂ )yCH ₂ O)- or -((CH ₂ )yCH(CH ₃ )O)- in the formula (i) or the formula (ii) is preferably a terminal bond on the oxygen atom side. Formed on X.

The compound represented by the formula (i) or the formula (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), it is preferred that all of the six X groups are acrylonitrile groups.

In addition, the total content of the compound represented by the formula (i) or the formula (ii) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

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

Among the compounds represented by the general formula (i) or the general formula (ii), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferable.

Specifically, a compound represented by the following formula (a) to formula (f) (hereinafter also referred to as "exemplary compound (a) to exemplary compound (f)")) is preferable. The compound (a), the exemplified compound (b), the exemplified compound (e), and the exemplified compound (f) are shown by way of example.

[Chem. 26]

As a commercial item of the polymerizable compound represented by the general formula (i) or the general formula (ii), for example, a tetrafunctional acrylic acid having four ethylene glycol chains can be exemplified by Sartomer Co., Ltd. Ester SR-494, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, and TPA as a trifunctional acrylate having 3 extended isobutoxy chains -330 and so on.

In addition, as the polymerizable compound, an amine group as described in JP-A-48-41708, JP-A-53-37193, JP-A-2-332293, and JP-A No. 2-16765 Formate acrylates, or Japanese Patent Publication No. Sho 58-49860, Japanese Patent Special Publication No. 56-17654, Japanese A urethane compound having an ethylene oxide-based skeleton described in JP-A-62-39417 and JP-A-62-39418 is also suitable. Further, an addition having an amine structure or a sulfide structure in the molecule described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As a polymerizable compound, a polymerizable compound can obtain a curable composition having a very excellent photospeed.

As a commercial product of a polymerizable compound, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp company), UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.) , DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.).

The details of the method of using the polymerizable compound, the use alone or in combination, and the amount of addition can be arbitrarily set in combination with the final performance design of the photosensitive composition. For example, from the viewpoint of sensitivity, a structure having a large content of an unsaturated group per molecule is preferable, and in many cases, a difunctional or higher is preferable. Moreover, from the viewpoint of improving the strength of the cured film, a trifunctional or higher polymerizable compound is preferred, and further, the number of functional groups is different. A polymerizable compound having a different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound) is effective for adjusting both sensitivity and strength. Further, it is preferable to use a polymerizable compound having a trifunctional or higher functional group and a different ethylene oxide chain length to adjust the developability of the photosensitive composition, and to obtain an excellent pattern. In addition, for other components contained in the photosensitive composition (for example, a photopolymerization initiator, a base) The compatibility and dispersibility of soluble resins, etc., the choice of polymerizable compounds. The use method is also an important factor. For example, it is sometimes possible to improve the compatibility by using a low-purity compound or a combination of two or more. Moreover, a specific structure can also be selected from the viewpoint of improving the adhesion to a hard surface such as a support.

Specific examples of the polymerizable compound are listed below, but are not limited thereto.

Further, the polymerizable compound may be a compound having a polymerizable group and a decyl group (hereinafter, also referred to as a decyl group compound). When a photosensitive composition containing the fluorene-based compound is imparted (for example, coated) onto a support, the interaction between the Si atom of the fluorene-based compound and the component constituting the support, the photosensitive composition and the support Increased adhesion.

The fluorenyl group compound is preferably a compound represented by the following formula (a) (hereinafter also referred to as "specific decyl group compound") from the viewpoint of enhancing the interaction with the support and the compatibility.

In the formula (a), X is a hydrogen atom or an organic group, and preferably an organic group having one or more polymerizable groups and having an amine group. Y ¹ , Y ² , and Y ³ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an alkoxy group, a halogen atom, an aryloxy group, an amine group, a decyl group, a heterocyclic group, or a hydrogen. The atom is preferably an alkyl group or an alkoxy group.

Further, in the formula (a), X, Y ¹ , Y ² and Y ³ may have a polymerizable group (for example, a (meth) acrylate group, a (meth) acrylamide group, a styryl group, etc.) .

Examples of the decyl-alkyl compound include a fluorenylalkyl group having a polymerizable group in paragraphs 0056 to 0066 of JP-A-2009-242604. Things.

As the polymerizable compound, a thio(meth)acrylate compound described in paragraph 0024 to paragraph 0031 of Japanese Patent No. 4176717 (paragraph 0027 to paragraph 0033 of US2005/0261406) can also be used, and the contents thereof can be cited. And can be incorporated into the specification of the present application.

The content of the polymerizable compound in the photosensitive composition is preferably from 0.1% by mass to 90% by mass, more preferably from 1.0% by mass to 80% by mass, even more preferably 3% by mass based on the solid content of the photosensitive composition. %~30% by mass.

One type of the polymerizable compound may be used, or two or more types may be used in combination.

<Other ingredients>

The photosensitive composition of the present invention may contain other components than the above components. Specifically, an organic solvent, a surfactant, a adhesion promoter, a polymerization inhibitor may be added to the range of properties (heat resistance, mechanical strength, coatability, adhesion, etc.) of the film obtained by using the composition without loss. Additives such as UV absorbers, antioxidants, and anti-agglomerants.

Hereinafter, the components will be described in detail.

<organic solvent>

The photosensitive composition of the present invention may also contain an organic solvent. The organic solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the composition. In particular, it is preferably selected in consideration of solubility, coatability, and safety of the alkali-soluble resin.

As the organic solvent, as the ester, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, and C can be suitably used. Butyl acrylate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl glycolate (eg methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate) (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-hydroxypropionate ( For example: methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, etc.)), alkyl 2-hydroxypropionate (for example: methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc. For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate )), methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropanoate (for example methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, 2-oxobutyric acid B Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and 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 single Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone, and aromatic hydrocarbons. For example, toluene, xylene, or the like can be suitably exemplified.

From the viewpoints of solubility of the alkali-soluble resin, improvement of the coating surface, and the like, a form in which two or more kinds of these organic solvents are mixed is also preferable. In this case, it is particularly preferred to be a mixed solution comprising methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexyl Two or more kinds of ketone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

From the viewpoint of the coating property, the content of the organic solvent in the photosensitive composition is preferably such that the total solid content concentration of the composition is from 5% by mass to 80% by mass, more preferably as a composition. The total solid content concentration is an amount of 5% by mass to 60% by mass, and particularly preferably an amount of the total solid content of the composition of 10% by mass to 50% by mass.

<Surfactant>

From the viewpoint of further improving the coatability, various photosensitive agents may be added to the photosensitive composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used, and a fluorine-based interface is preferable. Active agent.

The type of the surfactant to be used is not particularly limited, and examples thereof include the surfactants exemplified in paragraphs 0240 to 0244 of JP-A-2012-122045. More specifically, Megafac F-781F, Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, Di Ai Health (DIC) (shares) manufacturing, etc.

<Intimate accelerator>

The photosensitive composition of the present invention may contain any adhesion promoter insofar as it does not impair the object of the present invention. Examples of the adhesion promoter include 3-glycidoxypropyltrimethoxydecane, 1-methylpropenyloxypropylmethyldimethoxydecane, and 3-aminoglycidoxypropyl group. Triethoxy decane, 3-glycidoxy propyl methyl dimethoxy decane, 3-aminopropyl trimethoxy decane, and the like. Further, the compound described in paragraph 0048 of JP-A-2008-243945 is used.

The photosensitive composition of the present invention may contain an adhesion promoter or may not contain an adhesion promoter. When the adhesion promoter is contained, the preferred amount of the adhesion promoter is not particularly limited, and is usually relative to the total solid in the composition. The component is preferably 10% by mass or less, and particularly preferably 0.005% by mass to 5% by mass.

<Polymerization inhibitor>

In the photosensitive composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during the production of the photosensitive composition, it is preferred to add a small amount of a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, tert-butylcatechol, benzoquinone, 4,4'-sulfur. Bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine Trivalent strontium salt and the like.

Addition of a polymerization inhibitor relative to the total solid component mass of the photosensitive composition The amount is preferably from 0.01% by mass to 5% by mass.

<UV absorber>

The photosensitive composition of the present invention preferably contains an ultraviolet absorber, whereby the shape of the pattern can be made into a more excellent (fine) shape.

As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based or triazine-based ultraviolet absorber can be used. As a specific example of these, a compound of the paragraphs 0137 to 1 142 of the Japanese Patent Laid-Open Publication No. 2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012/0068292) can be used, and the contents can be referred to. And can be incorporated into the specification of this application.

Further, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) or the like can be suitably used.

The ultraviolet absorbing agent may, for example, be a compound exemplified in paragraphs 0134 to 0148 of JP-A-2012-32556.

The photosensitive composition may contain an ultraviolet absorber or may not contain an ultraviolet absorber. When the ultraviolet absorber is contained, the content of the ultraviolet absorber is preferably 0.001% by mass to 15% by mass based on the total solid content of the photosensitive composition. % is more preferably 0.01% by mass to 10% by mass.

<alkaline compound>

The photosensitive composition of the present invention preferably contains a basic compound, whereby the residue of the unexposed portion can be reduced. The structure of the basic compound is not particularly limited, but is preferably an amine compound, and particularly preferably an amine group-containing resin.

The resin containing an amine group is preferably a resin (hereinafter also referred to as a specific resin) having (i) a main chain portion containing a nitrogen atom in the side chain and (ii) a functional group having a pKa of 14 or less. And a group "X" which is bonded to a nitrogen atom existing in the main chain portion, and (iii) an oligomer chain or a polymer chain "Y" having a number average molecular weight of 500 to 1,000,000. Hereinafter, the specific resin will be described in detail.

(i) The main chain portion containing a nitrogen atom preferably has a main chain portion containing an oligomer or a polymer containing a primary amine group or a secondary amine group. As the oligomer or polymer containing an amine group, specifically, it is preferably selected from the group consisting of poly(lower alkylene imine), polyallylamine, polydiallylamine, and m-xylenediamine- A main chain structure in an epichlorohydrin polycondensate, a polyvinylamine or the like. The poly(lower alkylene imide) may be in the form of a chain or a network.

The number average molecular weight of the main chain portion is preferably from 100 to 10,000, more preferably from 200 to 5,000, most preferably from 300 to 2,000. The molecular weight of the main chain portion can be determined from the ratio of the terminal group of the main chain portion and the hydrogen atom integrated value measured by the nuclear magnetic resonance spectroscopy, or the amino group-containing oligomer or polymer as a raw material. The molecular weight was measured and determined.

(ii) The group "X" containing a functional group having a pKa of 14 or less represents a group containing a functional group having a pKa of 14 or less at a water temperature of 25 °C. The "pKa" described herein refers to the pKa of the definition described in "Chemical Fact (II)" (Revision 4, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.).

The "functional group having a pKa of 14 or less" is particularly preferably a functional group having a pKa of 12 or less, and preferably a functional group having a pKa of 11 or less. Specific examples thereof include carboxylic acid (pKa of about 3 to 5), sulfonic acid (pKa of about -3 to 2), -COCH ₂ CO- (pKa of about 8 to 10), and -COCH ₂ CN ( pKa is about 8~11), -CONHCO-, phenolic hydroxyl group, -RFCH ₂ OH or -(RF) ₂ CHOH (RF stands for perfluoroalkyl group, pKa is about 9~11), sulfonamide group (pKa is Between 9 and 11), etc., particularly preferred are carboxylic acids, sulfonic acids, and -COCH ₂ CO-.

The group "X" containing the functional group having a pKa of 14 or less is usually directly bonded to a nitrogen atom contained in the main chain structure, and the nitrogen atom of the main chain portion of the specific resin and X can be not only covalently bonded. The form in which the salt is formed is linked, and it is also possible to form a salt by ion bonding.

(iii) An oligomer chain or a polymer chain "Y" having a number average molecular weight of 500 to 100,000, such as polyester, polyamine, polyimine, or poly(methyl) which can be bonded to a main chain portion of a specific resin A well-known polymer chain such as acrylate. The bonding site of Y with a specific resin is preferably an end.

Y is preferably bonded to a nitrogen atom of the main chain portion. The bonding mode of Y to the main chain portion is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the bonding mode of Y to the main chain portion is a covalent bond: ion bonding = 100:0 to 0:100, preferably 95:5 to 5:95, and most preferably 90:10 to 10:90. . If it is outside this range, solvent solubility will become low.

Y is preferably a guanidine bond with a nitrogen atom of the main chain portion or an ionic bond with a carboxylate.

The number average molecular weight of Y can be measured by a polystyrene equivalent value obtained by a GPC method. The number average molecular weight of Y is particularly preferably from 1,000 to 50,000, and is on developability. From the point of view, the best is 1,000 to 30,000.

It is preferable to link two or more side chain structures represented by Y to one molecule of the resin, and it is preferable to link five or more side chain structures represented by Y to the resin.

As the resin containing an amine group, for example, a compound exemplified in paragraphs 0074 to 0084 of JP-A-2010-6932 can be used, and the contents can be cited and incorporated into the specification of the present application.

The photosensitive composition may not contain a basic compound, but when the basic compound is contained, the content of the basic compound is preferably 0.001% by mass to 15% by mass based on the total solid content of the photosensitive composition, and more preferably 0.01% by mass to 10% by mass.

The photosensitive composition may further comprise a high refractive index low molecular compound. The high refractive index low molecular compound may be a low molecular compound (high refractive index low molecular compound) having a structure exhibiting a high refractive index, and may also contain a polymerizable group. In other words, the high refractive index low molecular compound may be a "polymerizable monomer" (a compound containing a polymerizable group) or a "low molecular compound" (a compound containing no polymerizable group), but is preferably a "low molecular weight". Compound". The high refractive index low molecular compound is a compound different from the alkali soluble resin.

The molecular weight of the high refractive index low molecular compound is not particularly limited, but is preferably 3,000 or less, more preferably 800 or less, still more preferably 600 or less.

In the photosensitive composition, the high refractive index low molecular compound also functions as a sensitivity adjuster, and by optimizing the content, the yield can be improved in the film formation process. The content of the high refractive index low molecular compound is not particularly limited, and the alkali can be used. The content of the soluble resin is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less based on the content of the alkali-soluble resin. By adding a trace amount of the high refractive index low molecular compound, the refractive index can be further increased as compared with the alkali-soluble resin having the repeating unit represented by the formula (X).

The high refractive index low molecular compound preferably has the same structure as the structure exhibiting a high refractive index of the alkali-soluble resin having a repeating unit represented by the formula (X). Specifically, the high refractive index low molecular compound may be exemplified by a low molecular compound having a carbazole structure (for example, the vinyl carbazole or the like or a carbazole; methyl carbazole, ethyl carbazole or the like having a hydrocarbon group on N ( A preferred carbazole having 1 to 30 carbon atoms, a carbazole having a hydrocarbon group (preferably having a carbon number of 1 to 30, etc.) or a compound having a naphthalene structure (for example, the vinyl naphthalene or the like) And naphthalene, and a naphthene having a hydrocarbon group (preferably having a carbon number of 1 to 30).

Further, in the photosensitive composition, the content of the salt such as NaCl is preferably small, and is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, still more preferably 25 ppm by mass or less, and particularly preferably 10 or less. The mass is ppm or less, particularly preferably 1 ppm by mass or less, and most preferably 0.1 ppm by mass or less. The content of the salt can be adjusted by a refining operation such as distillation or filtration of each raw material.

Further, in the photosensitive composition, the content of the sodium element is preferably small, and is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, still more preferably 25 ppm by mass or less, and particularly preferably 10 ppm by mass. Below ppm. The content of the sodium element can be adjusted by a refining operation such as distillation or filtration of each raw material.

Further, the coating film obtained from the photosensitive composition is reduced by the sodium element Or the surface defects of the cured film (color filter) and the like are further suppressed, and as a result, the yield of the product is improved.

As a method of measuring the amount of sodium element, as described above, for example, an ICP-MS (Inductively Coupled Plasma Mass Spectrometer) can be employed.

The photosensitive composition of the present invention is preferably a transparent composition, and more specifically, when a cured film having a film thickness of 1 μm is formed by a composition, light transmittance in the thickness direction of the cured film is spread throughout The entire region of the wavelength region of 400 nm to 700 nm becomes 90% or more.

The photosensitive composition of the present invention exhibits a sufficient function as a white filter pixel for the white filter pixel contained in the color filter, and preferably has a light transmittance of 400 nm to 700 nm. The entire area of the wavelength region is 90% or more (that is, the entire area of the wavelength region of 400 nm to 700 nm is required to be 90% or more in order to perform photographing in the image sensor with high sensitivity).

Further, the light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100% in the entire wavelength region of 400 nm to 700 nm.

In the photosensitive composition of the present invention, it is preferred that the metal content as an impurity is sufficiently small. The metal concentration in the composition can be measured with high sensitivity by the ICP-MS method or the like. In this case, the metal content other than the transition metal is preferably 300 ppm by mass or less, and more preferably 100 ppm by mass or less.

The method for producing the photosensitive composition is not particularly limited, and when an organic solvent is contained, it is obtained by adding each component of the composition to an organic solvent and stirring.

The composition is preferably used for film formation by filtering by a filter to remove insoluble matter, gelatinous component, or the like. The filter used at this time preferably has a pore diameter of 0.05 μm to 2.0 μm, a pore diameter of preferably 0.05 μm to 1.0 μm, and an optimum pore diameter of 0.05 μm to 0.5 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene, polypropylene, nylon, more preferably polytetrafluoroethylene, polyethylene and nylon.

In order to remove foreign matter, reduce defects, and the like, it is preferred to filter the photosensitive composition of the present invention with a filter. It is not particularly limited as long as it is a filter used for filtration purposes or the like from the past. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon, a polyolefin resin such as polyethylene or polypropylene (high density, and an ultrahigh molecular weight) may be used. filter. Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore diameter of the filter is suitably from about 0.1 μm to about 7.0 μm, preferably from about 0.2 μm to about 2.5 μm, more preferably from about 0.2 μm to about 1.5 μm, and still more preferably from 0.3 μm to 0.7 μm. By setting it as this range, it is possible to suppress clogging of the pigment by filtration, and it is possible to reliably remove fine foreign matter such as impurities or aggregates contained in the pigment.

Different filters can also be combined when using filters. At this time, the filtration by the first type of filter may be performed only once or twice or more. When two or more filters are combined by using different filters, it is preferred that the pore diameter after the second filtration is equal to or larger than the pore diameter of the first filtration. Further, the first type of filters having different pore diameters may be combined in the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., Japan Nihon Entegris Co., Ltd. (formerly Japan, Mykrolis Co., Ltd.), or Choose from a variety of filters available from Kitz Microfilter Co., Ltd., etc.

As the second filter, a filter formed of the same material as the first filter or the like can be used. The pore diameter of the second filter is suitably from about 0.2 μm to about 10.0 μm, preferably from about 0.2 μm to about 7.0 μm, more preferably from about 0.3 μm to about 6.0 μm. By setting it as the range, the foreign matter mixed in the mixed liquid can be removed in a state where the component particles contained in the mixed solution remain.

For example, the filtration by the first type of filter may be carried out only in the dispersion, and after the other components are mixed, the second filtration is performed.

<Use (Color Filter)>

The photosensitive composition of the present invention is preferably used as a photosensitive composition for forming a color filter or a photosensitive composition for a microlens, and more specifically, preferably used as a color filter for a solid-state imaging element. The white filter is made of a photosensitive composition.

A method of manufacturing a color filter of a solid-state imaging device of the present invention (hereinafter also referred to as a color filter for a solid-state imaging device) includes: coating a color filter for forming a solid-state imaging device of the present invention described above The photosensitive layer is formed into a coating layer (photosensitive composition layer) (hereinafter also referred to as "photosensitive composition layer forming step"), and the coating layer is exposed (hereinafter also referred to as "exposure step") And developing, thereby forming a pattern, and obtaining a cured film of a white filter pixel in a color filter as a solid-state imaging element.

Further, the color filter for solid-state imaging elements of the present invention is manufactured by the method for producing a color filter for solid-state imaging elements of the present invention.

The color filter for a solid-state imaging device of the present invention may have at least a transparent (white) pattern (white filter pixel) manufactured by the method for producing a color filter for solid-state imaging elements of the present invention. As a specific form of the color filter for solid-state imaging elements of the present invention, for example, a form of a color filter of a plurality of colors in which a transparent pattern and another colored pattern are combined is used (for example, at least a transparent pattern, a red pattern, and Blue color pattern and color filter of 4 colors or more of green pattern).

Hereinafter, the color filter for solid-state imaging elements may be simply referred to as a "color filter".

<Photosensitive Composition Layer Formation Step>

In the photosensitive composition layer forming step, it is preferred that the photosensitive composition of the present invention is applied to a support to form a photosensitive composition layer.

As a support which can be used for this step, for example, a solid-state imaging element in which a photographic 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 ruthenium substrate) can be used. Substrate.

The transparent pattern in the present invention may be formed on the imaging element forming surface side (surface) of the solid-state imaging element substrate, or may be formed on the non-imaging element forming surface side (back surface).

A light shielding film may be provided between each of the imaging elements in the solid-state imaging element substrate or the back surface of the solid-state imaging element substrate.

Further, in order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or to flatten the surface of the substrate, an undercoat layer may be provided on the support as needed.

As a method of imparting the photosensitive composition layer of the present invention to a support, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be applied. .

The film thickness of the photosensitive composition layer is preferably 0.1 μm to 10 μm, more preferably 0.1 μm to 3 μm, still more preferably 0.1 μm to 2 μm.

The drying (prebaking) of the photosensitive composition layer coated on the support can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds by means of a hot plate, an oven or the like.

<Exposure step>

In the exposure step, for example, a photosensitive composition layer formed in the photosensitive composition layer forming step is subjected to pattern exposure by using an exposure device such as a stepper through a mask having a predetermined mask pattern.

The radiation (light) which can be used for exposure includes visible light rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like. In particular, ultraviolet rays such as g-rays and i-rays can be preferably used (particularly i-rays). ). Irradiation amount (exposure amount) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 1000mJ / cm} 2, and further more preferably ^{80mJ / cm 2 ~ 500mJ / cm} 2.

<Development step>

Then, an alkali development treatment is performed, whereby the photosensitive composition layer of the unirradiated portion of the light in the exposure step is eluted into the alkaline aqueous solution, and only the photocured portion remains.

As the developer, it is desirable not to damage the underlying photographic element or circuit. Harmful organic alkaline developer. The development temperature is usually 20 ° C to 30 ° C, and the development time is previously 20 seconds to 90 seconds. In order to further remove the residue, in recent years, there have been cases in which 120 seconds to 180 seconds have been carried out. Further, in order to further improve the residue removal property, the following steps may be repeated a plurality of times: the developer is shaken off every 60 seconds, and the developer is supplied again.

As the alkaline developing solution, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, and diethylamine can be used. Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethyl hydroxide Ammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyl hydroxide Tetraalkylammonium hydroxide such as methylammonium, methyltriammonium hydroxide or dibutylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, and hydroxide A quaternary ammonium salt such as triethylbenzylammonium or an alkaline aqueous solution such as a cyclic amine such as pyrrole or piperidine. Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution for use. The alkali concentration of the alkaline developer is usually from 0.1% by mass to 20% by mass. The pH of the alkaline developer is usually from 10.0 to 15.0. The alkali concentration and pH of the alkaline developer can be appropriately adjusted and used. The alkaline developer may also be added by using a surfactant or an organic solvent.

Further, when a developer containing such an aqueous alkaline solution is used, it is usually washed (rinsed) with pure water after development.

Then, it is preferred to carry out heat treatment (post-baking) after drying. If a pattern of a plurality of colors is formed, the steps can be repeated for each color to produce a hardened film. Thereby, a color filter can be obtained.

The post-baking is a heat treatment for developing after development which is completely hardened, and is usually subjected to a heat hardening treatment at 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C.

A heating plate or a convection oven (hot air circulation dryer), a high-frequency heating device or the like can be used to form the condition, and the developed coating film can be subjected to the continuous or batch type. Baking treatment.

Further, the production method of the present invention may have a step known as a method of producing a color filter for a solid-state image sensor as needed. For example, after the photosensitive composition layer forming step, the exposing step, and the developing step, a hardening step of hardening the formed transparent pattern by heating and/or exposure may be included as needed.

In addition, when the photosensitive composition of the present invention is used, for example, there is a case where clogging of the nozzle or the piping portion of the coating device discharge portion or adhesion of the photosensitive composition or inorganic particles in the coating machine occurs. . precipitation. Pollution caused by drying, etc. Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The cleaning liquid described in the Japanese Patent Laid-Open Publication No. Hei. No. 2007-291191, the Japanese Patent Publication No. 2007-2101, the Japanese Patent Publication No. 2007-2102, and the Japanese Patent Publication No. 2007-281523 can also be suitably used. The cleaning and removal of the photosensitive composition used in the present invention.

Among them, an alkylene glycol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether are preferred.

These solvents may be used singly or in combination of two or more. When two or more kinds are mixed, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. Particularly preferred is a mixed solvent of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and Propylene Glycol Monomethyl Ether (PGME) in a ratio of 60/40. Furthermore, in order to increase the permeability of the cleaning solution to the contaminants, the surfactant associated with the composition may also be added to the cleaning solution.

The color filter for a solid-state imaging device of the present invention is obtained by using the photosensitive composition of the present invention as a white filter pixel contained in the color filter, so that it has an excellent pattern shape and high resolution. And the state in which the development residue is reduced is formed. Further, the white filter pixel in the color filter preferably has a refractive index of more than 1.62 for light having a wavelength of 633 nm.

By mounting the solid-state imaging element of the present invention in a color sensor with a color filter, it is possible to perform imaging in an image sensor with high sensitivity and high quality.

The color filter for solid-state imaging elements of the present invention can be suitably used for solid-state imaging elements such as CCDs and CMOSs, and is particularly suitable for high-resolution CCDs or CMOSs of more than one million pixels. The color filter for solid-state imaging elements of the present invention can be used, for example, as a color filter disposed between a light receiving portion constituting each pixel of a CCD or CMOS and a microlens for collecting light.

The film thickness of the colored pattern (colored pixel or white filter pixel) in the color filter for a solid-state imaging device is preferably 2.0 μm or less, and more preferably 1.0 μm or less. Here, the term "coloring" of the colored pattern (coloring pixel) means 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 it has good lithiation properties, it is suitable for use in such a small coloring pattern.

[Solid photographic components]

The solid-state imaging element of the present invention includes the color filter for solid-state imaging elements of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has a configuration in which the color filter for a solid-state imaging device of the present invention is provided as a solid-state imaging device, and the following configuration is exemplified.

The configuration includes a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, etc.) and a transfer electrode including a polysilicon or the like on the support, and the photodiode And a light-shielding film containing tungsten or the like which is opened only to the light-receiving portion of the photodiode, and has a nitriding film formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. The element protective film of 矽 or the like has the color filter for solid-state imaging elements of the present invention on the element protective film.

Further, it may have a configuration such as a concentrating device (for example, a microlens or the like) on the element protective layer and under the color filter (on the side close to the support). The configuration of the same) or the configuration of the concentrating device on the color filter.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, "parts" and "%" are quality standards unless otherwise specified.

Further, in the present Example, each of the dispersions described later and after the preparation of the photosensitive composition described later were filtered using DFA4201 NXEY (0.45 μm nylon filter) manufactured by Pall Japan.

<Example A: Example 1 to Example 8, Comparative Example 1>

(Preparation of zirconia dispersion)

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

~Comment~

Zirconia (first rare element chemical industry (stock) manufacturing, UEP-100): 24.4 parts

Exemplary compound 29 or Solsperse 71000 (made by Lubrizol, Ltd.): 5.6 parts

Propylene glycol monomethyl ether acetate (PGMEA): 70.0 parts

[化29]

(Preparation of photosensitive composition)

The zirconia dispersion (dispersion composition) obtained above and the alkali-soluble resin shown in Table 3 were mixed in the following composition to obtain a photosensitive composition. Further, the numbers of the examples of the resin of the alkali-soluble resin in Tables 3 and 4 below correspond to the exemplified resins in Table 1.

~Comment~

32.79 parts of the zirconia dispersion (dispersion composition) prepared above

Photopolymerization initiator A1 (IRGACURE OXE-01 (K-1) manufactured by BASF Corporation) 1.14 parts

Polymeric compound B1 (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., T-1 below) 4.23 parts

Polymeric compound B2 (M-1) 0.10 parts

Alkali-soluble resin (refer to Table 3 below) 3.09 parts

58.65 parts of propylene glycol monomethyl ether acetate (PGMEA)

[化30]

(Measurement of refractive index and transmittance)

The photosensitive composition obtained above was applied onto a ruthenium wafer by a spin coating method, and then heated on a hot plate at 100 ° C for 3 minutes to obtain a photosensitive composition layer having a film thickness of 1 μm.

Then, the obtained photosensitive composition layer was subjected to total exposure at an exposure amount of 1000 mJ/cm ² at a wavelength of 365 nm using an i-ray stepper FPA-3000i5+ (manufactured by Canon).

With respect to the obtained cured film, the refractive index of light having a wavelength of 550 nm was measured using an ellipsometer (VASE) manufactured by J.A. Woollam Japan Co., Ltd. In addition, about the cured film, the light transmittance of the entire region of the wavelength region of 400 nm to 700 nm was measured using the MCPD series manufactured by Otsuka Electronics Co., Ltd.

Further, the refractive index was evaluated in accordance with the following criteria.

"A": the case where the refractive index exceeds 1.62

"B": the case where the refractive index is 1.62 or less

Further, the light transmittance was evaluated in accordance with the following criteria.

"A": the case where the light transmittance exceeds 90%

"B": The case where the light transmittance is 90% or less

(production of transparent pattern)

In the photosensitive composition layer described in the above (measurement of the refractive index and the transmittance), a mask pattern of 4 mm × 3 mm in a region of 1.1 μm is placed on the substrate, and i is used. The ray stepper FPA-3000i5+ (manufactured by Canon Co., Ltd.) was exposed at a wavelength of 365 nm at an exposure amount of 1000 mJ/cm ² .

The photosensitive composition layer after the exposure was subjected to a liquid-contact development at 23 ° C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. Thereafter, it was rinsed by spin spraying and water, and then washed with pure water. Thereafter, the water droplets are splashed by the high-pressure air, and the germanium wafer is naturally dried, and then baked at 200 ° C for 300 seconds on the hot plate to obtain a transparent film having a thickness of 1 μm on the germanium wafer. Pattern (hardened film).

(Micrograph performance evaluation (lithographic evaluation))

The surface roughness (Ra) of the obtained transparent pattern was measured using an Atomic Force Microscopy (AFM) (manufactured by Digital Instruments, Inc., Nano Scope). The smaller the value of the surface roughness Ra, the better. The lithography performance was evaluated according to the following criteria. Practically, it is preferably "A" or "B".

"A": less than 30nm

"B": 30 nm or more and 50 nm or less

"C": more than 50nm

(Refractive index evaluation after heat resistance test)

The cured film obtained in the above (measurement of refractive index and transmittance) was heated on a hot plate at 265 ° C for 5 minutes. The refractive index evaluation after the heat resistance test was evaluated according to the following criteria.

"A": the case where the refractive index exceeds 1.62

"B": the case where the refractive index is 1.62 or less

In addition, "N-1" in Table 2 below is the following compound. The numerical values in the formula represent the molar % of each repeating unit.

As shown in Table 3, the photosensitive composition of the present invention is also excellent in lithographic properties, and the cured film obtained by using the composition exhibits an excellent refractive index. Further, the obtained cured film was excellent in transmittance and excellent in refractive index after heat resistance test.

In particular, as is clear from the comparison between Example 3 and Example 4, it has been confirmed that when a naphthyl group is used as the condensed aromatic ring group, the lithographic performance is more excellent.

On the other hand, when the photosensitive composition disclosed in Patent Document 1 is used, the lithographic performance and the refractive index characteristics are not preferable.

To each of the photosensitive compositions of Examples 1 to 8, 50 mass ppm, 30 mass ppm, or 5 mass ppm of NaCl was added to prepare a composition.

A cured film was formed in the same manner as in Examples 1 to 8 except that the photosensitive compositions were used. It has been confirmed that each evaluation of the obtained cured film is the same as that of the above-described embodiment, and generation of defects of the cured film is reduced. In addition, it has been confirmed that the storage stability is improved in the composition to which 5 ppm by mass of NaCl is added.

In each of the photosensitive compositions of Examples 1 to 8, 10% by mass, 7% by mass, or 5% by mass of carbazole (molecular weight: 167) was further added to the total mass of the alkali-soluble resin to prepare a composition. .

A cured film was formed in the same manner as in Examples 1 to 8 except that the photosensitive compositions were used. It has been confirmed that each evaluation of the obtained cured film is the same as that of the above-described embodiment, and the refractive index of the cured film is further increased, and the curing can be promoted even if the exposure amount is reduced.

<Example B>

<Example 10>

(Preparation of titanium oxide dispersion 1)

Using a Ultra Apex Mill (trade name) manufactured by Shou Industrial Co., Ltd. as a circulating type dispersing device (bead mill), a mixed liquid of the following composition was subjected to dispersion treatment to obtain a titanium oxide dispersion liquid.

~Comment~

Titanium oxide (TTO-51C manufactured by Ishihara Industry): 2.36 parts

Crystalline: rutile, TiO ₂ %: 79%~85%, surface treatment with Al ₂ O ₃ and stearic acid, specific surface area of 50m ² /g~60m ² /g, primary particle size of 10nm~30nm, Oil absorption is 24g/100g~30g/100g

Exemplary compound 29 (30% PGMEA solution): 2.13 parts

Propylene glycol monomethyl ether acetate (PGMEA): 5.51 parts

(Preparation of photosensitive composition)

The titanium oxide dispersion liquid (dispersion composition) obtained above and the alkali-soluble resin shown in Table 4 were mixed in the following composition to obtain a photosensitive composition. The numbering of the examples of the alkali-soluble resin in the following Table 4 is equivalent to the exemplified resin in Table 1 or Table 2.

~Comment~

The weight average molecular weight (Mw) of A-2 was 9000, and the copolymerization ratio (mol ratio) was as described above.

(Measurement of refractive index and transmittance)

The photosensitive composition obtained above was applied onto a ruthenium wafer by a spin coating method, and then heated on a hot plate at 90 ° C for 2 minutes to obtain a photosensitive composition layer having a film thickness of 0.6 μm.

Then, the obtained photosensitive composition layer was subjected to total exposure at an exposure amount of 1000 mJ/cm ² at a wavelength of 365 nm using an i-ray stepper FPA-3000i5+ (manufactured by Canon).

With respect to the obtained cured film, the refractive index of light having a wavelength of 550 nm was measured using an ellipsometer (VASE) manufactured by J.A. Woollam Japan Co., Ltd. In addition, about the cured film, the light transmittance of the entire region of the wavelength region of 400 nm to 700 nm was measured using the MCPD series manufactured by Otsuka Electronics Co., Ltd. Further, the refractive index and the transmittance were evaluated in accordance with the following criteria.

. Refractive index

"A": the case where the refractive index exceeds 1.74

"B": the case where the refractive index is 1.74 or less

. Transmission rate

"A": the case where the light transmittance exceeds 90%

"B": The case where the light transmittance is 90% or less

(Micrograph performance evaluation (lithographic evaluation))

In the photosensitive composition layer described in the above (measurement of the refractive index and the transmittance), a mask pattern of 4 mm × 3 mm in a region of 1.1 μm is placed on the substrate, and i is used. The ray stepper FPA-3000i5+ (manufactured by Canon Co., Ltd.) was exposed at a wavelength of 365 nm at an exposure amount of 1000 mJ/cm ² .

The photosensitive composition layer after the exposure was subjected to a liquid-contact development at 23 ° C for 60 seconds using a 0.2% by mass aqueous solution of tetramethylammonium hydroxide. Thereafter, it was rinsed by spin spraying and water, and then washed with pure water. Thereafter, the water droplets were splashed by the high-pressure air, and the germanium wafer was naturally dried, and then baked at 200 ° C for 480 seconds on the hot plate to obtain a film thickness of 0.6 μm on the germanium wafer. Transparent pattern (hardened film). The lithography performance was evaluated according to the following criteria.

"A": The pattern is rectangular and clear with no residue.

"B": The pattern is rectangular and clear, but has a residue.

"C": The pattern is broken and unclear, but there is no residue.

"D": The pattern is broken and unclear, with residue.

(Refractive index evaluation after heat resistance test)

The cured film obtained in the above (measurement of refractive index and transmittance) was heated on a hot plate at 265 ° C for 5 minutes. The refractive index after the heat resistance test was evaluated in accordance with the following criteria.

"A": the case where the refractive index exceeds 1.74

"B": the case where the refractive index is 1.74 or less

<Example 11>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 12>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 13>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 14>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 15>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 16>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 17>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 18>

In the preparation of the pigment dispersion liquid (titanium oxide dispersion) and the preparation of the photosensitive composition, the composition was changed as described below, and each evaluation was carried out in accordance with the same procedure as in Example 10.

(Preparation of titanium oxide dispersion 2)

~TiO2 dispersion composition~

Titanium oxide (TTO-51C manufactured by Ishihara Industry): 2.05 parts

Crystalline: rutile, TiO ₂ %: 79%~85%, surface treatment with Al ₂ O ₃ and stearic acid, specific surface area of 50m ² /g~60m ² /g, primary particle size of 10nm~30nm, Oil absorption is 24g/100g~30g/100g

Exemplary Compound 29 (30% PGMAI solution): 1.50 parts

Propylene glycol monomethyl ether acetate (PGMEA): 6.45 parts

~ Composition ~ (photosensitive composition)

<Example 19>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 20>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 21>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

<Example 22>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

Cyclohexanone 41.21 parts

<Example 23>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below.

~Comment~

As shown in Table 4, when titanium oxide was used as the inorganic particles, the lithographic properties of the composition were also excellent, and the cured film obtained by using the composition also exhibited an excellent refractive index.

In each of the photosensitive compositions of Examples 10 to 23, 50 mass ppm, 30 mass ppm, or 5 mass ppm of NaCl was added to prepare a composition.

A cured film was formed in the same manner as in Examples 10 to 23 except that the photosensitive compositions were used. It has been confirmed that each evaluation of the obtained cured film is the same as that of the above-described embodiment, and generation of defects of the cured film is reduced. In addition, it has been confirmed that the storage stability is improved in the composition to which 5 ppm by mass of NaCl is added.

In each of the photosensitive compositions of Examples 10 to 23, 10% by mass, 7% by mass, or 5% by mass of carbazole was further added to the total mass of the alkali-soluble resin to prepare a composition.

A cured film was formed in the same manner as in Examples 10 to 23 except that the photosensitive compositions were used. It has been confirmed that each evaluation of the obtained cured film is the same as that of the above-described embodiment, and the refractive index of the cured film is further increased, and the curing can be promoted even if the exposure amount is reduced.

<Example 24>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below. In addition, the components contained in the photosensitive composition of the following are the same as the components in the photosensitive composition of Example 11, but the amount of sodium element and the composition derived from the alkali-soluble resin are adjusted as shown in Table 5 below. The amount of sodium contained in the product.

~Comment~

<Example 25>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below. In addition, the components contained in the photosensitive composition of the following are the same as the components in the photosensitive composition of Example 12, but the amount of the sodium element and the composition derived from the alkali-soluble resin are adjusted as shown in Table 5 to be described later. The amount of sodium contained in the product.

~Comment~

<Example 26>

Each evaluation was performed according to the same procedure as in Example 10 except that the composition of the photosensitive composition was changed as described below. In addition, the components contained in the photosensitive composition of the following are the same as the components in the photosensitive composition of Example 21, but the amount of sodium element and the composition derived from the alkali-soluble resin are adjusted as shown in Table 5 to be described later. The amount of sodium contained in the product.

~Comment~

In the examples 24 to 26, the evaluation results of the "photopic evaluation", "refractive index evaluation of the cured film", "refractive index evaluation after heat resistance test", and "transmittance evaluation" are respectively as in the examples. 11. The same degree as in Example 12 and Example 21.

(surface observation)

The photosensitive compositions of Example 11, Example 12, Example 21, and Example 24 to Example 26 were respectively applied onto a 8 Å ruthenium wafer to form a coating film, and the surface of the coating film was observed by an optical microscope. The total number of foreign bodies and pores of 1 μm or more was evaluated. The results are summarized and shown in Table 5.

Further, the amount of sodium element in Table 5 was evaluated by ICP-MS and determined.

Hereinafter, in Table 5, "<0.01 mass ppm" means less than 0.01 mass. Ppm.

The column "Na amount (derived from alkali-soluble resin)" refers to the amount of sodium element derived from the alkali-soluble resin, and the column "Na amount (photosensitive composition)" means the amount of sodium contained in the composition (total amount) ).

As shown in the above table, when it is confirmed that the amount of sodium element is small, the number of defects is small. In particular, when it is confirmed that the amount of the sodium element derived from the alkali-soluble resin is small, the defects are small.

Claims (16)

A photosensitive composition comprising at least an alkali-soluble resin having a repeating unit represented by the formula (X), inorganic particles, a dispersing agent, a photopolymerization initiator, and a polymerizable compound, (In the formula (X), R ¹ represents a hydrogen atom or an alkyl group; L ¹ represents a single bond or a divalent linking group; and A represents a substituted or unsubstituted condensed aromatic ring group). A photosensitive composition comprising at least an alkali-soluble resin having a glass transition temperature (Tg) of from 100 ° C to 250 ° C, inorganic particles, a dispersant, a photopolymerization initiator, and a polymerizable compound. The photosensitive composition according to claim 1, wherein the alkali-soluble resin has a glass transition temperature (Tg) of from 100 ° C to 250 ° C. The photosensitive composition according to claim 1 or 3, wherein the A is selected from the group consisting of carbazolyl, naphthyl, benzothiazolyl, benzoxazolyl, and benzotriazole The group consisting of. The photosensitive composition according to claim 1 or 3, wherein the A is a carbazolyl group or a naphthyl group. The photosensitive group according to any one of claims 1 to 3 An article wherein the alkali-soluble resin further has a repeating unit containing a hydrophilic group (excluding an acid group). The photosensitive composition according to claim 6, wherein the hydrophilic group is a hydroxyl group. The photosensitive composition according to any one of claims 1 to 3, wherein the dispersing agent is an oligoimide-based dispersing agent or contains any one of formula (1) to formula (4). a resin of a structural unit represented by one, (In the formulae (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group; and R' represents a branched or linear alkylene group; The groups; Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group; and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a hydrogen atom or a monovalent organic group; And m, p, and q are each independently an integer of 1 to 500; j and k each independently represent an integer of 2 to 8; and R represents a hydrogen atom or a monovalent organic group). The photosensitive composition according to any one of claims 1 to 3, wherein the inorganic particles comprise titanium oxide or zirconium oxide. The photosensitive composition according to any one of claims 1 to 3, further comprising a low molecular compound having a carbazole structure. The photosensitive composition according to any one of claims 1 to 3, further comprising NaCl. The photosensitive composition according to any one of the items 1 to 3, which is used as a photosensitive composition for forming a color filter. A method of producing a color filter of a solid-state photographic element, comprising: coating a photosensitive composition for forming a color filter according to claim 12 of the patent application to form a coating layer, and coating the coating layer The layer is exposed and developed, thereby forming a pattern to obtain a cured film. A color filter obtained by using the photosensitive composition according to any one of claims 1 to 12. A solid-state photographic element comprising the color filter of claim 14 of the patent application. A dispersion composition comprising at least an alkali solubility having a glass transition temperature (Tg) of 100 ° C or more and having a repeating unit represented by the formula (X) and a repeating unit containing a hydrophilic group (excluding an acid group) Resins, inorganic particles, and dispersants, (In the formula (X), R ¹ represents a hydrogen atom or an alkyl group; L ¹ represents a single bond or a divalent linking group; and A represents a substituted or unsubstituted condensed aromatic ring group).